WO2012174844A1

WO2012174844A1 - Semiconductor photocatalyst for hydrogen production from biomass derivatives by photocatalytic reforming, and preparation method and use thereof

Info

Publication number: WO2012174844A1
Application number: PCT/CN2012/000064
Authority: WO
Inventors: 吴骊珠; 李治军; 李成博; 李旭兵; 李嘉欣
Original assignee: 中国科学院理化技术研究所
Priority date: 2011-06-23
Filing date: 2012-01-13
Publication date: 2012-12-27

Abstract

A semiconductor photocatalyst for hydrogen production from biomass derivatives by photocatalytic reforming. The atomic composition ratio thereof is M~N-A_x, wherein M~N is II-VI group elements or III-V group elements, A is one or more of the following elements: cobalt, nickel, iron, copper, chromium, palladium, platinum, ruthenium, rhodium, iridium or silver, and 0.02% ≤ x ≤ 1.0%. The semiconductor photocatalyst is prepared in situ from quantum dots by a photoreaction method without calcination.

Description

Semiconductor photocatalyst for photocatalytic reforming and hydrogen production of biomass derivatives, and preparation method and application thereof

The present invention relates to a photocatalytic system for photocatalytic reforming of biomass derivatives and hydrogen production, and more particularly to a semiconductor photocatalyst for photocatalytic reforming of biomass derivatives and hydrogen production and preparation method thereof And application. Background technique

To date, the main source of global energy has relied on fossil fuels. However, fossil fuels as a non-renewable energy source cannot always meet the growing energy needs of mankind. At the same time, the negative effects of using fossil fuels such as environmental pollution and climate change are receiving more and more attention. It is imminent to use new environmentally friendly non-fossil energy sources. Currently, the best alternative to fossil fuels is solar energy because solar energy is an environmentally friendly and sustainable energy source. Therefore, the storage and utilization of solar energy has attracted much attention, and research frenzy has already started around the world. However, with current research progress, it is not practical to completely replace fossil fuels with solar energy. Therefore, transforming an infinite energy source of solar energy into non-fossil fuel energy has become a major aspect of scientists' research. For example, direct conversion of solar energy into chemical energy, especially hydrogen energy, is the main breakthrough for scientists today and the main challenge for scientists in the next few decades.

Biomass is the most widespread substance on earth. It includes all animals, plants and microorganisms, as well as many organic matter derived, excreted and metabolized by these living things. All kinds of biomass have a certain amount of energy. Biomass is the biomass and the energy produced by biomass is biomass. Biomass energy is a form of energy in which solar energy is stored in the form of chemical energy, either directly or indirectly from the photosynthesis of plants. The energy consumed by plants on photosynthesis on Earth only accounts for 0.2% of the total radiation of the Earth. This ratio is not large, but the absolute value is amazing: the energy of photosynthesis is 40 times of the total human energy consumption. . It can be seen that biomass energy is a huge energy source. However, despite the vast amount of biomass in the world, biomass has the obvious disadvantage of low energy density and resource dispersion. Hydrogen is a high-energy, high-efficiency, clean, high-quality energy source. Hydrogen can be transported as long as it can be stored for long periods of time, and the density of hydrogen hydride is higher than that of natural gas. Therefore, the conversion of a large amount of dispersed biomass into hydrogen, and the centralized storage and transportation of hydrogen is easier than the centralized storage and transportation of biomass, which is an important way to store and concentrate biomass. More importantly, the photocatalytic reforming biomass hydrogen production technology can be carried out under normal temperature and pressure, using sunlight as a driving force for the reaction, and is a clean and sustainable hydrogen production technology. The essence of its energy conversion is to convert the inexhaustible solar energy into the energy required by human beings, which is not only renewable but also environmentally friendly.

Therefore, the development of efficient and low-cost solar hydrogen production technology has great and far-reaching strategic significance for improving energy structure, protecting the ecological environment, and promoting sustainable economic and social development.

Japanese scientist Kawai et al. [Chem. Lett. 1981, 81-84; Nature. 1980, 286, 474-476] Photocatalytic reforming in water using Pt/Ru0 ₂ /TiO ₂ catalyst as early as the 1980s The biomass derivative produces hydrogen. Subsequently, a large number of literatures have reported on the use of various biomass derivatives to produce hydrogen [J. Phys. Chem. 1983, 87, 801-805; J. Am. Chem. Soc. 1985, 107, 1773-1774; Chem Phys. Lett. 1981, 80, 341-344; Photochem. Reviews 2003, 4, 5-18; Catal. Lett. 2004, 98, 61; Chem. Chmman. 2004, 2192-2193], eg: methanol, ethanol , lactic acid, glycine, glutamic acid, proline, sugar, soluble starch, self-gelatin protein, seaweed, corpse corpse, human urine, animal dung, shredded filter paper (mainly cellulose).

At the same time, there are related patent reports on the use of solar energy to catalyze the hydrogen production of biomass derivatives. Japanese Patent No. 57,156,302 discloses a method for producing hydrogen by photocatalytic reforming of methanol using Ti0 ₂ , CdS , GaP; Japanese Patent No. 59,203,701 discloses "a method for photocatalytic reforming of water by 1:1 water-methanol to produce hydrogen", the catalyst is Ti0 ₂ and one of CrB, Ni ₂ B, Co ₂ P, Mo ₂ C, Cr ₃ C ₂ is supported on the surface thereof. Irradiation with a 500 W UV lamp produces a hydrogen production rate of 0.28 to 0.96 ml/h. Japanese Patent No. 6,186,943 also discloses "a method for photocatalytic reforming of 1:1 water-ethanol hydrogen production" using an amorphous Si-loaded Pt. When irradiated with a 100W halogen lamp, the hydrogen production rate can reach 0.03 ml/h. In addition, Li Can et al. of the Dalian Institute of Chemical Physics, Chinese Academy of Sciences reported three different catalysts for photocatalytic reforming of biomass derivatives. Hydrogen production, Chinese patent CN200410031517.3 discloses a novel composite photocatalyst which can be used for photocatalytic reforming of biomass derivatives under ultraviolet light and a preparation method thereof, and the atomic composition ratio of the catalyst is A^TaOs: B _x , wherein X is 0 or 1; A is an alkali metal element; and B is a ruthenium or osmium element. Chinese Patent No. 200810240366.0 discloses a heterojunction photocatalyst for reforming biomass-derived hydrogen and a preparation method thereof, wherein the photocatalyst has a composition of m% WO _x S _y /CdS (where X is oxygen in a tungsten species) The amount fraction of the substance, 0 ≤ x ≤ l; y is the amount fraction of the substance of sulfur in the tungsten species, 0 < y ≤ 2 _; m is the weight percentage of the tungsten element, 0 < m ≤ 10). The photocatalyst is based on the concept of semiconductor heterojunction. The precursor of W is supported on the CdS catalyst by a dipping method using a CdS catalyst as a carrier. Then, the sulfur (oxygen) of W is assembled in CdS by high temperature baking. On the surface, a hydrogen heterojunction photocatalyst for the preparation of a hydrazine active reforming biomass derivative is prepared. Chinese Patent No. 200910136643.8 well Jian a photocatalytic hydrogen production reforming of biomass derivative Ή0 ₂ photocatalyst, the crystal phase of anatase and rutile phase may be regulated within a wide range, the catalyst can be light Ti0 ₂ In the hydrogen production reaction of photocatalytic reforming biomass derivatives, the hydrogen production activity is greatly improved and the formation of carbon monoxide is effectively inhibited. In the photocatalytic reforming methanol reaction, the hydrogen generating activity of the Ti0 ₂ photocatalyst is Ti0. _{2 The} reference agent (P25) is about five times lower, and the CO content in hydrogen is reduced by at least two orders of magnitude, even below 5 ppm.

But so far, there are no patents or literature reports on the use of quantum dots and salts or complexes of transition metals such as cobalt, nickel, iron, copper, chromium, palladium, platinum, rhodium, ruthenium, gold, silver, manganese, ruthenium or osmium. Under mild conditions, photochemical methods are used to generate high-efficiency, stable and simple semiconductor catalysis for the photocatalytic reforming of biomass-derived hydrogen. Summary of the invention

A first technical problem to be solved by the present invention is to provide a semiconductor photocatalyst for photocatalytic reforming of biomass derivatives and hydrogen production.

A second technical problem to be solved by the present invention is to provide a method for producing the above semiconductor photocatalyst. A third technical problem to be solved by the present invention is to provide a system comprising photocatalytic reforming of a biomass derivative of the above semiconductor photocatalyst and producing hydrogen gas.

A fourth technical problem to be solved by the present invention is to provide a method for photocatalytic reforming of a biomass derivative by using the above semiconductor photocatalyst and producing hydrogen.

In order to solve the above first technical problem, the present invention relates to a semiconductor photocatalyst for photocatalytic reforming of biomass derivative hydrogen production, comprising the following technical features:

The atomic composition ratio of the semiconductor photocatalyst is M:NA _X; one by one

Where: ~ is a family element ~ family element or ~ is a family element ~ family element;

Wherein A is one or more elements of cobalt, nickel, iron, copper, chromium, palladium, platinum, rhodium, ruthenium, gold, silver, manganese, ruthenium or osmium; wherein 0.02% ≤ x ≤ 1.0 %.

In the present invention, M to N means a group II element and a corresponding group VI element; or a group III element and a corresponding group V element.

Among them, Group II elements are lib group elements Zn, Cd; Group VI elements are Via group 3, Se, Te; Group III is Ilia group elements In; V is Va group elements P, As.

Further, the atomic composition ratio of the semiconductor photocatalyst is Ti0 ₂ -M to NA _x , Sn0 ₂ -M to NA _x or ZnO-M to NA _x .

In order to solve the above second technical problem, the method for preparing the semiconductor photocatalysts M to NA _X of the present invention comprises the following steps:

1) adding a quantum dot composed of a group II~VI element or a group 111~ in the reactor;

2) a cobalt salt, a cobalt complex, a nickel salt, a nickel complex, an iron salt, an iron complex, a copper salt, a chromium salt, a palladium salt, a platinum salt, or a platinum salt, are added to the reactor. a solution of strontium salt, barium salt, barium salt, gold salt, silver salt, manganese salt, barium salt, barium salt solution or a solution of barium;

3) adding an aqueous solution of the biomass derivative to the above solution hydrazine to obtain a mixed solution B; 4) adjusting the pH of the mixed solution B to 3 to 10 to obtain a mixed solution C; the method of adjusting the pH is: adding 1 mol/L NaOH or 1 mol/L HCl to the mixed solution B.

5) passing an inert gas into solution C of step 4), or vacuuming the above reactor; irradiating the reactor with a mixed light beam of ultraviolet light, visible light or ultraviolet light and visible light in an inert gas or vacuum atmosphere, in situ A semiconductor catalyst having an atomic composition ratio of M to NA _X was obtained.

Further, the biomass derivative is methanol, ethanol, propanol, butanol, ethylene glycol, glycerol, glucose, sucrose, fructose, maltose, mannose, ascorbic acid, L-valine or L-half Cystine.

Further, the preparation method of the semiconductor photocatalyst Ti0 ₂ -M~N- A _x , Sn0 ₂ -M~NA _x or ZnO-M~NA _x of the present invention comprises the following steps:

In the reactor, a quantum dot composed of a group II~VI element or a group 111~ is added, and Ti0 ₂ , Sn0 ₂ , ZnO are added to adjust the pH 7; centrifugation, the supernatant is removed, and the precipitate is retained;

To the precipitate, one or a mixture of two or more of the following: a salt of cobalt, a complex of cobalt, a salt of nickel, a complex of nickel, a salt of iron, a complex of iron, a salt of copper, and a chromium Salt, palladium salt, platinum salt, barium salt, barium salt, barium salt, gold salt, silver salt, manganese salt, barium salt, barium salt;

Adding an aqueous solution of the biomass derivative to the precipitate;

Irradiating the reactor with ultraviolet and/or visible light in an inert gas or vacuum atmosphere to obtain a semiconductor photocatalyst having an atomic composition ratio of Ti0 ₂ -M~NA _x , Sn0 ₂ -M~NA _x or ZnO-M~NA _x ;

Further, the biomass derivative is triethanolamine, triethylamine, methanol, ethanol, propanol, butanol, ethylene glycol, glycerol, glucose, sucrose, fructose, maltose or mannose.

Further, step 1) in the quantum dot density or 111~ II~VI elements, is greater than I xl0_ ⁴ g / L; refers to the concentration of the quantum dots quantum After all reactants are added to a vessel and dilute System Point concentration

The quantum dots composed of the group II to VI elements include composite structure quantum dots composed of one or more of CdS, CdSe, CdTe, PbS, PbSe, ZnS, and ZnSe.

The quantum dots composed of the group III to V elements include a composite structure quantum dot composed of one or two of InP and InAs.

Further, in the step 2), the cobalt salt, the cobalt complex, the nickel salt, the nickel complex, the iron salt, the iron complex, the copper salt, the chromium salt, the palladium salt, the platinum The concentration of salt, barium salt, barium salt, barium salt, gold salt, silver salt, manganese salt, barium salt and/or barium salt in the reaction system ≥ l xl (r ⁶ m ₀ l /L _; that is, the cobalt salt, the cobalt complex, the nickel salt, the nickel complex, the iron salt, the iron complex, the copper salt, the chromium salt, the palladium salt, the platinum salt, the ruthenium Salt, barium salt, barium salt, gold salt, silver salt, manganese salt, barium salt, barium salt in the whole reaction system can reach the cobalt salt, cobalt complex, nickel Salt, nickel complex, iron salt, iron complex, copper salt, chromium salt, palladium salt, platinum salt, barium salt, barium salt, barium salt, gold salt, silver Saturated concentration of salt, manganese salt, barium salt, barium salt; theoretically it can continue to be added, but without any theoretical and economic value; Cobalt halides, cobalt sulfate, cobalt nitrate, cobalt carbonate, cobalt oxalate, cobalt acetate, cobalt phosphate, cobalt, or chromium;

The cobalt complex is a cobalt-ammonia complex [Co(NH ₃ ) ₆ ] ³⁺ , a cobalt-cyano complex [Co(CN) ₆ ] ⁴ cobalt-thiocyanate complex [Co(SCN) ₄ ] ² Cobalt-carbonyl complex [Co(CO) ₄ ; r, cobalt-nitro complex [Co(N0 ₃ ) ₄ f, cobalt-nitroso complex [Co(N0 ₂ ) ₆ ] ³ _ or cobalt - a dimethylglyoxime complex; wherein the cobalt-butanedione oxime complex and its derivative are of the following structural formula:

Wherein L is 3⁄40 or CH ₃ CN; R 3⁄4H, N(CH ₃ ) 2 or (COOCH ₃ );

The salt of nickel is nickel halide, nickel sulfate, nickel nitrate, nickel carbonate, nickel oxalate, nickel acetate, nickel phosphate or nickel chromite;

The complex of nickel is a nickel-ammonia complex [Ni(NH ₃ ) ₆ ] ²⁺ , a nickel-cyanide complex Ni(CN) ₄ f, a nickel-chelate [Ni(en) ₃ ] ^{2 +} , nickel-carbonyl coordination compound Ni(CO) ₄ or nickel-ethyl coordination compound (C ₂ 3⁄4) ₂ Ni;

The iron salt is iron halide, iron sulfate, iron nitrate, iron carbonate, iron oxalate, iron acetate, iron phosphate, iron chromate, ferrous halide, ferrous sulfate, ferrous nitrate, ferrous carbonate, ferrous oxalate , ferrous acetate, ferrous phosphate, ferrous chromite or ammonium ferrous sulfate;

The iron complex is an iron-cyano complex [Fe(CN) ₆ f, a ferrous-cyano complex [Fe(CN) ₆ ] ⁴ iron-thiocyanate complex Fe(SCN) ₃ , an iron-sulfur complex [Fe ₂ S ₂ (CO) ₆ ], iron-carbonyl complex Fe(CO) ₅ , iron-carbonyl complex Fe ₂ (CO) ₉ or iron-carbonyl complex Fe ₃ (CO) ₁₂ .

The copper salt is copper halide, copper sulfate (pentahydrate, monohydrate and anhydrous), copper nitrate, copper carbonate, copper oxalate, copper acetate, copper phosphate, copper chromate, copper pyrophosphate, copper cyanide, fatty acid Copper, copper bismuth citrate, cuprous halide, cuprous sulfate, cuprous carbonate or cuprous acetate;

The salt of chromium is chromium halide, chromium sulfate, chromium nitrate, chromium carbonate, chromium oxalate, chromium acetate or chromium phosphate; the salt of the palladium is potassium chloropalladium, palladium halide, palladium sulfate, palladium nitrate or palladium acetate ;

The salt of platinum is potassium chloroplatinate, platinum halide or platinum nitrate;

The salt of the cerium is cerium halide, cerium sulfate, cerium nitrate or cerium acetate; The salt of the cerium is cerium halide, cerium sulfate, cerium nitrate or cerium acetate;

The salt of gold is gold or chloroauric acid;

The silver salt is silver halide, silver sulfate, silver nitrate or silver acetate;

The salt of manganese is manganese halide, manganese sulfate, manganese nitrate or manganese acetate;

The salt of the cerium is cerium halide or chloroantimonic acid;

The salt of ruthenium is pentacarbonylphosphonium chloride or pentacarbonylpentadium bromide;

Further, the concentration of the biomass derivative in the step 3) is ≥1×10 ⁻⁴ mol/L or the molar percentage ≥0.01% in the whole reaction system; the concentration or the mole percentage of the biomass derivative can reach the highest Saturated concentration in the system; theoretically, it can be added, but without any theoretical and economic value; To solve the above third technical problem, the present invention comprises a photocatalytic reforming biomass derivative comprising a semiconductor photocatalyst M~NA _X And a system for preparing hydrogen,

Contains the following ingredients:

1) quantum dots composed of II~VI or 111~ group elements;

2) one or a mixture of two or more of the following: a salt of cobalt, a complex of cobalt, a salt of nickel, a complex of nickel, a salt of iron, a complex of iron, a salt of copper, a salt of chromium, a salt of palladium, a salt of platinum, a salt of cerium, a salt of cerium, a salt of cerium, a salt of gold, a salt of silver, a salt of cerium, a salt of cerium, a salt of cerium;

3) an aqueous solution of a biomass derivative;

And includes the following conditions:

ρΗ value is 3~10;

UV and / or visible light irradiation conditions.

The invention provides a system for photocatalytic reforming biomass derivatives comprising semiconductor photocatalysts Ti0 ₂ -M~NA _x , Sn0 ₂ -M~NA _x or ZnO-M~NA _x and preparing hydrogen, characterized in that - The following ingredients:

1) quantum dots composed of II~VI or III~V elements;

2) Ti0 ₂ , Sn0 ₂ or ZnO;

3) one or a mixture of two or more of the following: cobalt salt, cobalt complex, nickel salt, nickel complex, iron salt, iron complex, copper salt, chromium salt, a salt of palladium, a salt of platinum, a salt of cerium, a salt of cerium, a salt of cerium, a salt of gold, a salt of silver, a salt of manganese, a salt of cerium, a salt of cerium;

4) an aqueous solution of a biomass derivative;

And includes the following conditions:

Alkaline conditions and UV and / or visible light irradiation conditions.

Further, the quantum dot concentration of the II~VI or 111~ group element is greater than l xliT L; the quantum dot concentration refers to the quantum dot concentration of the system after all reactants are added to the container and the volume is constant;

The quantum dots composed of the ΠΙ~ν group elements include a composite structure quantum dot composed of one or two of InP and InAs.

Further, the cobalt salt, the cobalt complex, the nickel salt, the nickel complex, the iron salt, the iron complex, the copper salt, the chromium salt, the palladium salt, the platinum salt, the ruthenium The concentration of the salt, the barium salt, the barium salt, the gold salt, the silver salt, the manganese salt, the barium salt and/or the barium salt in the whole reaction system is ≥ lxl (T ⁶ mol / L _; a salt of cobalt, a complex of cobalt, Nickel salt, nickel complex, iron salt, iron complex, copper salt, chromium salt, palladium salt, platinum salt, barium salt, barium salt, barium salt, gold salt, The concentration of silver salt, manganese salt, barium salt and barium salt in the whole reaction system can reach cobalt salt, cobalt complex, nickel salt, nickel complex, iron salt and iron. , copper salt, chromium salt, palladium salt, platinum salt, barium salt, barium salt, barium salt, gold salt, silver salt, manganese salt, barium salt, barium salt Saturated concentration; theoretically can continue to join, but without any theoretical and economic value;

The cobalt salt is cobalt halide, cobalt sulfate, cobalt nitrate, cobalt carbonate, cobalt oxalate, cobalt acetate, cobalt phosphate or cobalt chromate; the cobalt complex is a cobalt-ammonia complex [Co(NH ₃ ) ₆ ³⁺ , cobalt-cyano complex [Co(CN) ₆ ] ⁴ _, cobalt-thiocyanate complex [Co(SCN) ₄ f, cobalt-carbonyl complex [Co(CO)4]-, cobalt-nitrogen a complex [Co(N0 ₃ ) ₄ f, a cobalt-nitroso complex [Co(N0 ₂ ) ₆ ] ³ - or a cobalt-butanedione oxime complex; wherein, a cobalt-butanedione ruthenium complex and Its derivatives are of the following structural formula -

Wherein L is 3⁄40 or CH ₃ CN; RJ3⁄4H, N(CH ₃ ) ₂ or (COOCH ₃ );

The nickel salt is a nickel halide, nickel sulfate, nickel nitrate, nickel carbonate, nickel oxalate, nickel acetate, nickel phosphate or chromic acid. The complex of nickel is a nickel-ammonia complex [Ni(NH ₃ ) ₆ ] ²⁺ , nickel-cyano complex [Ni(CN) ₄ f, nickel-chelate [Ni(en) ₃ ] ²⁺ , nickel-carbonyl complex Ni(CO) ₄ or nickel-ethyl Compound (C ₂ H ₅ ) ₂ Ni _;

The iron salt is iron, iron sulfate, iron nitrate, iron carbonate, iron oxalate, iron acetate, iron phosphate, iron chromate, ferrous halide, ferrous sulfate, ferrous nitrate, ferrous carbonate, ferrous oxalate , ferrous acetate, ferrous phosphate, ferrous chromite or ammonium ferrous sulfate;

The iron complex is an iron-cyano complex [Fe(CN) ₆ ] ³ _, a ferrous-cyano complex [Fe(CN) ₆ f, iron-thiocyanate complex Fe(SCN) ₃ , iron-sulfur complex [Fe ₂ S ₂ (CO) ₆ ], iron-carbonyl complex Fe(CO) ₅ , iron-carbonyl complex Fe ₂ (CO) ₉ or iron-carbonyl complex Fe ₃ (CO) ₁₂ .

The copper salt is copper halide, copper sulfate (pentahydrate, monohydrate and anhydrous), copper nitrate, copper carbonate, copper oxalate, copper acetate, copper phosphate, copper chromate, copper pyrophosphate, copper cyanide, fatty acid Copper, copper naphthenate, cuprous halide, cuprous sulfate, cuprous carbonate or cuprous acetate;

The salt of the cerium is cerium halide, cerium sulfate, cerium nitrate or cerium acetate;

The salt of gold is gold halide or chloroauric acid;

The manganese salt is manganese halide, sulfuric acid manganese, manganese nitrate or manganese acetate;

The salt of the cerium is cerium halide or chloroantimonic acid;

Further, the biomass concentration ≥1 derivative in the whole reaction system><10- ⁴ mol / L or molar percentage ≥ 0.01%; derivative of said raw material concentration or molar percentage of the system which can be up to The saturation concentration in the middle; theoretically it can be added, but without any theoretical and economic value. In order to solve the above fourth technical problem, the present invention provides a method for photocatalytic reforming a biomass derivative using a semiconductor photocatalyst M~NA _X and preparing hydrogen gas, comprising the following steps -

1) adding a quantum dot composed of II~VI or 111~ group elements in the reactor;

2) Add one or more of the following substances to the reactor: cobalt salt, cobalt complex, nickel salt, nickel complex, iron salt, iron complex, copper salt, chromium Salt, palladium salt, platinum salt, barium salt, barium salt, barium salt, gold salt, silver salt, manganese salt, barium salt, barium salt, to obtain a solution;

3) adding an aqueous solution of the biomass derivative to the above solution to obtain a mixed solution B;

4) adjusting the pH of the mixed solution B to 3 to 10 to obtain a mixed solution C; the method of adjusting the pH is: adding 1 mol/L NaOH or 1 mol/L HCL to the mixed solution B.

5) passing an inert gas into solution C of step 4), or vacuuming the above reactor; irradiating the reactor with a mixed light beam of ultraviolet light, visible light or ultraviolet light and visible light in an inert gas or vacuum atmosphere, in situ The resulting catalyst is capable of photocatalytic reforming of biomass derivatives and preparation of hydrogen.

The biomass derivative is methanol, ethanol, propanol, butanol, ethylene glycol, glycerol, glucose, sucrose, fructose, maltose, mannose, ascorbic acid, L-valine or L-cysteine. .

The invention provides a method for photocatalytic reforming a biomass derivative by using a semiconductor photocatalyst Ti0 ₂ -M~NA _x , Sn0 ₂ -M~NA _x or ZnO-M~NA _x and preparing hydrogen, comprising the following steps -

1) adding a quantum dot composed of a group II~VI element or a 111~ group element in the reactor, adding Ti0 ₂ , Sn0 ₂ or ZnO to adjust the pH 7; centrifuging, removing the supernatant liquid, and retaining the precipitate;

2) one or a mixture of two or more of the following substances is added to the precipitate: a salt of cobalt, a complex of cobalt, a salt of nickel, a complex of nickel, a salt of iron, a complex of iron, a salt of copper, a salt of chromium, a salt of palladium, a salt of platinum, a salt of cerium, a salt of cerium, a salt of cerium, a salt of gold, a salt of silver, a salt of manganese, a salt of cerium, a salt of cerium;

3) adding an aqueous solution of the biomass derivative to the precipitate to adjust the pH 7;

4) Irradiating the reactor with ultraviolet light and/or visible light in an inert gas or vacuum atmosphere to obtain a composite semiconductor photocatalyst, simultaneously reforming the biomass derivative and generating hydrogen gas.

The biomass derivative is triethanolamine, triethylamine, methanol, ethanol, propanol, butanol, ethylene glycol, glycerol, glucose, sucrose, fructose, maltose or mannose. Further, in the step 1), the quantum dot concentration of the II~VI or 111~ group element is greater than 1 x 10 ^-4 g/L; the quantum dot concentration refers to the system in which the reactants are added to the container and the volume is constant. Quantum dot concentration;

Further, in the step 2), the cobalt salt, the cobalt complex, the nickel salt, the nickel complex, the iron salt, the iron complex, the copper salt, the chromium salt, the palladium salt, the platinum salts, ruthenium salts, rhodium salts, iridium salts, gold salts, silver salts, the concentration of manganese salt, iridium salt and / or rhenium salt in the reaction system ≥ ^ 10- ⁶ ^ 1 ₀ 1 That is, the cobalt salt, the cobalt complex, the nickel salt, the nickel complex, the iron salt, the iron complex, the copper salt, the chromium salt, the palladium salt, the platinum salt, the barium salt The salt of barium, the salt of barium, the salt of gold, the salt of silver, the salt of barium, the salt of barium, the salt of barium, the highest concentration in the reaction system can reach cobalt salt, cobalt complex, nickel salt, nickel Complex, iron salt, iron complex, copper salt, chromium salt, palladium salt, platinum salt, barium salt, barium salt, barium salt, gold salt, silver salt, manganese The saturated concentration of salt, barium salt, and barium salt; theoretically, it can continue to be added, but without any theoretical and economic value;

The cobalt salt is cobalt halide, cobalt sulfate, cobalt nitrate, cobalt carbonate, cobalt oxalate, cobalt acetate, cobalt phosphate or cobalt chromate;

The cobalt complex is a cobalt-ammonia complex [Co(NH ₃ ) ₆ ] ³⁺ , a cobalt-cyano complex [Co(CN) ₆ f, a cobalt-thiocyanate complex [Co(SCN) ₄ ] ² Cobalt-carbonyl complex [Co(CO) ₄ ] cobalt-nitro complex [Co(N0 ₃ ) ₄ f, cobalt-nitroso complex [ ³ _ or cobalt-butanedione oxime complex; The cobalt-butanedione oxime complex and its derivatives are of the following structural formula:

Or ;

Wherein L is 3⁄40 or CH ₃ CN; RJ3⁄4H, N(CH ₃ ) ₂ or (COOCH ₃ );

The nickel complex is a nickel-ammonia complex [Ni(NH ₃ ) ₆ ] ²⁺ , a nickel-cyanide complex [Ni(CN) ₄ ] ² _, a nickel-chelate [Ni(en) ₃ ] ²⁺ , nickel-carbonyl coordination compound Ni(CO) ₄ or nickel-ethyl coordination compound (C ₂ H ₅ ) ₂ Ni _;

The iron salt is iron halide, iron sulfate, iron nitrate, iron carbonate, iron oxalate, iron acetate, iron phosphate, iron chromate, ferrous halide, ferrous sulfate, ferrous nitrate, ferrous carbonate, ferrous oxalate. , ferrous acetate, ferrous phosphate, ferrous chromite or ferrous sulfate hinge;

The iron complex is an iron-cyano complex [Fe(CN) ₆ f, a ferrous-cyano complex [Fe(CN) ₆ ] ⁴ _, an iron-thiocyanate complex Fe(SCN) ₃ , iron - Sulfur complex [Fe ₂ S ₂ (CO) ₆ ], iron-carbonyl complex Fe(CO) ₅ , iron-carbonyl complex Fe ₂ (CO) ₉ or iron-carbonyl complex Fe ₃ (CO) ₁₂ .

The chromium salt is a chromium halide, a chromium sulfate, a chromium nitrate, a chromium carbonate, a chromium oxalate, a chromium acetate or a chromium phosphate; the salt of the palladium is potassium chloropalladium, palladium, palladium sulfate, palladium nitrate or acetic acid. Palladium

The salt of gold is gold halide or chloroauric acid;

The fierce salt is manganese halide, manganese sulfate, manganese nitrate or manganese acetate;

The salt of the cerium is cerium halide or chloroantimonic acid;

Further, the concentration of the biomass derivative in the step 3) is ≥ l xl (T ⁴ mol/L or mole percentage ≥ 0.01% in the whole reaction system; the concentration or the mole percentage of the biomass derivative can be up to Its saturation concentration in the system; theoretically it can be added, but without any theoretical and economic value;

The reforming degradation of the biomass is to reform and decompose biomass derivatives (mainly composed of carbon, hydrogen and oxygen) into hydrogen and other small molecules, for example, C0 ₂ , CO, CH _{4 ,} etc. Many intermediate species can also be produced in the reaction solution. It should be noted that there will be differences in the types and proportions of different reaction substrate products.

The intermediate species that may be formed in the reaction solution are complex, different biomass derivatives, different reaction conditions (such as - concentration, temperature, pH, etc.) and the selection of different quantum dots will cause a great change in the type and proportion of the product. Here, it is impossible to enumerate them one by one, but it is certain that H ₂ is always one of the important products of the reaction.

The invention has the following beneficial effects:

The invention can realize the in-situ preparation of high-efficiency semiconductor catalyst by quantum dots through visible light-driven photoreaction and catalytic reforming of biomass derivatives and preparation of hydrogen gas. More importantly, the method can generate a high-efficiency, stable and simple synthesis semiconductor photocatalytic reforming biomass hydrogen production catalyst in situ under illumination without harsh conditions such as calcination. The method of the invention has high efficiency, simple operation and practicality.

DRAWINGS

1 is an ultraviolet-visible absorption spectrum and an emission spectrum of an CdSe quantum dot of the present invention (excitation wavelength: 400 nm); FIG. 2 is an ultraviolet-visible absorption spectrum and an emission spectrum of a CdS quantum dot of the present invention (excitation wavelength: 400 nm); FIG. 3 is an ultraviolet-visible absorption spectrum and an emission spectrum of an CdTe quantum dot of the present invention (excitation wavelength: 400 nm); FIG. 4 is an ultraviolet-visible absorption spectrum of a ZnS quantum dot of the present invention;

Figure 5 is a view showing the ultraviolet-visible absorption spectrum and the emission spectrum of the ZnSe quantum dots of the present invention;

6 is an ultraviolet-visible absorption spectrum and an emission spectrum of an CdSe/CdS quantum dot of the present invention (excitation wavelength: 400 nm);

7 is a topographical view of a CdSe quantum dot of the present invention under HRTEM (high resolution transmission electron microscope); FIG. 8 is a topographical view of a CdS quantum dot of the present invention under HRTEM observation;

Figure 9 is a topographical view of a CdTe quantum dot of the present invention under HRTEM observation;

Fig. 10 is a screenshot showing the peak spectrum of the product produced by photocatalytic reaction of the photocatalytic reforming ethanol system of Example 1.

Figure 11 is in Example 108: l _. Ti0 _{2 ;} 2. Ή 0 ₂ and CdSe quantum dots after adsorption; 3. Ti0 ₂ and CdSe quantum dots after adsorption after adding various types of transition metal salts; 4. Ti0 ₂ and CdSe quantum After the adsorption, various transition metal salts were added and the light was irradiated for 8 hours _; the absorption curves of the four groups of samples on the DRS spectrum;

12 is the same as in Example 109: l _. Ti0 _{2 ;} 2. Ti0 ₂ and CdSe quantum dots after adsorption; 3. Ή 0 ₂ and CdSe quantum dots after adsorption and then various types of transition metal salts; 4. Ti0 ₂ and CdSe quantum After the adsorption, various transition metal salts were added and the light was irradiated for 8 hours; the absorption curves of the four groups of samples on the DRS spectrum;

13 is in Example 110: l _. Ti0 _{2 ;} 2. Ή 0 ₂ and CdSe quantum dots after adsorption; 3. Ti0 ₂ and CdSe quantum dots after adsorption of various transition metal salts; 4. Ti0 ₂ and CdSe quantum After the adsorption, various transition metal salts were added and the light was irradiated for 8 hours _; the absorption curves of the four groups of samples on the DRS spectrum;

14 is the following in Example 111: 1. Ή0 _{2 ;} 2. Ή0 ₂ and CdSe quantum dots after adsorption; 3. Ti0 ₂ and CdSe quantum dots after adsorption of various transition metal salts; 4. Ti0 ₂ and CdSe quantum After the adsorption, various transition metal salts were added and the light was irradiated for 8 hours; the absorption curves of the four groups of samples on the DRS spectrum;

Figure 15 is in Example 112: l. Ti0 ₂ ; 2. Ti0 ₂ and CdSe quantum dots after adsorption; 3. Ti0 ₂ and CdSe quantum dots after adsorption after adding various types of transition metal salts; 4. Ή0 ₂ and CdSe quantum After the adsorption, various transition metal salts were added and the light was irradiated for 8 hours _; the absorption curves of the four groups of samples on the DRS spectrum;

Figure 16 is the same as in Example 113: 1. Ή0 _{2 ;} 2. Ti0 ₂ and CdSe quantum dots after adsorption; 3. Ti0 ₂ and CdSe quantum dots after adsorption of various transition metal salts; 4. Ή0 ₂ and CdSe quantum After the adsorption, various transition metal salts were added and the light was irradiated for 8 hours _; the absorption curves of the four groups of samples on the DRS spectrum;

17 is the same as in Example 114: 1. Ή0 _{2 ;} 2. Ti0 ₂ and CdSe quantum dots after adsorption; 3. Ti0 ₂ and CdSe quantum dots after adsorption of various transition metal salts; 4. Ti0 ₂ and CdSe quantum After the adsorption, various transition metal salts were added and the light was irradiated for 8 hours _; the absorption curves of the four groups of samples on the DRS spectrum;

18 is the embodiment 115: LTi0 _{2 ;} 2. Ti0 ₂ and CdSe quantum dots after adsorption; 3. Ή 0 ₂ and CdSe quantum dots after adsorption of various transition metal salts; 4. Ή0 ₂ and CdSe quantum dot adsorption After adding various transition metal salts, the light is illuminated for 8 hours; the absorption curves of the four sets of samples on the DRS spectrum;

It can be seen from the figure that P-25 type Ti0 ₂ exhibits a typical Ti0 ₂ ultraviolet absorption characteristic. When CdSe quantum dots are adsorbed with Ή0 ₂ , the system simultaneously exhibits P-25 type Ή0 ₂ and CdSe quantum dot absorption. Superposition, which proves the adsorption of CdSe quantum dots on the surface of Ti0 ₂ ; when further adding the transition metal salt, based on the superposition of the absorption of P-25 Ti0 ₂ and CdSe quantum dots, it is located in the reddish position (500-700). A new broad absorption band appears in nm; when further illumination occurs, a new distinct absorption occurs in the reddered area, indicating a new structure is created. DETAILED DESCRIPTION OF THE INVENTION Embodiment 1

A method for preparing hydrogen by photocatalytic reforming of biomass derivatives using a semiconductor photocatalyst:

Add 1 x lO^g/L core-shell cadmium selenide/cadmium sulfide quantum dots (CdSe/CdS quantum dot solution concentration IxlO-'g/L) to Pyrex tube, then add 0.5 ml of aqueous nickel dichloride solution (original Concentration 4.2xl (T ³ mol / L, containing 0.5 mg of nickel dichloride hexahydrate), 41 ^ ethanol (original concentration 17.161 ^ 01 / 20 ° C), adjust the pH value of 7, the total volume is 10ml, and The test tube was irradiated with a 500 W high pressure mercury lamp (400 nm long pass type glass filter) in a sealed nitrogen atmosphere.

The atomic composition ratio of the semiconductor photocatalyst was CdSeS-Nix; wherein the X value was measured by ICP (Inductively Coupled Plasma Atomic Emission Spectrometer) as: x = 0.16%.

Ethanol can be produced on a large scale from biomass fermentation, so photocatalytic reforming of ethanol to produce hydrogen has practical significance. FIG. 10 is a screenshot of the peak spectrum of the gas phase produced by the photocatalytic reaction of the photocatalytic reforming ethanol system of Example 1 on a gas chromatograph (TCD thermal conductivity detector). It can be seen from the figure that peaks of _3⁄4 and CH ₄ (C is an internal standard) appear successively at different retention times. The hydrogen production is 107 μπιοΗι- i-mg

Example 2

Add 1xlO-ig/L core-shell cadmium selenide/cadmium sulfide quantum dots (CdSe/CdS quantum dot solution concentration 2xlO-L) to Pyrex tube. Then add 0.5 ml of cobalt dichloride aqueous solution (original concentration 4.2xl (T ³ mol/L, containing 0.5 mg of cobalt dichloride hexahydrate), 41^methanol (original concentration 24.751^1, 20 °C), adjusting pH to 6, total volume to 10 ml, and making it sealed The tube was irradiated with a 500 W high pressure mercury lamp (400 nm long pass glass filter) in a nitrogen atmosphere.

During the reaction, the hydrogen gas generated in the reaction was detected by gas chromatography (TCD thermal conductivity detector).

The atomic composition ratio of the semiconductor photocatalyst was CdSeS-Co _{x ;} wherein the X value was measured by ICP (Inductively Coupled Plasma Atomic Emission Spectrometer) to be: x = 0.13%. The hydrogen production is 87μπιοΗ— ^mg^

Example 3:

A method for preparing hydrogen by photocatalytic reforming of biomass derivatives by using semiconductor photocatalyst - adding 1 x 1 O ^ g / L core shell cadmium selenide / cadmium sulfide quantum dots (PdSe / CdS quantum dot stock solution) to Pyrex test tube Concentration 2xlO g / L), then add 0.5 ml of cobalt sulfate aqueous solution (original concentration 4.2xlO ³ mol / L, containing 0.59 mg cobalt sulfate heptahydrate), 4ml ethanol (original concentration 17.16mol / L, 20V), adjust the pH value 7. The total volume is 10 ml and placed in a sealed nitrogen atmosphere. The tube is irradiated with a 500 W high pressure mercury lamp (400 nm long pass glass filter).

The atomic composition ratio of the semiconductor photocatalyst was CdSeS-Co _{x ;} wherein the X value was measured by ICP (Inductively Coupled Plasma Atomic Emission Spectrometer) to be: x = 0.23%. The hydrogen production is 81 μπιοΗι— ^mg—

Example 4:

Add 1xli^g/L core-shell cadmium selenide/cadmium sulfide quantum dots (CdSe/CdS quantum dot solution concentration 2xlO-L) to Pyrex tube and add 0.5 ml of cobalt nitrate aqueous solution (original concentration 4.2xl (T ³ mol) /L, containing 0.61 mg of cobalt nitrate hexahydrate), 41 ^ ethanol (original concentration 17.161 ^ 1 / 20 ° C), adjusting the pH to 7, the total volume is 10 ml, and placed in a sealed nitrogen atmosphere, The tube was irradiated with a 500 W high pressure mercury lamp (400 nm long pass type glass filter).

The atomic composition ratio of the semiconductor photocatalyst was CdSeS-Co _{x ;} wherein the X value was measured by ICP (Inductively Coupled Plasma Atomic Emission Spectrometer) to be: x = 0.26%. The amount of hydrogen produced is Q moH^mg - Example 5:

Add 1xlO^g/L core-shell cadmium selenide/cadmium sulfide quantum dots (CdSe/CdS quantum dot solution concentration 2xlO- ^! g/L) to Pyrex tube, then add 0.5 ml of nickel nitrate solution (original concentration 4.2xlO_ ³⁾ Mol/L, containing 0.61 mg of hexahydrate hexahydrate Nickel), 4ml ethanol (original concentration 17.16mol/L, 20V), adjusted to pH 7, total volume to 10ml, and in a sealed nitrogen atmosphere, with 500W high pressure mercury lamp (400 nm long wave pass) Type glass filter) Irradiate the test tube.

The atomic composition ratio of the semiconductor photocatalyst was CdSeS-Ni _{x ;} wherein the X value was measured by ICP (Inductively Coupled Plasma Atomic Emission Spectrometer) as: x = 0.18%. The amount of hydrogen produced is 102 μπιο1·1 -1 mg.

Example 6:

Add 1xlO^g/L core-shell cadmium selenide/cadmium sulfide quantum dots (CdSe/CdS quantum dot solution concentration 2xlO' ^! g/L) to Pyrex tube, then add 0.5 ml of nickel sulfate solution (original concentration 4.2xl ( T ³ mol/L, containing 0.55 mg of nickel sulfate hexahydrate), 41^1 ethanol (original concentration 17.161101^, 20), adjusted to pH 7, total volume to 10 ml, and in a sealed nitrogen atmosphere The tube was irradiated with a 500 W high pressure mercury lamp (400 nm long pass type glass filter).

The atomic composition ratio of the semiconductor photocatalyst was CdSeS-Ni _{x ;} wherein the X value was determined by ICP (Inductively Coupled Plasma Atomic Emission Spectrometer) to be: x = 0.21%. The amount of hydrogen produced is K^ mol'h mg—

Example 7

A method for preparing hydrogen by photocatalytic reforming of biomass derivatives by using semiconductor photocatalyst - adding lxlO^g/L core-shell cadmium selenide/cadmium sulfide quantum dots to Pyrex tube (CdSe/CdS quantum dot solution concentration 2 10 "3⁄4> Then add 0.51 ^ nickel dichloride aqueous solution (original concentration 4.2 10 - ³ 1 ^ 1 / 1, containing 0.5 mg of nickel dichloride hexahydrate), 4 ml of sucrose aqueous solution (original concentration 0.25mol / L, 20 ° C ), adjust the pH to 7, the total volume is 10 ml, and place it in a sealed nitrogen atmosphere. The tube is irradiated with a 500W high pressure mercury lamp (400 nm long pass glass filter).

The atomic composition ratio of the semiconductor photocatalyst was measured by ICP (Inductively Coupled Plasma Atomic Emission Spectrometer) as follows: x = 0.13%. Hydrogen production is δ

Example 8

A method for preparing hydrogen by photocatalytic reforming of biomass derivative by using semiconductor photocatalyst - adding lxlO^g/L core-shell cadmium selenide/cadmium sulfide quantum dot to Pyrex test tube (CdSe/CdS quantum dot solution concentration 2x10- ^)' Then add 0.5 ml of aqueous nickel dichloride solution (original concentration 4.2xlO- ³ mol/L, containing 0.5 mg of nickel dichloride hexahydrate), 4 ml aqueous dextrose solution (original concentration 0.25 mol/L, 20 V), adjust The pH value is 7, the total volume is 10 ml, and it is in a sealed nitrogen atmosphere. The atomic composition ratio of the semiconductor photocatalyst is irradiated by a 500 W high-pressure mercury lamp (400 nm long-wavelength glass filter). CdSeS-Ni _x; wherein the X value was determined by ICP (Inductively Coupled Plasma Atomic Emission Spectrometer) as: x = 0.12%. The amount of hydrogen produced is moH^mg^

Example 9

Add 1 χ 1 (^g/L core-shell cadmium selenide/cadmium sulfide quantum dots (CdSe/CdS quantum dot stock solution 2X10-L)' to the Pyrex tube and add 0.5 ml of aqueous nickel dichloride solution (original concentration 4.2). xlO— ³ mol/L, containing 0.5 mg of nickel dichloride hexahydrate), 4 ml of ethylene glycol (original concentration: 17.9 mol/L, 20 V), adjusting the pH to 7, the total volume is 10 ml, and It was placed in a sealed nitrogen atmosphere and the tube was illuminated with a 500 W high pressure mercury lamp (400 nm long pass glass filter).

The atomic composition ratio of the semiconductor photocatalyst was CdSeS-Ni _{x ;} wherein the X value was measured by ICP (Inductively Coupled Plasma Atomic Emission Spectrometer) to be: x = 0.19%. The amount of hydrogen produced is SS moHi mg^

Example 10

Add 1xlO^g/L core-shell cadmium selenide/cadmium sulfide quantum dots (CdSe/CdS quantum dot solution concentration 2xl0-'g/L) to Pyrex tube and add 0.5 ml of nickel dichloride aqueous solution (original concentration 4.2). Xl (T ³ mol/L, containing 0.5 mg of nickel dichloride hexahydrate), 4 ml of glycerol (original concentration 13.7 mol/L, 20 V), adjusted to pH 7, total volume to 10 ml, and Place it in a sealed nitrogen atmosphere and illuminate with a 500W high pressure mercury lamp (400 nm long pass glass filter) Tube.

The atomic composition ratio of the semiconductor photocatalyst was CdSeS-Ni _{x ;} wherein the X value was measured by ICP (Inductively Coupled Plasma Atomic Emission Spectrometer) as: x = 0.15%. The hydrogen production is 21 μπιοΗι- ^mg

Example 11:

The whole reaction system was added to the Pyrex tube at a concentration of lxl (T ⁴ g/L of core-shell cadmium selenide/cadmium sulfide quantum dots (CdSe/CdS quantum dot solution concentration Zx lO-ig/L), and then added to the whole reaction system. at a concentration of 1><10- ⁶ mol / L aqueous solution of chromium sulfate, 0.1 mol / L L- cysteine adjust the PH value of 3, the reactor was evacuated and 500 W high pressure mercury lamp with a short (400 nm in Through-glass filter) Irradiate the tube.

The atomic composition ratio of the semiconductor photocatalyst was CdSeS-C _rx; wherein the X value was measured by ICP (Inductively Coupled Plasma Atomic Emission Spectrometer) as: x = 0.23%. The amount of hydrogen produced is 3 μπιοΗι— ^mg— '.

Example 12 _:

Add the whole reaction system concentration to lxl (T ³ g/L core-shell cadmium selenide/cadmium sulfide quantum dots (CdSe/CdS quantum dot solution concentration Zx lO^g/L) to Pyrex tube, and then add the whole reaction system. Cobalt-nitro complex [Co(N0 ₃ )4] ² _ at a concentration of 1 χ 10_ ⁵ mol/L, sucrose at a concentration of lx lCT ³ mol/L, adjusted to a pH of 10, and The test tube was irradiated with a 500 W high pressure mercury lamp (the glass tube itself was permeable to ultraviolet light plus visible light) in a sealed nitrogen atmosphere.

The atomic composition ratio of the semiconductor photocatalyst was CdSeS-Co _{x ;} wherein the X value was measured by ICP (Inductively Coupled Plasma Atomic Emission Spectrometer) as: x = 0.25%. The amount of hydrogen produced is όΑ μπιοΗι· ¹ ·]^—

Example 13

Add the whole reaction system concentration to lxl (T ² g/L core-shell cadmium selenide/cadmium sulfide quantum dots (CdSe/CdS quantum dot solution concentration Sx lO^g/L) to the Pyrex tube, and then add the whole reaction system concentration. It is a cobalt-nitroso complex [Co(N0 ₂ ) ₆ f of 2.1 χ10· ⁴ mol/L, glucose of 0.1 mol/L in the whole reaction system, pH 8 is adjusted, and it is sealed nitrogen. In the atmosphere, the test tube was irradiated with a 500 W high pressure mercury lamp (400 nm long pass type glass filter).

The atomic composition ratio of the semiconductor photocatalyst was CdSeS-Co _{x ;} wherein the X value was measured by ICP (Inductively Coupled Plasma Atomic Emission Spectrometer) to be: x = 0.10%. The amount of hydrogen produced is SQ mol'h mg—

Example 14

Example 1 was repeated except that the doping compound was nickel dibromide and the biomass derivative was L-valine at a concentration of 0.1 mol/L.

Example 15

Example 1 was repeated except that the doping compound was nickel sulfate and the biomass derivative was L-cysteine at a concentration of 0.1 mol/L.

Example 16:

Example 1 was repeated except that the doping compound was nickel oxalate and the biomass derivative was propanol.

Example 17 _:

Example 1 was repeated except that the doping compound was nickel acetate and the biomass derivative was butanol.

Example 18

Example 1 was repeated except that the doping compound was nickel phosphate.

Example 19

Example 1 was repeated except that the doping compound was a nickel-ammonia complex [Ni(NH ₃ ) ₆ ] ²⁺ .

Example 20

Example 1 was repeated except that the doping compound was a nickel-cyanide complex [Ni(CN) ₄ f. Example 21:

Example 1 was repeated except that the doping compound was a nickel-chelate [Ni(en)3] ²⁺ .

Example 22:

Example 1 was repeated except that the doping compound was nickel tetracarbonyl Ni(CO) ₄ .

Example 23 _:

Example 1 was repeated except that the doping compound was a nickel-ethyl complex (C ₂ H ₅ ) ₂ Ni. Example 24 _:

Example 1 was repeated except that the doping compound was ferric chloride.

Example 25:

Example 1 was repeated except that the doping compound was ferrous chloride.

Example 26

Example 1 was repeated except that the doping compound was ferrous bromide.

Example 27

Example 1 was repeated except that the doping compound was ferrous sulfate.

Example 28

Example 1 was repeated except that the doping compound was iron fluoride.

Example 29 _:

Example 1 was repeated except that the doping compound was iron bromide.

Example 30

Example 1 was repeated except that the doping compound was iron iodide.

Example 31:

Example 1 was repeated except that the doping compound was iron sulfate.

Example 32:

Example 1 was repeated except that the doping compound was ferric nitrate.

Example 33:

Example 1 was repeated except that the doping compound was iron carbonate.

Example 34 _:

Example 1 was repeated except that the doping compound was iron oxalate.

Example 35

Example 1 was repeated except that the doping compound was iron acetate.

Example 36:

Example 1 was repeated except that the doping compound was iron phosphate.

Example 37

Example 1 was repeated except that the doping compound was iron chromate.

Example 38:

Example 1 was repeated except that the doping compound was ferrous fluoride.

Example 39

Example 1 was repeated except that the doping compound was ferrous iodide.

Example 40

Example 1 was repeated except that the doping compound was ferrous nitrate.

Example 41:

Example 1 was repeated except that the doping compound was ferrous carbonate.

Example 42 _:

Example 1 was repeated except that the cumbersome compound was ferrous oxalate.

Example 43 The repeated examples differ only in that the doping compound is ferrous acetate.

Example 44:

The repeated examples differ only in that the doping compound is ferrous phosphate.

Example 45:

The repeated examples differ only in that the doping compound is ferrous chromite.

Example 46:

The repeated examples differ only in that the doping compound is ammonium ferrous sulfate.

Example 47:

Example 48:

The repeated examples differ only in that the doping compound is an iron-cyano complex [Fe(CN) ₆ f. Example 49

The repeated examples differ only in that the doping compound is a ferrous-cyano complex [Fe(CN) ₆ ] ⁴ - Example 50:

The repeated examples differ only in that the doping compound is an iron-thiocyanate complex Fe(SCN) ₃ . Example 51:

The repeated examples differ only in that the doping compound is an iron-carbonyl complex Fe(CO) ₅ . Example 52 - The repeated examples differ only in that the doping compound is an iron-carbonyl complex Fe ₂ (CO) ₉ . Example 53

The repeated examples differ only in that the doping compound is an iron-carbonyl complex Fe ₃ (CO) ₁₂ Example 54:

The repeated examples differ only in that the doping compound is nickel nitrate.

Example 55

The repeated examples differ only in that the doping compound is nickel carbonate.

Example 56

The repeated examples differ only in that the murky compound is nickel chromite.

Example 57

The repeated examples differ only in that the doping compound is nickel fluoride.

Example 58

The repeated examples differ only in that the doping compound is nickel iodide.

Example 59

The repeated examples are different only in that the doping compound is cobalt difluoride.

Example 60

The repeated examples differ only in that the doping compound is cobalt bromide.

Example 61:

The repeated examples are different only in that the doping compound is cobalt iodide.

Example 62

The repeated examples differ only in that the doping compound is cobalt carbonate.

Example 63:

The repeated examples differ only in that the doping compound is cobalt oxalate.

Example 64:

The repeated examples are different only in that the doping compound is cobalt acetate.

Example 65

The repeated examples differ only in that the heterogeneous compound is cobalt phosphate. Example 66:

Example 1 was repeated except that the doping compound was a cobalt-ammonia complex [Co(NH ₃ ) ₆ ] ³⁺ .

Example 67:

Example 1 was repeated except that the doping compound was a cobalt-cyano complex [Co(CN) ₆ ] ⁴ -.

Example 68:

Example 1 was repeated except that the doping compound was a cobalt-thiocyanate complex [Co(SCN) ₄ f.

Example 69:

Example 1 was repeated except that the doping compound was a cobalt-carbonyl complex [c ₀ (co) ₄ r.

Example 70:

Example 1 was repeated except that the doping compound was a cobalt-nitro complex [Co(N0 ₃ ) ₄ f.

Example 71:

Example 1 was repeated except that the doping compound was a cobalt-nitroso complex [Co(N0 ₂ ) ₆ ] ³ -. Example 72:

Add 1 χ 1 to the Pyrex tube (^g/L core-shell cadmium selenide/cadmium sulfide quantum dots (CdSe/CdS quantum dot solution concentration)

2χ10" 3⁄4- Then add 0.8mg (2.1 xl (T ⁴ M) cobalt-butanedione oxime complex with the following structure, 4 ml ethanol (original concentration 17.16 mol/L, 20 ° C), adjust the pH to 7, The total volume was set to 10 ml and placed in a sealed nitrogen atmosphere. The tube was irradiated with a 500 W high pressure mercury lamp (400 nm long pass glass filter).

The atomic composition ratio of the semiconductor photocatalyst was CdSeS-Co _{x ;} wherein the X value was measured by ICP (Inductively Coupled Plasma Atomic Emission Spectrometer) as: x = 0.11%. The amount of hydrogen produced is ό μπιοΗ^η^

;

Where L = H ₂ 0.

Example 73:

Example 72 was repeated except that the doping compound was a cobalt-butanedione oxime complex having the following structure:

Where L = CH ₃ CN.

Example 74: Example 72 was repeated except that the doping compound was a cobalt-butanedione oxime complex having the following structure:

Where L = H ₂ 0.

Example 75

Example 72 was repeated except that the cryptic compound was a cobalt-butanedione oxime complex having the following structure:

F ^B where L = CH ₃ CN.

Example 76:

Where R=H.

Example 77:

Where R = N(C) ₂ .

Example 78 - Example 72 was repeated except that the doping compound was a cobalt-butanedione oxime complex having the following structure:

Wherein R = COOCH ₃ .

Example 79

Example 72 was repeated except that the cobalt-butanedione oxime complex is as follows:

Where L = H ₂ 0.

Example 80

Where L = CH ₃ CN. Example 81:

Example 82:

Example 83:

Example 84:

Example 85: Example 1 was repeated except that the doping compound was chromium dichloride. Example 86

Example 1 was repeated except that the doping compound was chromium trichloride. Example 87:

Example 1 was repeated except that the dopant compound was chromium dibromide. Example 88

Example 1 was repeated except that the doping compound was chromium tribromide. Example 89

Example 1 was repeated except that the doping compound was chromium nitrate.

Example 90

Example 1 was repeated except that the dopant compound was chromium carbonate.

Example 91:

Example 1 was repeated except that the doping compound was chromium oxalate.

Example 92

Example 1 was repeated except that the doping compound was chromium acetate.

Example 93

Example 1 was repeated except that the doping compound was chromium phosphate. Table 1 Comparison of the composition and hydrogen production rate of the hydrogen production system of the examples 1 to 10 and the control file

Alcohol (4 ml) glycerol (4 ml), pH 3~10; 500 W high pressure mercury lamp; 400 nm filter to ensure transmission of light through the required wavelength; gas chromatography to detect hydrogen generation (4 A molecular sieve column) , TCD detector, methane internal standard quantitation).

As can be seen from Table 1, the rate of hydrogen production in Examples 1 to 10 of the present invention is generally greater than that in Control Documents 1, 2, and the hydrogen production rate in Example 1 of the present invention is the most embarrassing, which is 107 moHi mg.

Example 94

A photocatalytic system comprising a composite semiconductor photocatalyst for reforming a biomass derivative and preparing hydrogen, comprising the steps of:

Add 5mg P-25 Ti0 ₂ and 5ml core-shell cadmium selenide/cadmium sulfide quantum dots to the Pyrex tube (CdSe/CdS quantum dot solution concentration based on cadmium ion concentration, cadmium ion concentration = lxl (T ³ mol / L), adjust the pH to 11 with 1mol/L sodium hydroxide, centrifuge, remove the supernatant, and retain the precipitate; then add 0.5ml of nickel dichloride solution (original concentration 4.2xl (T ³ mol / L contains 0.5mg six) Hydrated nickel dichloride), 4ml ethanol (original concentration 17.16 mol / L, 20 ° C), 1M NaOH adjusted pH = ll and the total volume is 10ml, so that it is in a sealed nitrogen atmosphere, with 500W high pressure mercury The lamp (400 nm long pass glass filter) illuminates the tube.

In this embodiment, the atomic composition ratio of the semiconductor photocatalyst is Ti0 ₂ -CdSeS-Ni _{x ;} wherein the X value is determined by ICP (Inductively Coupled Plasma Atomic Emission Spectrometer) as: x = 0.26%. The hydrogen production rate was 357 μπιοΗι. Example 95

Add 5mg P-25 Ti0 ₂ and 5ml core-shell cadmium selenide/cadmium sulfide quantum dots to the Pyrex tube (CdSe/CdS quantum dot solution concentration based on cadmium ion concentration, cadmium ion concentration = 1 x 10 - ³ mol /L), adjust the pH to 11 with 1 mol/L sodium hydroxide, centrifuge, remove the supernatant, and retain the precipitate; then add 0.5 ml of nickel dichloride aqueous solution (original concentration 4.2 l O" ³ mol/L, containing 0.5 Mg hexahydrate nickel dichloride), 4ml methanol (original concentration 24.75 mol / L, 20 ° C), lM NaOH adjust pH = ll and make the total volume to 10ml, so that it is in a sealed nitrogen atmosphere, with 500W A high pressure mercury lamp (400 nm long pass glass filter) illuminates the tube.

In this embodiment, the atomic composition ratio of the semiconductor photocatalyst is Ti0 ₂ -CdSeS-Ni _{x ;} wherein the X value is determined by ICP (Inductively Coupled Plasma Atomic Emission Spectrometer) as: x = 0.13%. The hydrogen production rate is 23441^)1·^. Example 96:

Add 5mg P-25 Ti0 ₂ and 5ml core-shell cadmium selenide/cadmium sulfide quantum dots to the Pyrex tube (CdSe/CdS quantum dot solution concentration based on cadmium ion concentration, cadmium ion concentration = lx lO - ³ mol / L), adjust the pH to 11 with ¹ mol/L sodium hydroxide, centrifuge, remove the supernatant, and retain the precipitate; then add 0.5 ml of cobalt sulfate aqueous solution (original concentration 4.2× 10- ³ mol/L containing 0.59 mg of heptahydrate sulfuric acid) Cobalt), 4ml ethanol (original concentration 17.16 mol/L, 20 °C), lM NaOH adjust pH=ll and make the total volume to 10ml, so that it is in a sealed nitrogen atmosphere, with 500W high pressure mercury lamp (400 nm) Long pass glass filter) Irradiate the tube. In this embodiment, the atomic composition ratio of the semiconductor photocatalyst is Ti0 ₂ -CdSeS-Co _{x ;} wherein the X value is determined by ICP (Inductively Coupled Plasma Atomic Emission Spectrometer) as: x = 0.24%. The hydrogen production rate is 286μπιοΗι-

Example 97

Add 5mg P-25 Ti0 ₂ and 5ml core-shell cadmium selenide/cadmium sulfide quantum dots to the Pyrex tube (CdSe/CdS quantum dot solution concentration based on cadmium ion concentration, cadmium ion concentration = 1 x 10 - ³ mol /L), adjust the pH to 11 with ¹ mol/L sodium hydroxide, centrifuge, remove the supernatant, and retain the precipitate; then add 0.5 ml of cobalt nitrate aqueous solution (original concentration 4.2x lO- ³ mol/L with 0.61 mg hexahydrate) Cobalt nitrate), 4ml ethanol (original concentration 17.16 mol/L, 20 °C), IM NaOH adjusted pH=ll and the total volume is 10ml, so that it is in a sealed nitrogen atmosphere, with 500W high pressure mercury lamp (400 Long-pass glass filter of nm) Irradiation of the test tube.

In this embodiment, the atomic composition ratio of the semiconductor photocatalyst is Ti0 ₂ -CdSeS-Co _{x ;} wherein the X value is determined by ICP (Inductively Coupled Plasma Atomic Emission Spectrometer) as: x = 0.19%. The hydrogen production rate is 265μπιο1·1ι—

Example 98

Add 5mg P-25 Ti0 ₂ and 5ml core-shell cadmium selenide/cadmium sulfide quantum dots to the Pyrex tube (CdSe/CdS quantum dot solution concentration based on cadmium ion concentration, cadmium ion concentration = 1 x 10 - ³ mol /L), adjust the pH to 11 with lmol/L sodium hydroxide, centrifuge, remove the supernatant, and retain the precipitate; then add 0.5ml of nickel nitrate solution (original concentration 4.2x 10" ³ mol / L, containing 0.61mg six Hydrated nickel nitrate), 4ml ethanol (original concentration 17.16 mol / L, 20 ° C), IM NaOH adjusted pH = ll and the total volume is 10ml, so that it is in a sealed nitrogen atmosphere, with a 500W high pressure mercury lamp ( A 400 nm long pass glass filter is used to illuminate the tube.

In this embodiment, the atomic composition ratio of the semiconductor photocatalyst is Ti0 ₂ -CdSeS-Ni _{x ;} wherein the X value is determined by ICP (Inductively Coupled Plasma Atomic Emission Spectrometer) as: x = 0.17%. The hydrogen production rate is 323μπιο1·1ι—

Example 99

Add 5mg P-25 Ti0 ₂ and 5ml core-shell cadmium selenide/cadmium sulfide quantum dots to the Pyrex tube (CdSe/CdS quantum dot solution concentration based on cadmium ion concentration, cadmium ion concentration = 1 x 10 - ³ mol /L), adjust the pH to 11 with ¹ mol/L sodium hydroxide, centrifuge, remove the supernatant, and retain the precipitate; then add 0.5 ml of nickel sulfate aqueous solution (original concentration 4.2 l O" ³ mol/L, containing 0.61 mg seven Hydrated nickel sulfate), 4ml ethanol (original concentration 17.16 mol/L, 20 °C), IM NaOH adjusted pH=ll and the total volume is 10ml, so that it is in a sealed nitrogen atmosphere, using a 500W high pressure mercury lamp ( A 400 nm long pass glass filter is used to illuminate the tube.

In this embodiment, the atomic composition ratio of the semiconductor photocatalyst is Ti0 ₂ -CdSeS-Ni _{x ;} wherein the X value is determined by ICP (Inductively Coupled Plasma Atomic Emission Spectrometer) as: x = 0.25%. The hydrogen production rate is 3494^101·^.

Example 100:

Add 5mg P-25 Ti0 ₂ and 5ml core-shell cadmium selenide/cadmium sulfide quantum dots to the Pyrex tube (CdSe/CdS quantum dot solution concentration based on cadmium ion concentration, cadmium ion concentration = lxl (T ³ mol / L), adjust the pH to 11 with 1mol/L sodium hydroxide, centrifuge, remove the supernatant, and retain the precipitate; then add 0.5ml of nickel dichloride solution (original concentration 4.2xl (T ³ mol / L contains 0.5mg six) Hydrated nickel dichloride), 4ml sucrose aqueous solution (original concentration 0.25 mol / L, 20 ° C), IM NaOH adjusted pH = ll and the total volume is 10ml, so that it is in a sealed nitrogen atmosphere, with 500W high pressure Mercury lamps (400 nm long pass glass filters) are irradiated to the tubes.

In this embodiment, the atomic composition ratio of the semiconductor photocatalyst is Ti0 ₂ -CdSeS-Ni _x; wherein the X value is passed through the ICP (electrical The inductively coupled plasma optical emission spectrometer was determined to be: x = 0.12%. The hydrogen production rate is 69μηι ₀ Ηι—

Example 101:

Add 5mg P-25 Ti0 ₂ and 5ml core-shell cadmium selenide/cadmium sulfide quantum dots to the Pyrex tube (CdSe/CdS quantum dot solution concentration based on cadmium ion concentration, cadmium ion concentration = lxl O - ³ mol / L), adjust the pH to 11 with lmol/L sodium hydroxide, centrifuge, remove the supernatant, and retain the precipitate; then add 0.5ml of nickel dichloride aqueous solution (original concentration 4.2xl O_ ³ mol/L with 0.5mg hexahydrate) Nickel dichloride), 4ml aqueous glucose solution (original concentration 0.25 mol/L, 20 °C), pH=ll adjusted by lM NaOH and the total volume is 10ml, so that it is in a sealed nitrogen atmosphere, with 500W high pressure mercury The lamp (400 nm long pass glass filter) illuminates the tube.

In this embodiment, the atomic composition ratio of the semiconductor photocatalyst is Ti0 ₂ -CdSeS-Ni _{x ;} wherein the X value is determined by ICP (Inductively Coupled Plasma Atomic Emission Spectrometer) as: x = 0.16%. The hydrogen production rate is 87μπι ₀ Ηι—

Example 102:

A photocatalytic system comprising a composite semiconductor photocatalyst for reforming a biomass derivative and preparing hydrogen: comprising the following steps:

Add 5mg P-25 Ti0 ₂ and 5ml core-shell cadmium selenide/cadmium sulfide quantum dots to the Pyrex tube (CdSe/CdS quantum dot solution concentration based on cadmium ion concentration, cadmium ion concentration = lxl O_ ³ mol/L ), adjust the pH to 11 with ¹ mol/L sodium hydroxide, centrifuge, remove the supernatant, and retain the precipitate; then add 0.5 ml of aqueous nickel dichloride solution (original concentration 4.2 x l CT ³ mol/L with 0.5 mg hexahydrate) Nickel chloride), 4ml isopropanol (original concentration 13.1 mol/L, 20 °C), 1M NaOH adjusted pH=ll and the total volume is 10ml, so that it is in a sealed nitrogen atmosphere, with 500W high pressure mercury The lamp (400 nm long pass glass filter) illuminates the tube.

In this embodiment, the atomic composition ratio of the semiconductor photocatalyst is Ti0 ₂ -CdSeS-Ni _{x ;} wherein the X value is determined by ICP (Inductively Coupled Plasma Atomic Emission Spectrometer) to be: x = 0.23%. The hydrogen production rate is 351μπιοΗι-

Example 103:

Add 5mg P-25 Ti0 ₂ and 5ml core-shell cadmium selenide/cadmium sulfide quantum dots to the Pyrex tube (CdSe/CdS quantum dot solution concentration based on cadmium ion concentration, cadmium ion concentration = lx l0 - ³ mol / L), adjust the pH to 11 with 1mol/L sodium hydroxide, centrifuge, remove the supernatant, and retain the precipitate; then add 0.5ml of nickel dichloride solution (original concentration 4.2xl O_ ³ mol/L with 0.5mg hexahydrate) Nickel dichloride), 4ml n-butanol (original concentration 10.9 mol/L, 20 °C), 1M NaOH adjusted pH=7 and the total volume is 10ml, so that it is in a sealed nitrogen atmosphere, with 500W high pressure A mercury lamp (400 nm short-wavelength glass filter) is used to illuminate the tube.

In this embodiment, the atomic composition ratio of the semiconductor photocatalyst is Ti0 ₂ -CdSeS-Ni _{x ;} wherein the _X value is determined by ICP (Inductively Coupled Plasma Atomic Emission Spectrometer) as: x=0.11%. The hydrogen production rate is 31μπι ₀ Ηι—

Example 104

Add 5mg P-25 Ti0 ₂ and 5ml core-shell cadmium selenide/cadmium sulfide quantum dots to the Pyrex tube (CdSe/CdS quantum dot solution concentration based on cadmium ion concentration, cadmium ion concentration = 1 x 10 - ³ mol /L), adjust the pH to 11 with ¹ mol/L sodium hydroxide, centrifuge, remove the supernatant, and retain the precipitate; then add 0.5 ml of nickel dichloride aqueous solution (original concentration 4.2xl O- ³ mol/L 0.5mg) Chlorine hexahydrate), 4ml ethylene glycol (original concentration 17.9 mol/L, 20 ° C), 1M NaOH adjusted pH = 9 and the total volume is 10 ml, so that it is in a sealed nitrogen atmosphere, with A 500W high pressure mercury lamp (the glass tube itself can be passed through the UV plus visible light) illuminates the tube.

In this embodiment, the atomic composition ratio of the semiconductor photocatalyst is Ti0 ₂ -CdSeS-Ni _{x ;} wherein the X value is determined by ICP (Inductively Coupled Plasma Atomic Emission Spectrometer) as: _x = 0.18%. The hydrogen production rate is 87μπιοΗι- Example 105:

Add 5mg P-25 Ti0 ₂ and 5ml core-shell cadmium selenide/cadmium sulfide quantum dots to the Pyrex tube (CdSe/CdS quantum dot solution concentration based on cadmium ion concentration, cadmium ion concentration = lxl O_ ³ mol/L ), adjust the pH to 11 with ¹ mol/L sodium hydroxide, centrifuge, remove the supernatant, and retain the precipitate; then add 0.5 ml of aqueous nickel dichloride solution (original concentration 4.2 x l (T ³ mol/L with 0.5 mg hexahydrate) Nickel dichloride), 4ml glycerol (original concentration 13.7 mol L, 20 ° C), 1M NaOH adjusted pH = 12 and the total volume is 10 ml, so that it is in a sealed nitrogen atmosphere, with 500W high pressure mercury The lamp (400 nm long pass glass filter) illuminates the tube.

In this embodiment, the atomic composition ratio of the semiconductor photocatalyst is Ti0 ₂ -CdSeS-Ni _{x ;} wherein the X value is determined by ICP (Inductively Coupled Plasma Atomic Emission Spectrometer) as: x = 0.13%. The hydrogen production rate is 18μπι ₀ 1·1ι—

Example 106:

Add 5mg P-25 Ti0 ₂ and 5ml core-shell cadmium selenide/cadmium sulfide quantum dots to Pyrex tube (CdSe/CdS quantum dot solution concentration based on cadmium ion concentration, cadmium ion concentration = lxl (T ³ moI/ L), adjust the pH to 11 with 1mol/L sodium hydroxide, centrifuge, remove the supernatant, and retain the precipitate; then add 0.5ml of nickel dichloride solution (original concentration 4.2xl O_ ³ mol/L with 0.5mg hexahydrate) Nickel dichloride), 4ml of triethylamine solution (original concentration 0.25mol/L, 20°C), pH 14 adjusted by 1M NaOH and the total volume is 10ml, so that it is in a sealed nitrogen atmosphere, with 500W high pressure Mercury lamps (400 nm long pass glass filters) were irradiated to the tubes.

In this embodiment, the atomic composition ratio of the semiconductor photocatalyst is Ti0 ₂ -CdSeS-Ni _{x ;} wherein the X value is determined by ICP (Inductively Coupled Plasma Atomic Emission Spectrometer) as: x = 0.19%. The rate of hydrogen production is ΖΒΙμπιοΙ

Example 107:

Add 5mg P-25 Ti0 ₂ and 5ml core-shell cadmium selenide/cadmium sulfide quantum dots to the Pyrex tube (CdSe/CdS quantum dot solution concentration based on cadmium ion concentration, cadmium ion concentration = lxl O_ ³ mol/L ), adjust the pH to 11 with ¹ mol/L sodium hydroxide, centrifuge, remove the supernatant, and retain the precipitate; then add 0.5 ml of nickel dichloride aqueous solution (original concentration 4.2xl O- ³ mol/L with 0.5mg hexahydrate) Nickel dichloride), 4ml triethanolamine (original concentration 0.25 mol / L, 20 ° C), lM NaOH adjusted pH = 13 and the total volume is 10ml, so that it is in a sealed nitrogen atmosphere, with 500W high pressure mercury The lamp (400 nm long pass glass filter) illuminates the tube.

In this embodiment, the atomic composition ratio of the semiconductor photocatalyst is Ti0 ₂ -CdSeS-Ni _{x ;} wherein the X value is determined by ICP (Inductively Coupled Plasma Atomic Emission Spectrometer) as: x = 0.17%. The hydrogen production rate is 189μπιοΗι-

Example 108

Add 5mg P-25 Ti0 ₂ and 5ml core-shell cadmium selenide quantum dots to Pyrex tube (CdSe quantum dot solution concentration based on cadmium ion concentration, cadmium ion concentration = lxl (T ³ mol / L), with 1mol /L sodium hydroxide to adjust the pH to 11, centrifugation, remove the supernatant, retain the precipitate; then add 0.5ml of chromium trichloride aqueous solution (original concentration 4.2x 1 (T ³ moI / L contains 0.56mg hexahydrate trichlorinated Chromium), 4ml ethanol (original concentration 17.16 mol/L, 20 °C), 1M NaOH to adjust pH=ll and make the total volume to 10ml, in a sealed nitrogen atmosphere, with 500W high pressure mercury lamp (400 nm) Long pass glass filter) Irradiate the tube.

During the reaction, the hydrogen generated in the reaction was detected by gas chromatography (TCD thermal conductivity detector), and the hydrogen production rate was 56 μπιο1·1ι" ¹ °.

In this embodiment, the atomic composition ratio of the semiconductor photocatalyst is Ti0 ₂ -CdS _e -Cr _x; wherein the X value is passed through the ICP (electrical The inductively coupled plasma optical emission spectrometer was determined to be: x = 0.17%.

Example 109:

Add 5mg P-25 Ti0 ₂ and 5ml core-shell cadmium selenide quantum dots to the Pyrex tube (CdSe quantum dot solution concentration based on cadmium ion concentration, cadmium ion concentration = l xlO- ³ mol/L), with 1mol /L sodium hydroxide to adjust the pH to 11, centrifugation, remove the supernatant, retain the precipitate; then add 0.5ml potassium chloroplatinate solution (original concentration 4.2x10" ³ mol / L with 0.87mg potassium chloroplatinate) 4ml ethanol (original concentration 17.16 mol/L, 20 °C), IM NaOH adjust pH=ll and make the total volume to 10ml, so that it is in a sealed nitrogen atmosphere, with 500W high pressure mercury lamp (400 nm long wave) Through-glass filter) Irradiate the tube.

During the reaction, the hydrogen gas generated in the reaction was detected by gas chromatography (TCD thermal conductivity detector), and the hydrogen production rate was 71 μπιο1·1ι.

In this embodiment, the atomic composition ratio of the semiconductor photocatalyst is Ti0 ₂ -CdSe-Pt _x; wherein the X value is determined by ICP (Inductively Coupled Plasma Atomic Emission Spectrometer) to be: x=0.31%.

Example 110:

Add 5mg P-25 Ti0 ₂ and 5ml core-shell cadmium selenide quantum dots to Pyrex tube (CdSe quantum dot solution concentration based on cadmium ion concentration, cadmium ion concentration = l xl (T ³ mol/L), Lmol/L sodium hydroxide was adjusted to pH 11, centrifuged, the supernatant was removed, and the precipitate was retained. Then 0.5 ml of potassium chloropalladium solution (original concentration 4.2 lO) ³ mol/L containing 0.69 mg of potassium chloropalladium was added. ), 4ml ethanol (original concentration 17.16 mol / L, 20 ° C), IM NaOH adjust pH = ll and make the total volume to 10ml, so that it is in a sealed nitrogen atmosphere, with 500W high pressure mercury lamp (400 nm Long pass glass filter) Irradiate the tube.

During the reaction, the hydrogen gas generated in the reaction was detected by gas chromatography (TCD thermal conductivity detector), and the hydrogen production rate was 101 μπιο1· ^{1 -1} .

In this embodiment, the atomic composition ratio of the semiconductor photocatalyst is Ti0 ₂ -CdSe-Pd _x; wherein the X value is determined by ICP (Inductively Coupled Plasma Atomic Emission Spectrometer) as: x = 0.34%.

Example 111:

Add 5mg P-25 Ti0 ₂ and 5ml core-shell cadmium selenide quantum dots to the Pyrex tube (CdSe quantum dot solution concentration based on cadmium ion concentration, cadmium ion concentration = l xlO_ ³ mol/L), using 1mol/ L sodium hydroxide was adjusted to pH 11, centrifuged, the supernatant was removed, and the precipitate was retained; then 0.5 ml of an aqueous solution of antimony trichloride was added (original concentration 4.2 x 1 (T ³ mol/L containing 0.44 mg of antimony trichloride), 4 ml Ethanol (original concentration 17.16 mol/L, 20 °C), IM NaOH adjusts pH=ll and makes the total volume constant to 10 ml, so that it is in a sealed nitrogen atmosphere, using a 500W high pressure mercury lamp (400 nm long wave pass type) Glass filter) Irradiate the tube.

During the reaction, the hydrogen produced in the reaction was detected by gas chromatography (TCD thermal conductivity detector), and the hydrogen production rate was 218 μπιο1·1ι.

In this embodiment, the atomic composition ratio of the semiconductor photocatalyst is Ti0 ₂ -CdSe-Ru _{x ;} wherein the X value is determined by ICP (Inductively Coupled Plasma Atomic Emission Spectrometer) as: x = 0.36%.

Example 112:

Add 5mg P-25 Ti0 ₂ and 5ml core-shell cadmium selenide quantum dots to the Pyrex tube (CdSe quantum dot solution concentration based on cadmium ion concentration, cadmium ion concentration = lx lO- ³ mol/L), with 1mol /L sodium hydroxide adjusts the pH to 11, Centrifuge, remove the supernatant, and retain the precipitate; then add 0.5ml of copper sulfate solution (original concentration 4.2xl (T ³ mol / L containing 0.52mg copper sulfate pentahydrate), 4ml ethanol (original concentration 17.16 mol / L, 20 ° C), IM NaOH was adjusted to pH = ll and the total volume was made up to 10 ml, which was placed in a sealed nitrogen atmosphere, and the tube was irradiated with a 500 W high pressure mercury lamp (400 nm long pass type glass filter).

During the reaction, the hydrogen gas generated in the reaction was detected by gas chromatography (TCD thermal conductivity detector), and the hydrogen production rate was 20 μπιο1·1ι" ¹ .

In this embodiment, the atomic composition ratio of the semiconductor photocatalyst is Ti0 ₂ -CdSe-C _Ux; wherein the X value is determined by ICP (Inductively Coupled Plasma Atomic Emission Spectrometer) as: x = 0.13%.

Example 113:

A photocatalytic system comprising a composite semiconductor photocatalyst for reforming a biomass derivative and preparing hydrogen, comprising the following steps:

Add 5mg P-25 Ti0 ₂ and 5ml core-shell cadmium selenide quantum dots to the Pyrex tube (CdSe quantum dot solution concentration based on cadmium ion concentration, cadmium ion concentration = lxl O_ ³ mol/L), using 1mol/ L sodium hydroxide adjusted to pH 11, centrifuged, the supernatant removed, the precipitate was retained; 0.5ml aqueous manganese sulfate solution was then added (the original concentration of 4.2x 10- ³ mol / L manganese sulfate-containing 0.36mg), 4ml ethanol (original Concentration 17.16 mol/L, 20 °C), 1M NaOH adjust pH=ll and make the total volume to 10ml, so that it is in a sealed nitrogen atmosphere, with 500W high pressure mercury lamp (400 nm long wave pass glass filter) Tablet) Irradiate the tube.

During the reaction, the hydrogen produced in the reaction was detected by gas chromatography (TCD thermal conductivity detector), and the hydrogen production rate was Sl mol'h-

In this embodiment, the atomic composition ratio of the semiconductor photocatalyst is Ti0 ₂ -CdSe-Mn _{x ;} wherein the value of x is determined by ICP (Inductively Coupled Plasma Atomic Emission Spectrometer) as: x = 0.14%.

Example 114:

Add 5mg P-25 Ti0 ₂ and 5ml core-shell cadmium selenide quantum dots to Pyrex tube (CdSe quantum dot solution concentration based on cadmium ion concentration, cadmium ion concentration = lxl (T ³ mol / L), with 1mol /L sodium hydroxide to adjust the pH to 11, centrifugation, remove the supernatant, retain the precipitate; then add 0.5ml of silver nitrate aqueous solution (original concentration 4.2xl (T ³ mol / L containing 0.36mg silver nitrate), 4ml ethanol (original Concentration 17.16 mol/L, 20 °C), 1M NaOH adjust pH=ll and make the total volume to 10ml, so that it is in a sealed nitrogen atmosphere, with 500W high pressure mercury lamp (400 nm long wave pass glass filter) Tablet) Irradiate the tube.

During the reaction, the hydrogen gas generated in the reaction was detected by gas chromatography (TCD thermal conductivity detector), and the hydrogen production rate was 3 μπιο1·]ι ^-1 .

In this embodiment, the atomic composition ratio of the semiconductor photocatalyst is Ti0 ₂ -CdSe-Ag _{x ;} wherein the X value is determined by ICP (Inductively Coupled Plasma Atomic Emission Spectrometer) as: x = 0.17%.

Example 115:

Pyrex tube was added to 5mg P-25 type Ti0 _2, 5ml core shell quantum dots cadmium selenide (CdSe quantum dots stock concentration of cadmium ion concentration as a reference, the cadmium ion concentration ^{= 1 x 10- 3 mol / L} ), with Lmol / L sodium hydroxide to adjust the pH to 11, centrifugation, remove the supernatant, retain the precipitate; then add 0.5ml aqueous chloroauric acid (original concentration 4.2xl (T ³ mol / L contains 0.87mg chloroauric acid tetrahydrate) 4ml ethanol (original concentration 17.16 mol/L, 20 °C), IM NaOH adjust pH=ll and make the total volume to 10ml, so that it is in a sealed nitrogen atmosphere, with 500W high pressure mercury lamp (400 nm long wave) Through-glass filter) Irradiate the tube.

During the reaction, the hydrogen gas generated in the reaction was detected by gas chromatography (TCD thermal conductivity detector), and the hydrogen production rate was 2 μηιο1·1 " ¹ . In this embodiment, the atomic composition ratio of the semiconductor photocatalyst is Ti0 ₂ -CdSe-Au _x; wherein the X value is determined by ICP (Inductively Coupled Plasma Atomic Emission Spectrometer) as: x=0.12%.

Example 116:

Add 5mg P-25 type Ή0 ₂ and 5ml core-shell cadmium selenide quantum dots to Pyrex tube (CdSe quantum dot solution concentration based on cadmium ion concentration, cadmium ion concentration = lxl (T ³ mol / L), with 1mol /L sodium hydroxide to adjust the pH to 11, centrifugation, remove the supernatant, retain the precipitate; then add 0.5ml aqueous solution of barium chloride (original concentration 4.2x 10_ ³ mol / L containing 0.44mg hydrated barium chloride), 4ml ethanol (Original concentration: 17.16 mol/L, 20 °C), 1M NaOH adjusts pH=ll and makes the total volume constant to 10ml, so that it is in a sealed nitrogen atmosphere, using 500W high pressure mercury lamp (400 nm long wave pass glass) Filter) Irradiate the tube.

During the reaction, the hydrogen gas generated in the reaction was detected by gas chromatography (TCD thermal conductivity detector), and the hydrogen production rate was 6 μηιο1·1ι ^-1 .

In this embodiment, the atomic composition ratio of the semiconductor photocatalyst is Ti0 ₂ -CdSe-R _{x ;} wherein the X value is determined by ICP (Inductively Coupled Plasma Atomic Emission Spectrometer) as: x = 0.15%.

Example 117:

A photocatalytic system comprising a composite semiconductor photocatalyst for reforming a biomass derivative and preparing hydrogen comprises the following steps: adding 5 mg of P-25 type Ti0 ₂ and 5 ml of core-shell cadmium selenide quantum dots to a Pyrex tube (CdSe quantum dot solution concentration is based on cadmium ion concentration, cadmium ion concentration = lxl (T ³ mol / L), pH is adjusted to 11 with ¹ mol / L sodium hydroxide, centrifuged, the supernatant is removed, and the precipitate is retained; Add 0.5ml aqueous solution of potassium hexachloroantimonate (original concentration 4.2xl (T ³ mol / L containing 1.0 mg of potassium hexachloroantimonate), 4 ml of ethanol (original concentration 17.16 mol / L, 20 ° C), 1M NaOH to adjust the pH =ll and the total volume was made 10 ml, in a sealed nitrogen atmosphere, and the tube was irradiated with a 500 W high pressure mercury lamp (400 nm long pass glass filter).

During the reaction, the hydrogen gas generated in the reaction was detected by gas chromatography (TCD thermal conductivity detector), and the hydrogen production rate was 7 μηιο1· ^{1 -1} .

In this embodiment, the atomic composition ratio of the semiconductor photocatalyst is Ti0 ₂ -CdS _e -Re _{x ;} wherein the X value is determined by ICP (Inductively Coupled Plasma Atomic Emission Spectrometer) as: x = 0.13%.

Example 118:

A photocatalytic system comprising a composite semiconductor photocatalyst for reforming a biomass derivative and preparing hydrogen comprises the following steps: adding 5 mg of P-25 type Ti0 ₂ and 5 ml of core-shell cadmium selenide quantum dots to a Pyrex tube (CdSe quantum dot solution concentration based on cadmium ion concentration, cadmium ion concentration = 1 ><10-0]), adjust pH to 11 with 1 mol/L sodium hydroxide, centrifuge, remove the supernatant, and retain the precipitate; Add 0.5ml aqueous solution of chlorohydric acid (original concentration 4.2xl (T ³ mol/L containing 1.1 mg of chlorhexidine hexahydrate), 4 ml of ethanol (original concentration 17.16 mol/L, 20 ° C), 1M NaOH to adjust pH=ll The total volume was made up to a volume of 10 ml, which was placed in a sealed nitrogen atmosphere, and the tube was irradiated with a 500 W high pressure mercury lamp (400 nm long pass type glass filter).

During the reaction, the hydrogen gas generated in the reaction was detected by gas chromatography (TCD thermal conductivity detector), and the hydrogen production rate was 0.5 μη ο1·1ι.

In this embodiment, the atomic composition ratio of the semiconductor photocatalyst is Ti0 ₂ -CdS _e -Ir _{x ;} wherein the X value is determined by ICP (Inductively Coupled Plasma Atomic Emission Spectrometer) as: x = 0.11%.

Example 119

Add 5mg P-25 Ti0 ₂ and 1ml cadmium sulfide quantum dots to the Pyrex tube (CdS quantum dot solution concentration is cadmium The ion concentration is based on the cadmium ion concentration = 5x l O- ³ mol/L), the pH is adjusted to 11 with ¹ mol/L sodium hydroxide, centrifuged, the supernatant is removed, and the precipitate is retained; then 0.5 ml of chromium trichloride is added. Aqueous solution (original concentration 4.2xl (T ³ mol/L contains 0.56mg chromium trichloride hexahydrate), 4ml methanol (original concentration 24.75 mol/L, 20 °C), 1M NaOH adjusts pH=ll and makes the total volume constant For 10 ml, it was placed in a sealed nitrogen atmosphere, and the tube was irradiated with a 500 W high pressure mercury lamp (400 nm long pass type glass filter).

During the reaction, the hydrogen gas generated in the reaction was detected by gas chromatography (TCD thermal conductivity detector), and the hydrogen production rate was 1.8 μπιο1·1ι ^-1 .

In this embodiment, the atomic composition ratio of the semiconductor photocatalyst is Ti0 ₂ - CdS-Qr _{x ;} wherein the value of x is determined by ICP (Inductively Coupled Plasma Atomic Emission Spectrometer) as: x = 0.16%.

Example 120

A photocatalytic system comprising a composite semiconductor photocatalyst for reforming a biomass derivative and preparing hydrogen comprises the following steps: _ Adding 5 mg of P-25 type Ti0 ₂ and 5 ml of cadmium telluride quantum dots (CdTe) to a Pyrex tube The concentration of the quantum dot solution is based on the cadmium ion concentration, the cadmium ion concentration = lxl (T ³ mol / L), the pH is adjusted to 11 with ¹ mol / L sodium hydroxide, centrifuged, the supernatant is removed, and the precipitate is retained; then 0.5 is added. Ml chloroplatinate potassium solution (original concentration 4.2xl (T ³ mol / L containing 0.87mg potassium chloroplatinate), 4ml ethanol (original concentration 17.16 mol / L, 20 ° C), 1M NaOH to adjust pH = ll and total The volume was set to 10 ml, and it was placed in a sealed nitrogen atmosphere. The tube was irradiated with a 500 W high pressure mercury lamp (400 nm long pass type glass filter).

During the reaction, hydrogen gas generated in the reaction was detected by gas chromatography (TCD thermal conductivity detector), and the hydrogen production rate was 1.5 μπιο1·1ι ^-1 .

In this embodiment, the atomic composition ratio of the semiconductor photocatalyst is Ti0 ₂ -CdTe-Pt _x; wherein the X value is determined by ICP (Inductively Coupled Plasma Atomic Emission Spectrometer) as: x = 0.18%. It is apparent that the above-described embodiments of the present invention are merely illustrative of the present invention and are not intended to limit the embodiments of the present invention. Other variations or modifications of the various forms may be made by those skilled in the art in light of the above description. It is not possible to exhaust all implementations here. Obvious changes or variations that come within the scope of the invention are still within the scope of the invention.

Claims

Claim

A semiconductor photocatalyst for photocatalytic reforming of a biomass derivative for hydrogen production, characterized in that the atomic composition ratio of the semiconductor photocatalyst is M~NA _{X ;}

Wherein: M~N is a group II element to a group VI element or M~N is a group III element to a group V element;

Wherein A is one or more elements of cobalt, nickel, iron, copper, chromium, palladium, platinum, rhodium, ruthenium, gold, silver, manganese, ruthenium or osmium; wherein 0.02% < x < 1.0

2. A semiconductor photocatalyst according to claim 1 wherein:

The semiconductor photocatalyst atomic composition ratio of _{_{_{Ti0 2 -M~NA x, Sn0 2 -M~NA}}} x or ZnO-M~ NA _x.

3. A method of fabricating a semiconductor photocatalyst according to claim 1, comprising the steps of:

1) adding a quantum dot composed of a group II~VI element or a group ΠI~V element in the reactor;

2) One or a mixture of two or more of the following substances is added to the reactor: a salt of cobalt, a complex of cobalt, a salt of nickel, a complex of nickel, a salt of iron, a complex of iron, a salt of copper, a chromium salt, a palladium salt, a platinum salt, a barium salt, a barium salt, a barium salt, a gold salt, a silver salt, a manganese salt, a barium salt, a barium salt solution, to obtain a solution crucible;

4) adjusting the pH of the mixed solution B to 3~10, to obtain a mixed solution C; the method for adjusting the pH is: adding 1 mol/L NaOH or 1 mol/L HCl to the mixed solution B;

The method for preparing a semiconductor photocatalyst according to claim 3, wherein the biomass derivative is methanol, ethanol, propanol, butanol, ethylene glycol, glycerin, glucose, sucrose, fructose , maltose, mannose, ascorbic acid, L-valine or L-cysteine.

A method of preparing a semiconductor photocatalyst according to claim 2, comprising the steps of:

2) One or a mixture of two or more of the following substances is added to the precipitate: a salt of cobalt, a complex of cobalt, a salt of nickel, a complex of nickel, a salt of iron, a complex of iron, a salt of copper, a salt of chromium, a salt of palladium, a salt of platinum, a salt of cerium, a salt of cerium, a salt of cerium, a salt of gold, a salt of silver, a salt of manganese, a salt of cerium, a salt solution of cerium;

3) adding an aqueous solution of the biomass derivative to the precipitate;

4) irradiating the reactor with ultraviolet light and/or visible light in an inert gas or vacuum atmosphere to obtain a semiconductor having an atomic composition ratio of Ti0 ₂ -M~NA _x , Sn0 ₂ -M~NA _x or ZnO-M~NA _x catalyst of light.

The method for preparing a semiconductor photocatalyst according to claim 5, wherein the biomass derivative is triethanolamine, triethylamine, methanol, ethanol, propanol, butanol, ethylene glycol, or propylene Alcohol, glucose, sucrose, fructose, maltose or mannose<=

The method according to claim 3 or 5, wherein the quantum dots composed of the group II to VI elements include one or more of CdS, CdSe, CdTe, PbS, PbSe, ZnS, and ZnSe. The composite structure quantum dot is composed; the quantum dot composed of the ΠΙ~ν group element comprises a composite structure quantum dot composed of one or two of InP and InAs.

The method according to claim 3 or 5, wherein the quantum dot concentration of the II~VI or III~V elements in step 1) is greater than l xlO^g

The method according to claim 3 or 5, wherein in the step 2), the cobalt salt, the cobalt complex, the nickel salt, the nickel complex, the iron salt, the iron complex, The whole reaction of copper salt, chromium salt, palladium salt, platinum salt, barium salt, barium salt, barium salt, gold salt, silver salt, manganese salt, barium salt, barium salt System concentration > l lO" ⁶ mol / L;

The cobalt salt is cobalt halide, cobalt sulfate, cobalt nitrate, cobalt carbonate, cobalt oxalate, cobalt acetate, cobalt phosphate or cobalt chromate; the cobalt complex is a cobalt-ammonia complex [Co(N3⁄4) ₆ ] ³⁺ , cobalt-cyano complex [Co(CN) ₆ f, cobalt-thiocyanate complex [Co(SCN) ₄ ] ² \ cobalt-carbonyl complex [Co(CO) ₄ ] cobalt-nitro complex [ Co(N0 ₃ ) ₄ f, cobalt-nitroso complex [Co(N0 ₂ ) ₆ ] ³ — or cobalt-butanedione oxime complex; wherein, the cobalt-butanedione oxime complex and its derivative are The following structural formula:

Where L is 3⁄40 or C3⁄4CN; 1 is 1, N(CH ₃ ) 2 or (COOCH ₃ );

The nickel complex is a nickel-ammonia complex [Ni(NH ₃ ) ₆ ] ²⁺ , a nickel-cyanide complex [Ni(CN) ₄ f, a nickel-chelate [Ni(en) ₃ ] ²⁺ , nickel-carbonyl coordination compound Ni(CO) ₄ or nickel-ethyl coordination compound (C ₂ 3⁄4) ₂ Ni;

The iron salt is iron halide, iron sulfate, iron nitrate, iron carbonate, iron oxalate, iron acetate, iron phosphate, iron chromate, ferrous halide, ferrous sulfate, ferrous nitrate, ferrous carbonate, ferrous oxalate. , ferrous acetate, ferrous phosphate, ferrous chromite or ammonium ferrous sulfate;

The iron complex is an iron-cyano complex [Fe(CN) ₆ f, a ferrous-cyano complex [Fe(CN) ₆ ] ⁴ _, an iron-thiocyanate complex Fe(SCN) ₃ , iron - Sulfur complex [Fe ₂ S ₂ (CO) ₆ ], iron-carbonyl complex Fe(CO) ₅ , iron-carbonyl complex Fe ₂ (CO) ₉ Or an iron-carbonyl complex Fe ₃ (CO) _{12 ;}

The copper salt is copper halide, copper sulfate, copper nitrate, copper carbonate, copper oxalate, copper acetate, copper phosphate, copper chromate, copper pyrophosphate, copper cyanide, copper fatty acid, copper naphthenate, cuprous halide , cuprous sulfate, cuprous carbonate or cuprous acetate; the chromium salt is chromium halide, chromium sulfate, chromium nitrate, chromium carbonate, chromium oxalate, chromium acetate or chromium phosphate; the salt of the palladium is tetrachloropalladium Potassium acid, palladium halide, palladium sulfate, palladium nitrate or palladium acetate;

The salt of platinum is potassium tetrachloroplatinate, platinum halide or platinum nitrate;

The salt of gold is gold halide or chloroauric acid;

The manganese salt is manganese halide, manganese sulfate, nitric acid or manganese acetate;

The salt of the cerium is cerium halide or chloroantimonic acid;

10. The method according to claim 3 or 5, characterized in that the concentration of the biomass derivative in the entire reaction system is ≥ l xl (T ⁴ mol/L or mole percentage ≥ 0.01%).

A system comprising a photocatalytic reforming biomass derivative of the semiconductor photocatalyst according to claim 1 and producing hydrogen, characterized in that it comprises the following materials:

1) quantum dots composed of II-VI or III~V elements;

2) one or a mixture of two or more of the following: a salt of cobalt, a complex of cobalt, a salt of nickel, a complex of nickel, a salt of iron, a complex of iron, a salt of copper, a salt of chromium, a salt of palladium, a salt of platinum, a salt of cerium, a salt of cerium, a salt of cerium, a salt of gold, a salt of silver, a salt of manganese, a salt of cerium, a salt solution of cerium;

3) an aqueous solution of a biomass derivative;

And includes the following conditions:

pH value is 3~10;

UV and / or visible light irradiation conditions.

A system for photocatalytic reforming a biomass derivative comprising the semiconductor photocatalyst of claim 2 and producing hydrogen, characterized by:

Includes the following ingredients:

1) quantum dots composed of II-VI or πι~ν group elements;

2) Ti0 ₂ , Sn0 ₂ or ZnO;

3) one or a mixture of two or more of the following: cobalt salt, cobalt complex, nickel salt, nickel complex, iron salt, iron complex, copper salt, chromium salt, a salt of palladium, a salt of platinum, a salt of cerium, a salt of cerium, a salt of cerium, a salt of gold, a salt of silver, a salt of manganese, a salt of cerium, a salt solution of cerium;

4) an aqueous solution of a biomass derivative;

And includes the following conditions:

Alkaline conditions and UV and / or visible light irradiation conditions.

13. The system according to claim 11 or claim 12, wherein the concentration of the quantum dots or III~V II~VI elements, is greater than 1 X 10- ⁴ g / L;

The quantum dots composed of the group II~VI elements include composite structure quantum dots composed of one or more of CdS, CdSe, CdTe, PbS, PbSe, ZnS, and ZnSe;

The quantum dots composed of the ΙΠ~ν group elements include a composite structure quantum dot composed of one or two of InP and InAs.

The system according to claim 11 or 12, wherein the cobalt salt, the cobalt complex, the nickel salt, the nickel complex, the iron salt, the iron complex, the copper salt, a salt of chromium, a salt of palladium, a salt of platinum, a salt of barium, The concentration of barium salts, barium salts, gold salts, silver salts, manganese salts, barium salts and/or barium salts in the whole reaction system is ≥1 10 01 ;

The cobalt salt is cobalt halide, cobalt sulfate, cobalt nitrate, cobalt carbonate, cobalt oxalate, cobalt acetate, cobalt phosphate or cobalt chromate; the cobalt complex is a cobalt-ammonia complex [Co(NH ₃ ) ₆ ³⁺ , cobalt-cyano complex [Co(CN) ₆ wide, cobalt-thiocyanate complex [Co(SCN) ₄ f, cobalt-carbonyl complex [Co(CO) ₄ ]_, cobalt-nitro complex [Co(N0 ₃ ) ₄ f, cobalt-nitroso complex [Co(N0 ₂ ) ₆ ] ³ — or cobalt-butanedione oxime complex; wherein, cobalt-butanedione oxime complex and its derivatives The object is of the following structure:

Wherein L is H ₂ 0 or C 3⁄4CN; 1 is 1{, N(CH ₃ ) ₂ or (COOCH ₃ );

The iron complex is an iron-cyano complex [Fe(CN) ₆ ] ³ ferrous-cyano complex [Fe(CN) ₆ ] ⁴ _, iron-thiocyanate complex Fe(SCN) ₃ , iron - Sulfur complex [Fe ₂ S ₂ (CO) ₆ ], iron-carbonyl complex Fe(CO) ₅ , iron-carbonyl complex Fe ₂ (CO) ₉ or iron-carbonyl complex Fe ₃ (CO) _{12 ;}

The copper salt is a copper halide, copper sulfate, copper nitrate, copper carbonate, copper oxalate, copper acetate, copper phosphate, copper chromate, Copper pyrophosphate, copper cyanide, copper fatty acid, copper naphthenate, cuprous halide, cuprous sulfate, cuprous carbonate or cuprous acetate; the chromium salt is chromium halide, chromium sulfate, chromium nitrate, chromium carbonate, Chromium oxalate, chromium acetate or chromium phosphate; the salt of the palladium is potassium tetrachlorophosphinate, palladium halide, palladium sulfate, palladium nitrate or palladium acetate;

The salt of gold is gold halide or chloroauric acid;

The salt of the cerium is cerium halide or chloroantimonic acid;

The salt of ruthenium is pentacarbonylphosphonium chloride or pentacarbonylpentadium bromide.

15. The system according to claim 11, wherein the biomass derivative is methanol, ethanol, propanol, butanol, ethylene glycol, glycerol, glucose, sucrose, fructose, maltose, mannose. , ascorbic acid, L-proline or L-cysteine.

16. The system according to claim 12, wherein: the biomass derivative is triethanolamine, triethylamine, methanol, ethanol, propanol, butanol, ethylene glycol, glycerol, glucose, sucrose. , fructose, maltose or mannose.

A method of photocatalytic reforming a biomass derivative using the semiconductor photocatalyst according to claim 1 and producing hydrogen gas, comprising the steps of:

2) Add one or more of the following substances to the reactor: cobalt salt, cobalt complex, nickel salt, nickel complex, iron salt, iron complex, copper salt, chromium a salt, a palladium salt, a platinum salt, a barium salt, a barium salt, a barium salt, a gold salt, a silver salt, a manganese salt, a barium salt, a barium salt solution, to obtain a solution A;

3) adding an aqueous solution of the biomass derivative to the above solution A to obtain a mixed solution B;

4) adjusting the pH of the mixed solution B to 3~10, to obtain a mixed solution C;

18. A method of photocatalytic reforming a biomass derivative using the semiconductor photocatalyst of claim 2 and producing hydrogen gas, comprising the steps of:

The method according to claim 17 or 18, wherein the concentration of quantum dots composed of the group II~VI elements or the ΙΠ~V group elements is greater than 1 x 10 ^-4 g/L _;

The quantum dots composed of the group II to VI elements include composite structure quantum dots composed of one or more of CdS, CdSe, CdTe, PbS, PbSe, ZnS, and ZnSe;

20. The method according to claim 17 or 18, wherein the cobalt salt, cobalt in step 2) Complex, nickel salt, nickel complex, iron salt, iron complex, copper salt, chromium salt, palladium salt, platinum salt, barium salt, barium salt, barium salt, gold The concentration of salt, silver salt, manganese salt, barium salt and/or barium salt in the whole reaction system is ≥1 >< 10 ^-6 1^1/:1 _;

The antimony salt is cobalt halide, cobalt sulfate, cobalt nitrate, cobalt carbonate, cobalt oxalate, cobalt acetate, cobalt phosphate or cobalt chromate; the cobalt complex is a cobalt-ammonia complex [Co(NH ₃ ) ₆ ] ³⁺ , cobalt-cyano complex [Co(CN) ₆ f, cobalt-thiocyanate complex [Co(SCN) ₄ ] ² \ cobalt-carbonyl complex [Co(CO) ₄ ]-, cobalt-nitrate Base complex [Co(N0 ₃ ) ₄ f, cobalt-nitroso complex [Co(N0 ₂ ) ₆ f or cobalt-butanedione oxime complex; wherein, cobalt-butanedione oxime complex and its derivatives The object is of the following structure:

Where L is 3⁄40 or CH ₃ CN; IC3⁄4H, N(CH ₃ ) ₂ or (COOC3⁄4 );

The nickel salt is a nickel halide, nickel sulfate, nickel nitrate, nickel carbonate, nickel oxalate, nickel acetate, nickel phosphate or chromic acid mirror;

The iron complex is an iron-cyano complex [Fe(CN) ₆ f, a ferrous-cyano complex [Fe(CN) ₆ ] ⁴ iron-thiocyanate complex Fe(SCN) ₃ , an iron-sulfur complex [Fe ₂ S ₂ (CO) ₆ ], iron-carbonyl complex Fe(CO) ₅ , iron-carbonyl complex Fe ₂ (CO) ₉ or iron-carbonyl complex Fe ₃ (CO) _{12 ;} The copper salt is copper halide, copper sulfate, copper nitrate, copper carbonate, copper oxalate, copper acetate, copper phosphate, copper chromate, copper pyrophosphate, copper cyanide, copper fatty acid, copper naphthenate, cuprous halide , cuprous sulfate, cuprous carbonate or cuprous acetate; the chromium salt is chromium halide, chromium sulfate, chromium nitrate, chromium carbonate, chromium oxalate, chromium acetate or chromium phosphate; the salt of the palladium is tetrachloropalladium Potassium acid, palladium halide, palladium sulfate, palladium nitrate or palladium acetate;

The salt of gold is gold halide or chloroauric acid;

The salt of the cerium is cerium halide or chloroantimonic acid;

The method according to claim 17 or 18, wherein the step 3) the concentration of the biomass derivative in the entire reaction system is lx 10 - ⁴ mol / L or 0.01% by mole.

22. The method according to claim 17, wherein the biomass derivative is methanol, ethanol, propanol, butanol, ethylene glycol, glycerol, glucose, sucrose, fructose, maltose, mannose. , ascorbic acid, L-proline or L-cysteine.

23. The system according to claim 18, wherein: the biomass derivative is triethanolamine, triethylamine, methanol, ethanol, propanol, butanol, ethylene glycol, glycerol, glucose, sucrose. , fructose, maltose or mannose.