WO2012174844A1 - Photocatalyseur à semi-conducteur pour la production d'hydrogène à partir de dérivés de biomasse par reformage photocatalytique, procédé de préparation et utilisation de celui-ci - Google Patents

Photocatalyseur à semi-conducteur pour la production d'hydrogène à partir de dérivés de biomasse par reformage photocatalytique, procédé de préparation et utilisation de celui-ci Download PDF

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WO2012174844A1
WO2012174844A1 PCT/CN2012/000064 CN2012000064W WO2012174844A1 WO 2012174844 A1 WO2012174844 A1 WO 2012174844A1 CN 2012000064 W CN2012000064 W CN 2012000064W WO 2012174844 A1 WO2012174844 A1 WO 2012174844A1
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salt
complex
cobalt
nickel
iron
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PCT/CN2012/000064
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Chinese (zh)
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吴骊珠
李治军
李成博
李旭兵
李嘉欣
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中国科学院理化技术研究所
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Priority claimed from CN2011101702652A external-priority patent/CN102335618B/zh
Priority claimed from CN201110308867.XA external-priority patent/CN103041829B/zh
Priority claimed from CN201110344439.2A external-priority patent/CN103084190B/zh
Application filed by 中国科学院理化技术研究所 filed Critical 中国科学院理化技术研究所
Publication of WO2012174844A1 publication Critical patent/WO2012174844A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/043—Sulfides with iron group metals or platinum group metals
    • B01J27/045—Platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
    • B01J27/049—Sulfides with chromium, molybdenum, tungsten or polonium with iron group metals or platinum group metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/057—Selenium or tellurium; Compounds thereof
    • B01J27/0573—Selenium; Compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/057—Selenium or tellurium; Compounds thereof
    • B01J27/0576—Tellurium; Compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds

Definitions

  • 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
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • ⁇ is a family element ⁇ family element or ⁇ is a family element ⁇ family element;
  • 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 %.
  • 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.
  • 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.
  • 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 .
  • the method for preparing the semiconductor photocatalysts M to NA X of the present invention comprises the following steps:
  • 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.
  • step 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.
  • biomass derivative is methanol, ethanol, propanol, butanol, ethylene glycol, glycerol, glucose, sucrose, fructose, maltose, mannose, ascorbic acid, L-valine or L-half Cystine.
  • 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:
  • 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;
  • 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;
  • the biomass derivative is triethanolamine, triethylamine, methanol, ethanol, propanol, butanol, ethylene glycol, glycerol, glucose, sucrose, fructose, maltose or mannose.
  • 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.
  • 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
  • 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:
  • 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
  • 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;
  • the present invention comprises a photocatalytic reforming biomass derivative comprising a semiconductor photocatalyst M ⁇ NA X And a system for preparing hydrogen,
  • 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;
  • ⁇ value is 3 ⁇ 10
  • UV and / or visible light irradiation conditions UV and / or visible light irradiation conditions.
  • biomass derivative is methanol, ethanol, propanol, butanol, ethylene glycol, glycerol, glucose, sucrose, fructose, maltose, mannose, ascorbic acid, L-valine or L-half Cystine.
  • 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 -
  • quantum dots composed of II ⁇ VI or III ⁇ V elements
  • the biomass derivative is triethanolamine, triethylamine, methanol, ethanol, propanol, butanol, ethylene glycol, glycerol, glucose, sucrose, fructose, maltose or mannose.
  • 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 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 elements include a composite structure quantum dot composed of one or two of InP and InAs.
  • 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,
  • 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.
  • 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 -
  • 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 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 halide or chloroauric acid
  • the silver salt is silver halide, silver sulfate, silver nitrate or silver acetate
  • 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
  • the salt of ruthenium is pentacarbonylphosphonium chloride or pentacarbonylpentadium bromide
  • 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.
  • 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 -
  • the method of adjusting the pH is: adding 1 mol/L NaOH or 1 mol/L HCL to the mixed solution B.
  • step 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 -
  • 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;
  • the biomass derivative is triethanolamine, triethylamine, methanol, ethanol, propanol, butanol, ethylene glycol, glycerol, glucose, sucrose, fructose, maltose or mannose.
  • 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;
  • 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.
  • 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 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
  • 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:
  • L is 3 ⁇ 40 or CH 3 CN; RJ3 ⁇ 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 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 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 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.
  • 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 halide or chloroauric acid
  • the silver salt is silver halide, silver sulfate, silver nitrate or silver acetate
  • the fierce salt 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
  • 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.
  • reaction conditions such as - concentration, temperature, pH, etc.
  • H 2 is always one of the important products of the reaction.
  • 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.
  • FIG. 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.
  • FIG. 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. ⁇ 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;
  • Example 12 is the same as in Example 109: l . Ti0 2 ; 2. Ti0 2 and CdSe quantum dots after adsorption; 3. ⁇ 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;
  • Example 13 is in Example 110: l . Ti0 2 ; 2. ⁇ 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;
  • Example 14 is the following in Example 111: 1. ⁇ 0 2 ; 2. ⁇ 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;
  • 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. ⁇ 0 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. ⁇ 0 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. ⁇ 0 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;
  • Example 17 is the same as in Example 114: 1. ⁇ 0 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. ⁇ 0 2 and CdSe quantum dots after adsorption of various transition metal salts; 4. ⁇ 0 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;
  • P-25 type Ti0 2 exhibits a typical Ti0 2 ultraviolet absorption characteristic.
  • CdSe quantum dots are adsorbed with ⁇ 0 2
  • the system simultaneously exhibits P-25 type ⁇ 0 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.
  • CdSe/CdS quantum dot solution concentration IxlO-'g/L 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.
  • aqueous nickel dichloride solution original Concentration 4.2xl (T 3 mol / L, containing 0.5 mg of nickel dichloride hexahydrate), 41 ⁇ ethanol (
  • 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 ⁇ - i-mg
  • CdSe/CdS quantum dot solution concentration 2xlO-L 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.
  • a 500 W high pressure mercury lamp 400 nm long pass glass filter
  • the hydrogen production is 87 ⁇ — ⁇ mg ⁇
  • 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 hydrogen production is 81 ⁇ — ⁇ mg—
  • CdSe/CdS quantum dot solution concentration 2xlO-L 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 amount of hydrogen produced is Q moH ⁇ mg - Example 5:
  • CdSe/CdS quantum dot solution concentration 2xlO- ! g/L 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.
  • nickel nitrate solution original concentration 4.2xlO_ 3
  • 4ml ethanol original concentration 17.16mol/L, 20V
  • the amount of hydrogen produced is 102 ⁇ 1 ⁇ 1 -1 mg.
  • CdSe/CdS quantum dot solution concentration 2xlO' ! g/L 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 amount of hydrogen produced is K ⁇ mol'h mg—
  • 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 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 ⁇
  • the amount of hydrogen produced is SS moHi mg ⁇
  • CdSe/CdS quantum dot solution concentration 2xl0-'g/L 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 hydrogen production is 21 ⁇ - ⁇ mg
  • 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.
  • lxl T 4 g/L of core-shell cadmium selenide/cadmium sulfide quantum dots (CdSe/CdS quantum dot solution concentration Zx lO-ig/L)
  • the reactor was evacuated and 500 W high pressure mercury lamp with a short (400 nm in Through-glass filter) Irradiate the tube.
  • the amount of hydrogen produced is 3 ⁇ — ⁇ mg— '.
  • the amount of hydrogen produced is ⁇ ⁇ 1 ⁇ ] ⁇ —
  • 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 ⁇ 10 ⁇ 4 mol/L, glucose of 0.1 mol/L in the whole reaction system, pH 8 is adjusted, and it is sealed nitrogen.
  • the test tube was irradiated with a 500 W high pressure mercury lamp (400 nm long pass type glass filter).
  • the amount of hydrogen produced is SQ mol'h mg—
  • 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 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 1 was repeated except that the doping compound was nickel oxalate and the biomass derivative was propanol.
  • Example 1 was repeated except that the doping compound was nickel acetate and the biomass derivative was butanol.
  • Example 1 was repeated except that the doping compound was nickel phosphate.
  • Example 1 was repeated except that the doping compound was a nickel-ammonia complex [Ni(NH 3 ) 6 ] 2+ .
  • 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 1 was repeated except that the doping compound was nickel tetracarbonyl Ni(CO) 4 .
  • Example 1 was repeated except that the doping compound was a nickel-ethyl complex (C 2 H 5 ) 2 Ni.
  • Example 24 was repeated except that the doping compound was a nickel-ethyl complex (C 2 H 5 ) 2 Ni.
  • Example 1 was repeated except that the doping compound was ferric chloride.
  • Example 1 was repeated except that the doping compound was ferrous chloride.
  • Example 1 was repeated except that the doping compound was ferrous bromide.
  • Example 1 was repeated except that the doping compound was ferrous sulfate.
  • Example 1 was repeated except that the doping compound was iron fluoride.
  • Example 1 was repeated except that the doping compound was iron bromide.
  • Example 1 was repeated except that the doping compound was iron iodide.
  • Example 1 was repeated except that the doping compound was iron sulfate.
  • Example 1 was repeated except that the doping compound was ferric nitrate.
  • Example 1 was repeated except that the doping compound was iron carbonate.
  • Example 1 was repeated except that the doping compound was iron oxalate.
  • Example 1 was repeated except that the doping compound was iron acetate.
  • Example 1 was repeated except that the doping compound was iron phosphate.
  • Example 1 was repeated except that the doping compound was iron chromate.
  • Example 1 was repeated except that the doping compound was ferrous fluoride.
  • Example 1 was repeated except that the doping compound was ferrous iodide.
  • Example 1 was repeated except that the doping compound was ferrous nitrate.
  • Example 1 was repeated except that the doping compound was ferrous carbonate.
  • 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.
  • the repeated examples differ only in that the doping compound is ferrous phosphate.
  • the repeated examples differ only in that the doping compound is ferrous chromite.
  • the repeated examples differ only in that the doping compound is ammonium ferrous sulfate.
  • the repeated examples differ only in that the doping compound is ammonium ferrous sulfate.
  • the repeated examples differ only in that the doping compound is a ferrous-cyano complex [Fe(CN) 6 ] 4 - Example 50:
  • Example 51 The repeated examples differ only in that the doping compound is an iron-thiocyanate complex Fe(SCN) 3 .
  • the doping compound is an iron-thiocyanate complex Fe(SCN) 3 .
  • Example 52 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 nickel nitrate.
  • the repeated examples differ only in that the doping compound is nickel carbonate.
  • the repeated examples differ only in that the murky compound is nickel chromite.
  • the repeated examples differ only in that the doping compound is nickel fluoride.
  • the repeated examples differ only in that the doping compound is nickel iodide.
  • the repeated examples are different only in that the doping compound is cobalt difluoride.
  • the repeated examples differ only in that the doping compound is cobalt bromide.
  • the repeated examples are different only in that the doping compound is cobalt iodide.
  • the repeated examples differ only in that the doping compound is cobalt carbonate.
  • the repeated examples differ only in that the doping compound is cobalt oxalate.
  • the repeated examples are different only in that the doping compound is cobalt acetate.
  • Example 66 The repeated examples differ only in that the heterogeneous compound is cobalt phosphate.
  • Example 66 The repeated examples differ only in that the heterogeneous compound is cobalt phosphate.
  • Example 1 was repeated except that the doping compound was a cobalt-ammonia complex [Co(NH 3 ) 6 ] 3+ .
  • Example 1 was repeated except that the doping compound was a cobalt-cyano complex [Co(CN) 6 ] 4 -.
  • Example 1 was repeated except that the doping compound was a cobalt-thiocyanate complex [Co(SCN) 4 f.
  • Example 1 was repeated except that the doping compound was a cobalt-carbonyl complex [c 0 (co) 4 r.
  • Example 1 was repeated except that the doping compound was a cobalt-nitro complex [Co(N0 3 ) 4 f.
  • Example 1 was repeated except that the doping compound was a cobalt-nitroso complex [Co(N0 2 ) 6 ] 3 -.
  • Example 72
  • the amount of hydrogen produced is ⁇ ⁇
  • Example 72 was repeated except that the doping compound was a cobalt-butanedione oxime complex having the following structure:
  • Example 74 Example 72 was repeated except that the doping compound was a cobalt-butanedione oxime complex having the following structure:
  • Example 72 was repeated except that the cryptic compound was a cobalt-butanedione oxime complex having the following structure:
  • Example 72 was repeated except that the doping compound was a cobalt-butanedione oxime complex having the following structure:
  • Example 72 was repeated except that the doping compound was a cobalt-butanedione oxime complex having the following structure:
  • Example 78 - Example 72 was repeated except that the doping compound was a cobalt-butanedione oxime complex having the following structure:
  • R COOCH 3 .
  • Example 72 was repeated except that the cobalt-butanedione oxime complex is as follows:
  • Example 72 was repeated except that the cobalt-butanedione oxime complex is as follows:
  • Example 72 was repeated except that the cobalt-butanedione oxime complex is as follows:
  • Example 72 was repeated except that the doping compound was a cobalt-butanedione oxime complex having the following structure:
  • Example 72 was repeated except that the doping compound was a cobalt-butanedione oxime complex having the following structure:
  • Example 72 was repeated except that the doping compound was a cobalt-butanedione oxime complex having the following structure:
  • Example 85 Example 1 was repeated except that the doping compound was chromium dichloride.
  • Example 86 Example 86
  • Example 1 was repeated except that the doping compound was chromium trichloride.
  • Example 1 was repeated except that the dopant compound was chromium dibromide.
  • Example 88 is a group consisting of chromium dibromide.
  • 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 1 was repeated except that the dopant compound was chromium carbonate.
  • Example 1 was repeated except that the doping compound was chromium oxalate.
  • Example 1 was repeated except that the doping compound was chromium acetate.
  • 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).
  • 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.
  • a photocatalytic system comprising a composite semiconductor photocatalyst for reforming a biomass derivative and preparing hydrogen, comprising the steps of:
  • the hydrogen production rate was 357 ⁇ .
  • a photocatalytic system comprising a composite semiconductor photocatalyst for reforming a biomass derivative and preparing hydrogen, comprising the steps of:
  • the hydrogen production rate is 23441 ⁇ )1 ⁇ .
  • a photocatalytic system comprising a composite semiconductor photocatalyst for reforming a biomass derivative and preparing hydrogen, comprising the steps of:
  • the hydrogen production rate is 286 ⁇ -
  • a photocatalytic system comprising a composite semiconductor photocatalyst for reforming a biomass derivative and preparing hydrogen, comprising the steps of:
  • the hydrogen production rate is 265 ⁇ 1 ⁇ 1 ⁇ —
  • a photocatalytic system comprising a composite semiconductor photocatalyst for reforming a biomass derivative and preparing hydrogen, comprising the steps of:
  • the hydrogen production rate is 323 ⁇ 1 ⁇ 1 ⁇ —
  • a photocatalytic system comprising a composite semiconductor photocatalyst for reforming a biomass derivative and preparing hydrogen, comprising the steps of:
  • the hydrogen production rate is 3494 ⁇ 101 ⁇ .
  • a photocatalytic system comprising a composite semiconductor photocatalyst for reforming a biomass derivative and preparing hydrogen, comprising the steps of:
  • 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 hydrogen production rate is 69 ⁇ 0 ⁇ —
  • a photocatalytic system comprising a composite semiconductor photocatalyst for reforming a biomass derivative and preparing hydrogen, comprising the steps of:
  • the hydrogen production rate is 87 ⁇ 0 ⁇ —
  • a photocatalytic system comprising a composite semiconductor photocatalyst for reforming a biomass derivative and preparing hydrogen: comprising the following steps:
  • the hydrogen production rate is 351 ⁇ -
  • a photocatalytic system comprising a composite semiconductor photocatalyst for reforming a biomass derivative and preparing hydrogen, comprising the steps of:
  • the hydrogen production rate is 31 ⁇ 0 ⁇ —
  • a photocatalytic system comprising a composite semiconductor photocatalyst for reforming a biomass derivative and preparing hydrogen, comprising the steps of:
  • the hydrogen production rate is 87 ⁇ - Example 105:
  • a photocatalytic system comprising a composite semiconductor photocatalyst for reforming a biomass derivative and preparing hydrogen, comprising the steps of:
  • the hydrogen production rate is 18 ⁇ 0 1 ⁇ 1 ⁇ —
  • a photocatalytic system comprising a composite semiconductor photocatalyst for reforming a biomass derivative and preparing hydrogen, comprising the steps of:
  • the rate of hydrogen production is ⁇
  • a photocatalytic system comprising a composite semiconductor photocatalyst for reforming a biomass derivative and preparing hydrogen, comprising the steps of:
  • the hydrogen production rate is 189 ⁇ -
  • a photocatalytic system comprising a composite semiconductor photocatalyst for reforming a biomass derivative and preparing hydrogen, comprising the steps of:
  • the hydrogen generated in the reaction was detected by gas chromatography (TCD thermal conductivity detector), and the hydrogen production rate was 56 ⁇ 1 ⁇ 1 ⁇ " 1 °.
  • 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
  • a photocatalytic system comprising a composite semiconductor photocatalyst for reforming a biomass derivative and preparing hydrogen, comprising the steps of:
  • the hydrogen gas generated in the reaction was detected by gas chromatography (TCD thermal conductivity detector), and the hydrogen production rate was 71 ⁇ 1 ⁇ 1 ⁇ .
  • a photocatalytic system comprising a composite semiconductor photocatalyst for reforming a biomass derivative and preparing hydrogen, comprising the steps of:
  • the hydrogen gas generated in the reaction was detected by gas chromatography (TCD thermal conductivity detector), and the hydrogen production rate was 101 ⁇ 1 ⁇ 1 -1 .
  • a photocatalytic system comprising a composite semiconductor photocatalyst for reforming a biomass derivative and preparing hydrogen, comprising the steps of:
  • the hydrogen produced in the reaction was detected by gas chromatography (TCD thermal conductivity detector), and the hydrogen production rate was 218 ⁇ 1 ⁇ 1 ⁇ .
  • a photocatalytic system comprising a composite semiconductor photocatalyst for reforming a biomass derivative and preparing hydrogen, comprising the steps of:
  • the hydrogen gas generated in the reaction was detected by gas chromatography (TCD thermal conductivity detector), and the hydrogen production rate was 20 ⁇ 1 ⁇ 1 ⁇ " 1 .
  • a photocatalytic system comprising a composite semiconductor photocatalyst for reforming a biomass derivative and preparing hydrogen, comprising the following steps:
  • a photocatalytic system comprising a composite semiconductor photocatalyst for reforming a biomass derivative and preparing hydrogen, comprising the steps of:
  • the hydrogen gas generated in the reaction was detected by gas chromatography (TCD thermal conductivity detector), and the hydrogen production rate was 3 ⁇ 1 ⁇ ] ⁇ -1 .
  • a photocatalytic system comprising a composite semiconductor photocatalyst for reforming a biomass derivative and preparing hydrogen, comprising the steps of:
  • CdSe quantum dots stock concentration of cadmium ion concentration 1 x 10- 3
  • the hydrogen gas generated in the reaction was detected by gas chromatography (TCD thermal conductivity detector), and the hydrogen production rate was 2 ⁇ 1 ⁇ 1 " 1 .
  • a photocatalytic system comprising a composite semiconductor photocatalyst for reforming a biomass derivative and preparing hydrogen, comprising the steps of:
  • the hydrogen gas generated in the reaction was detected by gas chromatography (TCD thermal conductivity detector), and the hydrogen production rate was 6 ⁇ 1 ⁇ 1 ⁇ -1 .
  • the hydrogen gas generated in the reaction was detected by gas chromatography (TCD thermal conductivity detector), and the hydrogen production rate was 7 ⁇ 1 ⁇ 1 -1 .
  • the hydrogen gas generated in the reaction was detected by gas chromatography (TCD thermal conductivity detector), and the hydrogen production rate was 0.5 ⁇ ⁇ 1 ⁇ 1 ⁇ .
  • a photocatalytic system comprising a composite semiconductor photocatalyst for reforming a biomass derivative and preparing hydrogen, comprising the steps of:
  • CdS quantum dot solution concentration is cadmium
  • 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.
  • the hydrogen gas generated in the reaction was detected by gas chromatography (TCD thermal conductivity detector), and the hydrogen production rate was 1.8 ⁇ 1 ⁇ 1 ⁇ -1 .
  • CdTe cadmium telluride quantum dots
  • 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).

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Abstract

La présente invention concerne un photocatalyseur à semi-conducteur pour la production d'hydrogène à partir de dérivés de biomasse par reformage photocatalytique. Ledit photocatalyseur à semi-conducteur présente un rapport de composition d'atome de M~N-Ax, dans lequel M~N sont des éléments de groupe II-VI ou des éléments de groupe III-V, A est un ou plusieurs des éléments suivants : le cobalt, le nickel, le fer, le cuivre, le chrome, le palladium, le platine, le ruthénium, le rhodium, l'iridium ou l'argent, et 0,02 % ≤ x ≤ 1,0 %. Le photocatalyseur à semi-conducteur est préparé in situ à partir de points quantiques par un procédé de photoréaction sans calcination.
PCT/CN2012/000064 2011-06-23 2012-01-13 Photocatalyseur à semi-conducteur pour la production d'hydrogène à partir de dérivés de biomasse par reformage photocatalytique, procédé de préparation et utilisation de celui-ci WO2012174844A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
CN201110170265.2 2011-06-23
CN2011101702652A CN102335618B (zh) 2011-06-23 2011-06-23 半导体催化剂及其制备方法、包含半导体催化剂的催化制氢体系及其制氢方法
CN201110308867.XA CN103041829B (zh) 2011-10-12 2011-10-12 一种光催化重整生物质及其衍生物制氢的半导体光催化剂及制备与应用
CN201110308867.X 2011-10-12
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