CN116212918A - CABI@C 3 N 4 Heterojunction catalyst and preparation method and application thereof - Google Patents
CABI@C 3 N 4 Heterojunction catalyst and preparation method and application thereof Download PDFInfo
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- 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
- B01J27/24—Nitrogen compounds
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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
- 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
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- 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
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a CABI@C 3 N 4 Heterojunction catalyst and preparation method and application thereof, the preparation method comprises the following steps: will g-C 3 N 4 The nanotube powder is dispersed in a first solvent by ultrasonic to form g-C 3 N 4 A dispersion; csI, agI and BiI 3 Dissolving in a second solvent and vigorously stirring to obtain Cs 2 AgBiI 6 A precursor solution; cs is processed by 2 AgBiI 6 Dripping the precursor solution into g-C 3 N 4 Recrystallizing the dispersion liquid, vigorously stirring, and inducing instant supersaturation to form precipitate to obtain orange turbid liquid; centrifuging the orange turbid liquid, and removing supernatant to obtain a lower red precipitate; drying the precipitate to obtain CABI@C 3 N 4 Heterojunction catalysts. The heterojunction material has the advantages of no toxicity, excellent photoelectric response, strong light absorption capacity, wide light response range capacity,Visible light response, adjustable electronic structure, high separation efficiency of photon-generated carriers and the like.
Description
Technical Field
The invention relates to the technical field of perovskite catalysts, in particular to a CABI@C 3 N 4 Heterojunction catalyst and preparation method and application thereof.
Background
The energy demand and the environmental pollution thereof are two urgent problems facing the life and industrialization of human beings at present. It is estimated that by the end of this century, global energy demand will deplete severely dependent non-renewable energy sources (coal, oil and gas). In addition, greenhouse gases generated by burning these conventional energy sources, as well as harmful gases generated by impurities in fossil fuels, are important factors that cause current environmental problems. Accordingly, a great deal of research is being conducted to develop renewable energy sources to circumvent energy crisis while improving environmental problems. Among the alternative energy sources, solar energy is most attractive with hydrogen energy because the sun provides free, renewable, abundant and sustainable energy, the energy of sunlight reaching the earth's surface is 10000 times that we consume currently, and solar energy is expected to meet a significant part of the demands of global energy consumption in the future; meanwhile, the hydrogen energy has the advantages of cleanness, regeneration, high combustion, high heat value, low energy consumption, convenient storage and transportation and the like. One possible way to utilize solar energy is to convert it into chemical energy. Hydrogen can be extracted from water using photocatalysis, i.e., light is used to excite or improve chemical reactions. Therefore, it is important to develop efficient, stable, low cost photocatalytic hydrogen evolution catalysts that are oriented towards future sustainable development. Because of rich elements and good photocatalytic performance, the photocatalyst is expected to be cheaper and more suitable for application, and a series of high-efficiency photocatalytic materials, such as TiO, are discovered 2 、CdS、AgPO 4 、BiVO 4 Ag/AgCl, quantum dots, and metal-free catalysts, including carbon nitride, boron carbide, p-doped graphene, phosphorus, and organic polymers, among others. Although many photocatalysts are being developed and studied, most are still far from being industrially used due to their low conversion efficiency. In view of the increasing demand for clean energy and environmental remediation, an effective photocatalyst shouldThe material has the advantages of good energy band structure, large surface area, high crystallinity, no toxicity and safety, and can be produced and applied on a large scale.
Among the numerous semiconductor photocatalyst materials, perovskite and its derivatives have received a great deal of attention as photocatalytic materials due to their highly customizable structure and physicochemical properties. Because of the major contribution of the O-2p orbital to the density of states (DOS) surrounding the perovskite oxide VBM, fixing its VBM level around +3.0V, most perovskite oxide-based photocatalysts acquire very little visible light due to their wide band gap. Thus, in the past decade, researchers have investigated non-oxide perovskites, such as halide perovskites, which exhibit excellent photovoltaic properties. The general formula for halide perovskite is ABX 3 Wherein A is a monovalent cation, e.g. MA, FA, cs + Or Rb + The method comprises the steps of carrying out a first treatment on the surface of the B is a divalent metal ion, which may be Pb 2+ Or Sn (Sn) 2+ The method comprises the steps of carrying out a first treatment on the surface of the X is a halide ion (Cl, br and I).
The halide perovskite has the advantages of low synthesis cost, wide band gap adjustability, long carrier life, long diffusion distance, large absorption coefficient, good charge mobility and the like, and has good application prospects of solar cells, LEDs, lasers and photodetectors. At the same time, halide perovskites also have many desirable advantages in terms of photocatalysis, such as narrow band gap, slow electron-hole recombination, and fast carrier transport. Also, most halide perovskites have CBM's generally more negative than H due to the potential of the P orbital (X-3P) than the oxide (O-2P) 2 /H + More negative so as to drive more H 2 Is generated. However, only a few studies have reported the use of halide perovskite for the photocatalytic decomposition of aqueous hydrogen. Moreover, there are also some limitations to the field of photocatalytic hydrogen production of halide perovskite, such as that most of halide perovskite are unstable in water, contain toxic elemental lead, and the like.
Over the past few years, halide perovskite (CsPbX 3 ) Has remarkable charge transport capability in solar cells and therefore develops more rapidly in the field of photocatalysis than traditional oxide perovskites. However, csPbX 3 Is still in existenceThe following problems are solved:
(1) Unstable under illumination and is easy to be degraded by light;
(2) Water instability: instability under humid or polar solvent conditions, moisture and oxygen can induce degradation of the perovskite;
(3) Lead (Pb) 2+ ) Is a major bottleneck for halide perovskite: lead is an effective human and environmental toxin, and even under extremely low exposure conditions, it can cause serious health problems including nerve injury, renal failure, and impaired brain development;
(4) The problem of rapid electron-hole pair recombination still exists, and the charge separation and transfer efficiency is not high enough;
(5) The redox reaction proceeds with an insufficient number of active sites and the photo-reduction efficiency is low.
Thus, there would be a significant advance in the art to find low cost, non-toxic materials that mimic the optoelectronic properties of lead halide perovskite. Double perovskite (A) 2 BB’X 6 ) Proved to be a very universal framework which can accommodate the B and B' sites from 1 + To 7 + Is in an oxidized state. With typical ABX 3 Perovskite phase A 2 BB’X 6 Double perovskite greatly increases the diversity of cations that can occupy the B/B' sites in the perovskite lattice and allows greater modification and control of the electronic structure. Therefore, the double perovskite structure can effectively solve the toxicity problem of the traditional lead halide perovskite. Similarly, g-C 3 N 4 As a nontoxic and low-cost organic semiconductor material, the material has excellent visible light response capability, but still has the problems of easy recombination of photogenerated carriers and low photocatalytic activity efficiency.
Disclosure of Invention
In order to solve the technical problems, the invention provides a lead-free double perovskite@carbon nitride (inorganic/organic) heterojunction nanotube catalyst (Cs 2 AgBiI 6 @g-C 3 N 4 ，CABI@C 3 N 4 ) The method is applied to the photocatalytic decomposition of the water to produce the hydrogen for the first time. The heterojunction material has the advantages of no toxicity, excellent photoelectric response, strong light absorption capacity and wide applicationThe light response range capability, the visible light response, the adjustable electronic structure, the high photoproduction carrier separation efficiency and the like, and simultaneously Cs 2 AgBiI 6 And g-C 3 N 4 The energy band structure of the nanotube is well matched with the oxidation-reduction potential of water to HER and OER respectively, and has good light stability and water stability. The heterojunction photocatalyst material can be further applied to other fields of photocatalysis.
In order to achieve the technical effects, the invention provides the following technical scheme:
CABI@C 3 N 4 The preparation method of the heterojunction catalyst comprises the following steps: (1) Will g-C 3 N 4 The nanotube powder is dispersed in a first solvent by ultrasonic to form g-C 3 N 4 A dispersion; (2) CsI, agI and BiI 3 Dissolving in a second solvent and vigorously stirring to obtain Cs 2 AgBiI 6 A precursor solution; (3) Cs is processed by 2 AgBiI 6 Dripping the precursor solution into g-C 3 N 4 Recrystallizing the dispersion liquid, vigorously stirring, and inducing instant supersaturation to form precipitate to obtain orange turbid liquid; (4) Centrifuging the orange turbid liquid, and removing supernatant to obtain a lower red precipitate; drying the precipitate to obtain CABI@C 3 N 4 Heterojunction catalysts.
Further technical proposal is that the g-C 3 N 4 The preparation method of the nanotube powder comprises the following steps: (1) Dissolving melamine in deionized water and stirring uniformly to obtain a first solution, heating the first solution in a polytetrafluoroethylene reaction kettle for reaction, cooling to room temperature after the reaction is finished, centrifuging the reaction solution, and drying the centrifuged product to obtain g-C 3 N 4 Precursor powder of nanotubes; (2) Will g-C 3 N 4 Heating the precursor powder of the nanotube, and grinding to obtain g-C 3 N 4 Nanotube powder.
A further technical scheme is that the g-C in the step (1) 3 N 4 g-C in dispersion 3 N 4 The mass fraction of the nanotube powder is 10-50wt%, the ultrasonic time is 5-10 min, and the first solvent is selected from any one of isopropanol, toluene and hexaneA kind of module is assembled in the module and the module is assembled in the module.
The further technical proposal is that CsI, agI and BiI in the step (2) 3 The molar ratio of the solvent to the solvent is 2:1:1, the second solvent is dimethyl argon sulfone or dimethyl formamide, and the vigorous stirring time is 10-30 min.
The further technical proposal is that in the step (3), cs 2 AgBiI 6 Precursor solution and g-C 3 N 4 The volume ratio of the dispersion liquid is 1:25, and the intense stirring time is 10-30 min.
The further technical proposal is that the rotational speed of the centrifugation in the step (4) is 5000-8000 r/min, the time is 3-5 min, the drying temperature is 80-100 ℃, and the drying time is 8-12 h.
The further technical proposal is that in the step (1), the mass volume ratio of melamine to deionized water is 1g to 20mL, the stirring time is 1-2 hours, the heating reaction temperature is 200-220 ℃, and the heating reaction time is 10-14 hours.
The further technical scheme is that in the step (1), the reaction solution is transferred into a centrifuge tube for centrifugation, deionized water and absolute ethyl alcohol are sequentially used for centrifugation for 3 times respectively, the rotational speed of the centrifuge is set to 8000-11000 r/min, and the centrifugation time is set to 3-8 min; and drying the centrifuged product at 60-100 ℃ for 8-12 h.
The further technical proposal is that the heating temperature in the step (2) is 520-550 ℃, the heating time is 3-4 h, and the heating rate is 2-5 ℃/min.
The invention also provides the CABI@C prepared by the preparation method 3 N 4 Heterojunction catalysts.
The invention also provides a CABI@C 3 N 4 The heterojunction catalyst is applied to the field of hydrogen production by photocatalytic decomposition of water.
The invention is nontoxic Bi 3+ Incorporation of ABX as B site cation 3 In the perovskite framework; and the bismuth-based halide perovskite has good resistance to humidity, oxygen and light, and can exhibit excellent photocatalytic activity. To accommodate trivalent Bi in perovskite lattices 3+ A monovalent metal is then introduced to produce an ordered double perovskite structure: a is that I 2 B I Bi III X 6 . Ag according to radius ratio rule of filling in ionic solid + Having suitable dimensions to support octahedral coordination of iodide or bromide in perovskite lattices to build Cs 2 AgBiX 6 。Ag + And Bi (Bi) 3+ Ions occupy B and B' sites in the ordered double perovskite crystal lattice respectively, and the doping of Ag leads to the structural transformation from a two-dimensional layered structure to a rock salt double perovskite structure, so that the rock salt double perovskite crystal lattice has obvious absorption coefficient, longer electron-hole recombination service life and light and humidity stability. And the Ag 4d orbit can improve VBM and lead Cs to be 2 AgBiX 6 Exhibiting a narrower band gap, higher carrier mobility, and lower exciton binding energy. According to the invention, I element optimization is introduced into the X position: the electron absorption spectrum is widened from Cl to I, and the light absorption range is enhanced. This is because as the atomic weight increases, the electronegativity of the element becomes weaker and the covalent interactions in the bond with the metal ion B are enhanced. I electronegativity is lower than Br, resulting in a decrease in its bandgap, which in turn affects the position of VBM and CBM. Related studies indicate that Cs 2 AgBiI 6 Ratio Cs 2 AgBiX 6 (x= Cl, clBr, br, brI) has a more suitable band structure, and the CBM is more negative and favors the reduction reaction. CABI and g-C 3 N 4 The heterojunction between the two substrates inhibits the recombination of photo-generated charges, thereby remarkably improving the activity of the photocatalytic reduction reaction. g-C 3 N 4 And inorganic nanoparticle material Cs with unique optical properties 2 AgBiI 6 In situ self-assembly, g-C 3 N 4 The dispersibility and stability of CABI can be improved. Cs (cells) 2 AgBiI 6 (CABI) has not been reported in the prior art for the relevant application of photocatalytic hydrogen production.
Compared with the prior art, the invention has the following beneficial effects: the invention selects the all-inorganic dihalide lead-free perovskite material (Cs) which can respond to visible light 2 AgBiI 6 ) And an organic nonmetallic semiconductor material (g-C 3 N 4 ) And synthesizes a lead-free double perovskite@carbon nitride (inorganic/organic) heterojunction nanotube catalyst (Cs for the first time 2 AgBiI 6 @g-C 3 N 4 ，CABI@C 3 N 4 ) The method is applied to the photocatalytic decomposition of the water to produce the hydrogen for the first time. The heterojunction material has the advantages of no toxicity, excellent photoelectric response, strong light absorption capacity, wide light response range capacity, visible light response, adjustable electronic structure, high photogenerated carrier separation efficiency and the like, and meanwhile, cs 2 AgBiI 6 And g-C 3 N 4 The energy band structure of the nanotube is well matched with the oxidation-reduction potential of water to HER and OER respectively, and has good light stability and water stability. The heterojunction photocatalyst material can be further applied to other fields of photocatalysis.
Drawings
FIG. 1 is XRD patterns of comparative examples one, two and example one;
FIG. 2 is a graph showing diffuse reflection spectra of ultraviolet-visible light of comparative examples one, two and example one;
FIG. 3 shows the catalysts (. Alpha.hν) for comparative example one, comparative example two and example one 1/2 A graph of the energy band gap energy (hν);
FIG. 4 is a graph of CABI@C 3 N 4 A heterojunction energy band structure diagram of (2);
FIG. 5 is an SEM image of comparative examples one and two;
FIG. 6 is a photoluminescence spectrum of a comparative example I and an example I;
FIG. 7 is a photoluminescence spectrum of the second comparative example and the first example;
FIG. 8 is a graph of TRPL time resolved fluorescence spectra of comparative examples one, two and example one;
fig. 9 is a graph showing the hydrogen production rate of photocatalytic-decomposed water for comparative examples one, two and examples one to six.
Detailed Description
The invention is further illustrated by the following examples, which are for illustrative purposes only and do not limit the scope of the invention. The test methods in the following examples, in which specific conditions are not noted, generally follow conventional conditions.
Comparative example one:
2g of melamine is taken and dissolved in 40mL of deionized water, and stirring is continued for 2 hours at room temperature; transferring the solution into a 100mL polytetrafluoroethylene reaction kettle,and reacting for 12 hours at 200 ℃; after the reaction is finished and naturally cooled to room temperature, transferring the solution into a centrifuge tube for centrifugation, and sequentially and respectively centrifuging with deionized water and absolute ethyl alcohol for 3 times, wherein the rotation speed of the centrifuge is set to 8000r/min, and the centrifugation time is set to 5min; drying the centrifuged product at 60deg.C for 12h to obtain g-C 3 N 4 Precursor powders for nanotubes. Will g-C 3 N 4 The nanotube precursor powder is placed in a crucible with a cover, the crucible is placed in a muffle furnace, the temperature is set to 550 ℃, the heating time is 240min, and the heating rate is 2 ℃/min; after the muffle furnace is completely cooled to room temperature, opening the muffle furnace, collecting the product in the crucible, and fully grinding to obtain g-C 3 N 4 Nanotube powder.
Comparative example two:
0.0520g CsI (0.2 mmol), 0.0235g AgI (0.1 mmol) and 0.0590g BiI were weighed out separately 3 (0.1 mmol) in 5mL of dimethyl argon sulfone (DMSO) (or Dimethylformamide (DMF)) and vigorously stirred for 30min to give clear Cs 2 AgBiI 6 (CABI) precursor solution. Every 200 mu L of precursor liquid is dripped into 5mL of isopropanol (or toluene and hexane) to recrystallize, and the mixture is vigorously stirred for 10min, so that instant supersaturation is induced to form a precipitate, and an orange turbid liquid is obtained. Centrifuging the orange solution at 8000r/min for 5min, and removing supernatant to obtain lower-layer orange precipitate; drying the precipitate at 80 ℃ overnight to obtain the CABI nanocrystalline.
Embodiment one:
weighing 0.0054g g-C obtained in comparative example one 3 N 4 The nanotube powder is ultrasonically dispersed in 5mL of isopropanol and sonicated for 5min to form g-C 3 N 4 A dispersion; 0.0520g CsI (0.2 mmol), 0.0235g AgI (0.1 mmol) and 0.0590g BiI were weighed out separately 3 (0.1 mmol) was dissolved in 5mL of dimethyl argon sulfone (DMSO) and vigorously stirred for 30min to give Cs 2 AgBiI 6 (CABI) precursor solution. Every 200 mu L of precursor liquid is dripped into 5mL g-C 3 N 4 Recrystallizing the dispersion liquid, and vigorously stirring for 30min, and inducing instant supersaturation to form precipitate to obtain orange turbid liquid. The orange solution was subjected toCentrifuging at 8000r/min for 3min, and removing supernatant to obtain lower red precipitate; drying the precipitate at 80deg.C overnight to obtain 50wt% CABI@C 3 N 4 And a heterojunction. The 50wt% CABI@C 3 N 4 The heterojunction acts directly as a photocatalyst material.
Embodiment two:
weighing 0.0108g g-C obtained in comparative example one 3 N 4 The nanotube powder was sonicated in 5mL hexane for 10min to form g-C 3 N 4 A dispersion; 0.0520g CsI (0.2 mmol), 0.0235g AgI (0.1 mmol) and 0.0590g BiI were weighed out separately 3 (0.1 mmol) was dissolved in 5mL Dimethylformamide (DMF) and vigorously stirred for 20min to give Cs 2 AgBiI 6 (CABI) precursor solution. Every 200 mu L of precursor liquid is dripped into 5mL g-C 3 N 4 Recrystallizing the dispersion liquid, and vigorously stirring for 20min to induce instant supersaturation to form precipitate, thus obtaining orange turbid liquid. Centrifuging the orange solution at a rotation speed of 5000r/min for 5min, and removing the supernatant to obtain a lower red precipitate; drying the precipitate at 80deg.C overnight to obtain 33wt% CABI@C 3 N 4 And a heterojunction. The 33wt% of CABI@C 3 N 4 The heterojunction acts directly as a photocatalyst material.
Embodiment III:
weighing 0.0054g g-C obtained in comparative example one 3 N 4 The nanotube powder was sonicated in 5mL hexane for 8min to form g-C 3 N 4 A dispersion; 0.0520g CsI (0.2 mmol), 0.0235g AgI (0.1 mmol) and 0.0590g BiI were weighed out separately 3 (0.1 mmol) was dissolved in 5mL of dimethyl argon sulfone (DMSO) and vigorously stirred for 10min to give Cs 2 AgBiI 6 (CABI) precursor solution. Every 200 mu L of precursor liquid is dripped into 5mL g-C 3 N 4 Recrystallizing the dispersion liquid, and vigorously stirring for 10min to induce instant supersaturation to form precipitate, thus obtaining orange turbid liquid. Centrifuging the orange solution at 6000r/min for 4min, and removing the supernatant to obtain a lower red precipitate; drying the precipitate at 80deg.C overnight to obtain 50wt% CABI@C 3 N 4 And a heterojunction. The 50wt% CABI@C 3 N 4 The heterojunction acts directly as a photocatalyst material.
Embodiment four:
weighing 0.0054g g-C obtained in comparative example one 3 N 4 The nanotube powder is dispersed in 5mL of toluene by ultrasonic treatment for 10min to form g-C 3 N 4 A dispersion; 0.0520g CsI (0.2 mmol), 0.0235g AgI (0.1 mmol) and 0.0590g BiI were weighed out separately 3 (0.1 mmol) was dissolved in 5mL Dimethylformamide (DMF) and vigorously stirred for 15min to give Cs 2 AgBiI 6 (CABI) precursor solution. Every 200 mu L of precursor liquid is dripped into 5mL g-C 3 N 4 Recrystallizing the dispersion liquid, and vigorously stirring for 15min, and inducing instant supersaturation to form precipitate, thus obtaining orange turbid liquid. Centrifuging the orange solution at 8000r/min for 3min, and removing supernatant to obtain lower red precipitate; drying the precipitate at 80deg.C overnight to obtain 50wt% CABI@C 3 N 4 And a heterojunction. The 50wt% CABI@C 3 N 4 The heterojunction acts directly as a photocatalyst material.
Fifth embodiment:
weighing 0.0108g g-C obtained in comparative example one 3 N 4 The nanotube powder is ultrasonically dispersed in 5mL of isopropanol and sonicated for 5min to form g-C 3 N 4 A dispersion; 0.0520g CsI (0.2 mmol), 0.0235g AgI (0.1 mmol) and 0.0590g BiI were weighed out separately 3 (0.1 mmol) was dissolved in 5mL Dimethylformamide (DMF) and vigorously stirred for 20min to give Cs 2 AgBiI 6 (CABI) precursor solution. Every 200 mu L of precursor liquid is dripped into 5mL g-C 3 N 4 Recrystallizing the dispersion liquid, and vigorously stirring for 30min, and inducing instant supersaturation to form precipitate to obtain orange turbid liquid. Centrifuging the orange solution at a rotation speed of 5000r/min for 5min, and removing the supernatant to obtain a lower red precipitate; drying the precipitate at 80deg.C overnight to obtain 33wt% CABI@C 3 N 4 And a heterojunction. The 33wt% of CABI@C 3 N 4 The heterojunction acts directly as a photocatalyst material.
Example six:
weighing the sample of comparative example one, 0.0080g g-C 3 N 4 The nanotube powder is dispersed in 5mL of toluene by ultrasonic treatment for 10min to form g-C 3 N 4 A dispersion; 0.0520g CsI (0.2 mmol), 0.0235g AgI (0.1 mmol) and 0.0590g BiI were weighed out separately 3 (0.1 mmol) was dissolved in 5mL of dimethyl argon sulfone (DMSO) and vigorously stirred for 30min to give Cs 2 AgBiI 6 (CABI) precursor solution. Every 200 mu L of precursor liquid is dripped into 5mL g-C 3 N 4 Recrystallizing the dispersion liquid, and vigorously stirring for 20min to induce instant supersaturation to form precipitate, thus obtaining orange turbid liquid. Centrifuging the orange solution at 8000r/min for 3min, and removing supernatant to obtain lower red precipitate; drying the precipitate at 80deg.C overnight to obtain 40wt% CABI@C 3 N 4 And a heterojunction. The 40wt% of CABI@C 3 N 4 The heterojunction acts directly as a photocatalyst material.
The process parameter tables for examples one to six are shown in table 1.
Table 1 example process parameter table
The examples and comparative examples were characterized and tested and the test results are shown in table 2 and figures 1-9. Table 2 shows the average carrier lifetimes (. Tau.) for comparative example one, two and example one av ) Is a result of fitting of (a). The results were fitted from the fluorescence decay curve in fig. 8, and the formula for fitting the average carrier lifetime was: τ av ＝(A 1 τ 1 2 +A 2 τ 2 2 )/(A 1 τ 1 +A 2 τ 2 ). τ of comparative examples one, two and example one av 5.08, 97.96 and 4.21ns, respectively; example I compared to comparative examples I and II av The average carrier life is shortened, which indicates that carrier migration exists between the two after heterojunction is formed, fluorescence quenching occurs, and the fluorescence life is reduced.
TABLE 2 fluorescent lifetime fitting results for comparative example one, two and example one
| A 1 | τ 1 | A 2 | τ 2 | τ av (ns) | |
| Comparative example one | 53054.27 | 1.65 | 10641.02 | 8.43 | 5.08 |
| Comparative example two | 65237.23 | 1.01 | 1533.76 | 129.93 | 97.96 |
| Example 1 | 53744.71 | 1.34 | 10513.12 | 7.01 | 4.21 |
Figure 1 is an XRD pattern for comparative examples one, two and example one. Example one (CABI@C) 3 N 4 ) Correlation peaks for comparative example one and comparative example two were detected, indicating the formation of a composite material.
FIG. 2 is a graph showing the diffuse reflection spectrum of ultraviolet-visible light of comparative example I, comparative example II and example I, and it can be seen that g-C 3 N 4 The absorption edge of the nanotube (comparative example one) was about 440nm, the absorption edge of the CABI (comparative example two) was about 620nm, and CABI@C 3 N 4 The absorption edge of (embodiment one) is about: 600nm. And compared with g-C 3 N 4 Nanotubes, CABI@C 3 N 4 Is enhanced.
FIG. 3 shows the catalysts (. Alpha.hν) for comparative example one, comparative example two and example one 1/2 As can be seen from the graph of the energy band gap energy (hν), g-C 3 N 4 The band gap of the nano tube loaded with the CABI nano crystal is small, and the light absorption range is widened.
FIG. 4 is a graph of CABI@C 3 N 4 A heterojunction energy band structure diagram of (2).
Fig. 5 is an SEM image of comparative examples one and two. g-C 3 N 4 (comparative example one) exhibits nanotube morphology; CABI (comparative example two) presents agglomerated nanoplatelets and nanoparticulates.
FIG. 6 is a comparative example one (g-C 3 N 4 Nanotubes) and example one (CABI@C) 3 N 4 ) PL (Photoluminescence spectroscopy, photoluminescence spectrum) map of (b). The graph is g-C 3 N 4 Nanotubes and CABI@C 3 N 4 Steady state PL spectrum of heterojunction at excitation wavelength 550nm, with g-C 3 N 4 Compared with the nano tube, its CABI@C 3 N 4 The lower PL intensity of the heterojunction suggests g-C due to efficient charge separation at the heterojunction interface 3 N 4 Recombination of the photogenerated carriers is greatly affectedInhibiting.
FIG. 7 is a comparative example two (CABI nanocrystals) and example one (CABI@C) 3 N 4 ) PL diagram of (2). The graph is g-C 3 N 4 Nanotubes and CABI@C 3 N 4 Steady state PL spectrum of heterojunction at excitation wavelength 732nm, compared to CABI, cabi@c 3 N 4 The lower PL intensity of the heterojunction indicates that carrier recombination on CABI is also inhibited. FIGS. 6 and 7 further demonstrate CABI and g-C 3 N 4 Forming a heterojunction therebetween.
FIG. 8 is a graph of TRPL (Time-resolved PL spectra, time resolved fluorescence spectra) of comparative examples one, two and example one. The corresponding carrier lifetimes were fitted from the graph data as shown in table 3.
Fig. 9 is a graph showing the hydrogen production rate of photocatalytic-decomposed water for comparative examples one, two and examples one to six. It can be seen that CABI@C 3 N 4 I.e. the hydrogen production rate is better than that of single CABI or g-C 3 N 4 。
Although the invention has been described herein with reference to the above-described illustrative embodiments thereof, the above-described embodiments are merely preferred embodiments of the present invention, and the embodiments of the present invention are not limited by the above-described embodiments, it should be understood that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the scope and spirit of the principles of this disclosure.
Claims (11)
1. CABI@C 3 N 4 The preparation method of the heterojunction catalyst is characterized by comprising the following steps: (1) Will g-C 3 N 4 The nanotube powder is dispersed in a first solvent by ultrasonic to form g-C 3 N 4 A dispersion; (2) CsI, agI and BiI 3 Dissolving in a second solvent and vigorously stirring to obtain Cs 2 AgBiI 6 A precursor solution; (3) Cs is processed by 2 AgBiI 6 Dripping the precursor solution into g-C 3 N 4 Recrystallizing the dispersion liquid, vigorously stirring, and inducing instant supersaturation to form precipitate to obtain orange turbid liquid; (4) Centrifuging the orange turbid liquid, removing the supernatant to obtain the lower red precipitateA starch; drying the precipitate to obtain CABI@C 3 N 4 Heterojunction catalysts.
2. The cabi@c according to claim 1 3 N 4 A method for preparing a heterojunction catalyst is characterized in that the g-C 3 N 4 The preparation method of the nanotube powder comprises the following steps: (1) Dissolving melamine in deionized water and stirring uniformly to obtain a first solution, heating the first solution in a polytetrafluoroethylene reaction kettle for reaction, cooling to room temperature after the reaction is finished, centrifuging the reaction solution, and drying the centrifuged product to obtain g-C 3 N 4 Precursor powder of nanotubes; (2) Will g-C 3 N 4 Heating the precursor powder of the nanotube, and grinding to obtain g-C 3 N 4 Nanotube powder.
3. The cabi@c according to claim 1 3 N 4 A process for preparing a heterojunction catalyst characterized in that the g-C in step (1) 3 N 4 g-C in dispersion 3 N 4 The mass fraction of the nanotube powder is 10-50wt%, the ultrasonic time is 5-10 min, and the first solvent is selected from any one of isopropanol, toluene and hexane.
4. The cabi@c according to claim 1 3 N 4 The preparation method of the heterojunction catalyst is characterized in that CsI, agI and BiI in the step (2) 3 The molar ratio of the solvent to the solvent is 2:1:1, the second solvent is dimethyl argon sulfone or dimethyl formamide, and the vigorous stirring time is 10-30 min.
5. The cabi@c according to claim 1 3 N 4 A method for preparing a heterojunction catalyst is characterized in that Cs in the step (3) 2 AgBiI 6 Precursor solution and g-C 3 N 4 The volume ratio of the dispersion liquid is 1:25, and the intense stirring time is 10-30 min.
6. The cabi@c according to claim 1 3 N 4 The preparation method of the heterojunction catalyst is characterized in that the rotational speed of centrifugation in the step (4) is 5000-8000 r/min, the time is 3-5 min, the drying temperature is 80-100 ℃, and the drying time is 8-12 h.
7. The cabi@c according to claim 2 3 N 4 The preparation method of the heterojunction catalyst is characterized in that the mass volume ratio of melamine to deionized water in the step (1) is 1g to 20mL, the stirring time is 1-2 hours, the heating reaction temperature is 200-220 ℃, and the heating reaction time is 10-14 hours.
8. The cabi@c according to claim 2 3 N 4 The preparation method of the heterojunction catalyst is characterized in that in the step (1), the centrifugal operation is carried out by transferring the reaction liquid into a centrifuge tube for centrifugation, and then sequentially and respectively centrifuging for 3 times by using deionized water and absolute ethyl alcohol, wherein the rotating speed of the centrifuge is set to 8000-11000 r/min, and the centrifuging time is set to 3-8 min; and drying the centrifuged product at 60-100 ℃ for 8-12 h.
9. The cabi@c according to claim 2 3 N 4 The preparation method of the heterojunction catalyst is characterized in that the heating temperature in the step (2) is 520-550 ℃, the heating time is 3-4 h, and the heating rate is 2-5 ℃/min.
10. CABI@C 3 N 4 Heterojunction catalyst characterized in that it is prepared by the preparation method according to any one of claims 1-9.
11. A cabi@c according to claim 10 3 N 4 The heterojunction catalyst is characterized by being applied to the field of hydrogen production by photocatalytic water splitting.
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