CN110560124A - Efficient nano catalyst for hydrogen production by formic acid hydrolysis and preparation method thereof - Google Patents

Efficient nano catalyst for hydrogen production by formic acid hydrolysis and preparation method thereof Download PDF

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CN110560124A
CN110560124A CN201910836490.1A CN201910836490A CN110560124A CN 110560124 A CN110560124 A CN 110560124A CN 201910836490 A CN201910836490 A CN 201910836490A CN 110560124 A CN110560124 A CN 110560124A
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formic acid
rgo
catalyst
aqueous solution
aupdir
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鄢俊敏
刘冬雪
康霞
张野
段焱鑫
姚佳欣
李弘睿
高蕊
俞珍
王达年
蒋青
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Jilin University
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Abstract

The invention relates to the technical field of catalyst preparation, in particular to a high-efficiency nano catalyst for hydrogen production by formic acid hydrolysis, which is prepared by passing through-NH2-N bifunctional group modified graphene carrier NH2AuPdIr/NH obtained by doping gold-palladium-iridium nano particles on-N-rGO2-N-rGO high efficiency catalyst. By one-step rapid reductionThe method is prepared at room temperature, has short synthesis time and simple and convenient operation, still has extremely high catalytic activity, 100 percent formic acid conversion rate, 100 percent hydrogen selectivity and better circulation stability under the condition of no additive, and can realize the complete decomposition of the formic acid within 0.75 min. AuPdIr/NH2initial TOF value of-N-rGO 10224.9h‑1Is far higher than the AuPd/NH reported at present2TOF value of-N-rGO 4639.2h‑1。

Description

Efficient nano catalyst for hydrogen production by formic acid hydrolysis and preparation method thereof
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a high-efficiency nano catalyst for hydrogen production by formic acid hydrolysis and a preparation method thereof.
Background
hydrogen is considered to be a very potential energy carrier for transportation/mobile applications, playing an important role in the sustainable development of future renewable energy technologies. However, the very low critical point and the very low density of hydrogen make the efficient storage of hydrogen difficult to break through, which causes great inconvenience to the application of hydrogen-based fuel cells, so that the search for alternative materials is the focus of current research. Chemical hydrogen storage materials are currently gaining wide attention due to various advantageous properties at room temperature, such as formic acid. Formic acid (HC00H, FA) is the main product of biological process, is nontoxic, has extremely high stability at room temperature, has 4.4% of hydrogen content, and has various advantages, so that the formic acid can be used as a safe and convenient hydrogen carrier in a portable fuel cell. Formic acid can decompose along the hydrolysis pathway to produce hydrogen and carbon dioxide under the action of a suitable catalyst, but formic acid can also decompose along an undesirable dehydration pathway to produce carbon monoxide. It is well known that carbon monoxide poisons catalysts in fuel cells, resulting in a reduction or even loss of activity. Therefore, the formic acid decomposition reaction should be used to suppress the generation of carbon monoxide, for example, the components of the catalyst, the pH of the solution, and the reaction temperature should be adjusted. Recently, the development of selective decomposition of formic acid has been advanced, and particularly, the development of a catalyst has been studied more. For example, the metal complex heterogeneous catalyst has been applied to the hydrolysis reaction of formic acid under ambient conditions and shows a higher activity. Heterogeneous catalysts are widely used due to their advantages of easy control, convenient extraction, easy recovery, etc. Therefore, the search for heterogeneous catalysts with high activity and high selectivity in the hydrolysis of formic acid at room temperature is the focus of the research. The fine-sized metal particles have a unique catalytic activity compared to the bulk material because the small particles have a large specific surface area and a large number of active atoms at the edges and corners, and thus the fine-sized metal particles have raised a huge research heat surge in the field of catalysts. However, smaller particle sizes tend to agglomerate, especially at the nanometer level, due to surface energy considerations. The agglomeration has a great influence on the activity of the catalyst, and the activity cannot be fully expressed to show low activity. To avoid this problem, a variety of support materials are applied to the preparation of metal nanoparticle catalysts as substrates, promoting uniform distribution of small particles on their surface, thereby avoiding agglomeration. The graphene single-layer carbon material has great research attention due to the advantages of high conductivity, huge specific surface area, unique graphitized substrate structure, low preparation cost and the like. Due to these advantages of graphene, various nanomaterials based thereon have been applied to various fields such as sensors, electronics, electrochemical energy storage, high-efficiency catalysts, and the like. In the research in the field of catalysts, the interaction between graphene and metal nanoparticles plays an important role in improving the activity of the catalyst. Thus, graphene is a very promising substrate for many applications.
The subject group submits an invention patent application with the application number of 201810620905.2 to the national patent office in 2018 in the 6 th month, the invention name is a functionalized graphene supported gold-palladium nano catalyst and a preparation method and application thereof, and a simple and effective method is expected to be found for synthesizing a high-efficiency and good-dispersibility metal alloy nano catalyst to improve the efficiency of the formic acid dehydrogenation reaction, however, the catalyst prepared by the method still has an increased space for evaluation on the catalytic efficiency.
Disclosure of Invention
The invention provides a high-efficiency nano catalyst for hydrogen production by formic acid hydrolysis and a preparation method thereof, aiming at improving the catalytic efficiency of the catalyst, and can completely solve the technical problems.
The technical scheme for solving the technical problems is as follows:
The invention designs a high-efficiency catalyst for hydrogen production by formic acid hydrolysis, namely, the high-efficiency catalyst is prepared by passing through-NH2-N bifunctional group modified graphene carrier NH2AuPdIr/NH obtained by doping gold-palladium-iridium nano particles on-N-rGO2-N-rGO high efficiency catalyst.
The preparation method of the high-efficiency catalyst for hydrogen production by formic acid hydrolysis comprises the following steps:
(1) preparing graphene oxide GO in advance by adopting a Hummer's method, adding the prepared GO into a certain amount of water, and preparing a GO aqueous solution with the concentration of 1-5 mg/mL; carrying out ultrasonic treatment for 15-30 min to obtain a uniformly dispersed GO aqueous solution;
(2) Adding a proper amount of 3-aminopropyl-3-ethoxysilane APTS into the GO aqueous solution obtained in the step (1), continuing ultrasonic treatment for 5-15 min, and uniformly stirring to obtain a mixed solution A;
(3) PdCl with a molar ratio of 1:22Dissolving NaCl and NaCl in certain amount of distilled water, and stirring to obtain brown yellow Na2PdCl4An aqueous solution;
(4) The prepared Na2PdCl4Aqueous solution, HAuCl4Aqueous solution and IrCl3·xH2O water solution, taking a proper amount to be added into the step (2)continuously stirring the mixed solution A to obtain a mixed solution B; said Na2PdCl4Aqueous solution, HAuCl4Aqueous solution and IrCl3·xH2The concentration of the O aqueous solution is 0.02M;
the molar ratio of Pd (Au + Ir) is 1:1, wherein Au: the Ir molar ratio is 1-5: 1. the optimal molar ratio of Au to Pd to Ir is 7:10: 3.
(5) 30-100 mg of sodium borohydride NaBH4adding the reducing agent into the mixed solution B obtained in the step (4), and stirring and reducing to obtain a mixed solution C; the stirring reduction is carried out at room temperature, and the reduction time is 10-20 min.
(6) At room temperature, stirring and reducing the mixed solution C in the step (5) in the air, centrifuging at 8000-10000 rpm for 3-5 min after bubbles completely disappear, and washing with water for 3-5 times to obtain the AuPdIr/NH2-N-rGO high efficiency catalyst; the AuPdIr/NH2the-N-rGO high-efficiency catalyst is characterized in that AuPdIR nano particles are uniformly distributed in a-NH passing process2-N bifunctional group modified graphene carrier NH2-N-rGO.
the application of the high-efficiency catalyst for hydrogen production by formic acid hydrolysis has the concentration of 0.5-5M of formic acid aqueous solution, and the AuPdIr/NH2The mol ratio of the-N-rGO high-efficiency catalyst to the formic acid is 0.01-0.5.
Further, the AuPdIr/NH2the-N-rGO high-efficiency catalyst is used for hydrogen production reaction by the decomposition of aqueous solution of formic acid at room temperature; when AuPdIr/NH2When the actual dosage of the-N-rGO high-efficiency catalyst is 0.06mmol, 245mL of gas is generated within 0.75min, the gas is a 1:1 mixed gas of hydrogen and carbon dioxide generated by the formic acid dehydrogenation reaction, the formic acid conversion rate is 100%, and the hydrogen selectivity is 100%.
The invention has the beneficial effects that:
The invention synthesizes AuPdIr/NH by a one-step rapid reduction method2the-N-rGO high-efficiency catalyst can be prepared at room temperature, has short synthesis time and simple and convenient operation, and can obviously improve the NH content of AuPdIr nanoparticles2-dispersibility on N-rGO substrates, and reduction of particle size of metals; combining the AuPdIr-NH2the-N-rGO high-efficiency catalyst is used for catalyzing the formic acid aqueous solution to decompose and produce hydrogen at room temperature, has extremely high catalytic activity, 100 percent of formic acid conversion rate, 100 percent of hydrogen selectivity and better circulation stability under the condition of no additive, and can realize the complete decomposition of formic acid within 0.75 min. AuPdIr/NH2initial TOF value of-N-rGO 10224.9h-1Is far higher than the AuPd/NH reported at present2N-rGO (conversion 100%, TOF 4639.2 h)-1)、PdAu-MnOx/N-SiO2(conversion 92%, TOF 785h-1) Ag @ Pd (conversion 41%, TOF 13.1 h)-1) And the like. AuPdIr/NH2the performance of-N-rGO catalysts can even be compared to the performance of many homogeneous catalysts at higher reaction temperatures, e.g. RuBr3PPh (45% conversion, TOF 3630 h)-1)，Ru(H)2(meso-P4) (98% conversion, TOF 870h-1)、RuCl3(conversion 91%, TOF 150h-1) And the like. By passing through-NH2the-N bifunctional modified graphene is used as a substrate, so that the agglomeration of ultrafine AuPdIr nanoparticles is effectively inhibited, the activity of the catalyst can be obviously improved, and the catalyst has a good application prospect.
drawings
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
FIG. 1 is a Transmission Electron Microscope (TEM) and particle size distribution chart of example 1;
FIG. 2 is a Raman spectrum of example 1;
FIG. 3 is an X-ray diffraction (XRD) pattern of example 1;
FIG. 4a is a time-course plot of the catalytic formic acid decomposition at room temperature for the catalyst prepared in example 1;
FIG. 4b is a gas chromatogram of the catalyst prepared in example 1 catalyzing the decomposition of formic acid to produce gas;
FIG. 5 is a Transmission Electron Microscope (TEM) image of example 2;
FIG. 6 is a Raman spectrum of example 2;
FIG. 7 is an X-ray diffraction (XRD) pattern of example 2;
FIG. 8a is a time-course plot of the catalytic formic acid decomposition at room temperature for the catalyst prepared in example 2;
FIG. 8b is a gas chromatogram of the catalyst prepared in example 2 catalyzing the decomposition of formic acid to produce gas;
FIG. 9 is a Transmission Electron Microscope (TEM) image of example 3;
FIG. 10 is a Raman spectrum of example 3;
FIG. 11 is an X-ray diffraction (XRD) pattern of example 3;
FIG. 12a is a time-course plot of the catalytic formic acid decomposition at room temperature for the catalyst prepared in example 3;
FIG. 12b is a gas chromatogram of the catalyst prepared in example 3 catalyzing the decomposition of formic acid to produce gas;
FIG. 13 is a Transmission Electron Microscope (TEM) image of example 4;
FIG. 14 is a Raman spectrum of example 4;
FIG. 15 is an X-ray diffraction (XRD) pattern of example 4;
FIG. 16a is a time-course plot of the catalytic formic acid decomposition at room temperature for the catalyst prepared in example 4;
FIG. 16b is a gas chromatogram of the catalyst prepared in example 4 catalyzing the decomposition of formic acid to produce gas;
FIG. 17 is a Transmission Electron Microscope (TEM) image of example 5;
FIG. 18 is a Raman spectrum of example 5;
FIG. 19 is an X-ray diffraction (XRD) pattern of example 5;
FIG. 20a is a time-course plot of the catalytic formic acid decomposition at room temperature for the catalyst prepared in example 5;
FIG. 20b is a gas chromatogram of the catalyst prepared in example 5 catalyzing the decomposition of formic acid to produce gas;
FIG. 21 is a Transmission Electron Microscope (TEM) view of a comparative example;
FIG. 22a is a Raman spectrum of a comparative example;
FIG. 22b is an X-ray diffraction (XRD) pattern of comparative example 1;
FIG. 23a is a time-course plot of the catalytic formic acid decomposition at room temperature for a catalyst prepared in a comparative example;
FIG. 23b is a gas chromatogram of a catalyst prepared in comparative example catalyzing the decomposition of formic acid to produce gas.
Detailed Description
Graphene Oxide (GO) is prepared in advance by a Hummer's method, in order to facilitate transverse comparison of various performance parameters of products, the concentrations of graphene oxide adopted in examples 1-5 are all 1.5mg/mL, and in order to expand the protection range of the invention, the concentrations of GO and sodium borohydride NaBH are changed under the same conditions in examples 6-74The high-efficiency nano catalyst with the technical effect can be obtained by adding the amount of the catalyst.
wherein, Na2PdCl4aqueous solution, HAuCl4aqueous solution and IrCl3·xH2The concentration of the O aqueous solution is 0.02M; stirring reduction is carried out at room temperature, and the reduction time is 10-20 min. AuPdIr/NH2the-N-rGO high-efficiency catalyst is characterized in that AuPdIR nano particles are uniformly distributed in a-NH passing process2-N bifunctional group modified graphene carrier NH2-N-rGO.
When the catalyst is used for hydrogen production by formic acid hydrolysis, the concentration of the formic acid aqueous solution is 0.5-5M, and AuPdIr/NH2The mol ratio of the-N-rGO high-efficiency catalyst to the formic acid is 0.01-0.5.
example 1:
1. Preparing a high-efficiency catalyst:
Dispersing 30mg of GO in 20mL of ultrapure water, carrying out ultrasonic treatment for 15min, adding 0.4mL of APTS, and uniformly stirring; 0.035mmol HAuCl was respectively taken4solution, 0.05mmol of Na2PdCl4solution and 0.015mmol of IrCl3·xH2Dissolving the O solution in an aqueous solution of APTS + GO, and stirring for 3 min; at 25 deg.C, 30mg of NaBH is added4Uniformly stirring the mixed solution by magnetic force until no bubbles are generated, and completely reducing; centrifuging, washing to obtain Au0.35Pd0.5Ir0.15/NH2-N-rGO catalyst.
2. Sample detection:
(1) The prepared Au layer0.35Pd0.5Ir0.15/NH2-diluting the N-rGO catalyst, dropping on a carbon support membrane, and drying; referring to FIG. 1, the results of Transmission Electron Microscopy (TEM) and particle size analysis show that Au is0.35Pd0.5Ir0.15/NH2the-N-rGO sample has an ultra-fine particle size (2.58nm) and uniform dispersibility, and a high-resolution transmission electron microscope (HRTEM) shows that the lattice spacing of the nanoparticles is 0.231nm, Au (the lattice spacing is 0.235nm), Pd (the lattice spacing is 0.224nm) and Ir (the lattice spacing is 0.221nm) are between the (111) crystal planes, so that the alloy structure of the nanoparticles is proved.
(2) The prepared Au layer0.35Pd0.5Ir0.15/NH2-N-rGO catalyst and GO vacuum drying; referring to fig. 2, raman results show that GO is successfully reduced to rGO.
(3) the prepared Au is0.35Pd0.5Ir0.15/NH2-N-rGO catalyst vacuum drying; referring to fig. 3, the X-ray diffraction (XRD) result shows that the experimental method successfully synthesizes the functionalized graphene-supported AuPdIr trimetallic catalyst, wherein AuPdIr has an alloy structure.
3. Catalyzing formic acid hydrolysis to prepare hydrogen:
Mixing Au0.35Pd0.5Ir0.15/NH2-N-rGO catalyst was dispersed in water, 5mmol of formic acid was added and the hydrogen produced was measured by a gas burette. Au coating0.35Pd0.5Ir0.15/NH2the hydrogen production amount (mL) and time (min) of the hydrogen production process by catalyzing formic acid aqueous solution by the N-rGO catalyst is shown in a graph in FIG. 4a, and the amount of the generated gas in 0.75min by catalyzing the hydrogen production by hydrolyzing formic acid at room temperature is 245 mL. In addition, 5mmol of formic acid in Au was taken0.35Pd0.5Ir0.15/NH2The decomposition reaction is carried out under the action of-N-rGO catalyst, and mass spectrometry is carried out under Ar atmosphere, and the result of figure 4b proves that formic acid is completely decomposed into H2and CO2Hydrogen selectivity behavior is 100%.
Example 2:
1. preparing a high-efficiency catalyst:
dispersing 30mg of GO in 20mL of ultrapure water, carrying out ultrasonic treatment for 15min, adding 0.4mL of APTS, and uniformly stirring; 0.03mmol HAuCl is respectively taken4Solution, 0.05mmol of Na2PdCl4Solution and 0.02mmol of IrCl3·xH2Dissolving the O solution in an aqueous solution of APTS + GO, and stirring for 3 min; at 25 deg.C, 30mg of NaBH is added4uniformly stirring the mixed solution by magnetic force until no bubbles are generated, and completely reducing; centrifuging, washing to obtain Au0.3Pd0.5Ir0.2/NH2-N-rGO catalyst.
2. Sample detection:
(1) The prepared Au layer0.3Pd0.5Ir0.2/NH2-diluting the N-rGO catalyst, dropping on a carbon support membrane, and drying; referring to FIG. 5, the Transmission Electron Microscope (TEM) results show that Au0.3Pd0.5Ir0.2/NH2the-N-rGO samples had ultra-fine particle size and uniform dispersibility.
(2) The prepared Au layer0.3Pd0.5Ir0.2/NH2-N-rGO catalyst and GO vacuum drying; referring to fig. 6, raman results show that GO was successfully reduced to rGO.
(3) The prepared Au is0.3Pd0.5Ir0.2/NH2-N-rGO catalyst vacuum drying; referring to fig. 7, the X-ray diffraction (XRD) result shows that the experimental method successfully synthesizes the functionalized graphene-supported AuPdIr trimetallic catalyst, wherein AuPdIr has an alloy structure.
3. Catalyzing formic acid hydrolysis to prepare hydrogen:
Mixing Au0.3Pd0.5Ir0.2/NH2-N-rGO catalyst was dispersed in water, 5mmol of formic acid was added and the hydrogen produced was measured by a gas burette. Au coating0.3Pd0.5Ir0.2/NH2The hydrogen production amount (mL) and time (min) graph of the hydrogen production process by catalyzing the formic acid aqueous solution by the N-rGO catalyst is shown in FIG. 8a, and the amount of the gas produced by catalyzing the hydrogen production by hydrolyzing the formic acid at room temperature is 245mL in 0.95 min. In addition, 5mmol of formic acid in Au was taken0.3Pd0.5Ir0.2/NH2The decomposition reaction is carried out under the action of-N-rGO catalyst, mass spectrum test is carried out under Ar atmosphere, and the result of figure 8b proves that formic acid is completely decomposed into H2And CO2Hydrogen selectivity behavior is 100%.
example 3:
1. Preparing a high-efficiency catalyst:
Dispersing 30mg of GO in 20mL of ultrapure water, carrying out ultrasonic treatment for 15min, adding 0.4mL of APTS, and uniformly stirring; 0.0417mol of HAuCl is respectively taken4Solution, 0.05mol of Na2PdCl4Solution and 0.0083mol of IrCl3·xH2dissolving the O solution in an aqueous solution of APTS + GO, and stirring for 3 min; at 25 deg.C, 30mg of NaBH is added4Uniformly stirring the mixed solution by magnetic force until no bubbles are generated, and completely reducing; centrifuging, washing to obtain Au0.5Pd0.6Ir0.1/NH2-N-rGO catalyst.
2. Sample detection:
(1) The prepared Au layer0.5Pd0.6Ir0.1/NH2-diluting the N-rGO catalyst, dropping on a carbon support membrane, and drying; referring to FIG. 9, the Transmission Electron Microscope (TEM) results show that Au0.5Pd0.6Ir0.1/NH2the-N-rGO samples had ultra-fine particle size and uniform dispersibility.
(2) The prepared Au layer0.5Pd0.6Ir0.1/NH2-N-rGO catalyst and GO vacuum drying; referring to fig. 10, raman results show that GO was successfully reduced to rGO.
(3) The prepared Au is0.5Pd0.6Ir0.1/NH2-N-rGO catalyst vacuum drying; referring to fig. 11, the X-ray diffraction (XRD) result shows that the experimental method successfully synthesizes the functionalized graphene-supported AuPdIr trimetallic catalyst, wherein AuPdIr has an alloy structure.
3. Catalyzing formic acid hydrolysis to prepare hydrogen:
Mixing Au0.5Pd0.6Ir0.1/NH2dispersing the-N-rGO catalyst into water, adding 5mmol of formic acid, and introducingThe produced hydrogen gas was measured through a gas burette. Au coating0.5Pd0.6Ir0.1/NH2The hydrogen production amount (mL) and time (min) of the hydrogen production process by catalyzing formic acid aqueous solution by the N-rGO catalyst is shown in FIG. 12a, and the amount of the gas produced by catalyzing the hydrogen production by hydrolyzing formic acid at room temperature is 245mL in 0.92 min. In addition, 5mmol of formic acid in Au was taken0.5Pd0.6Ir0.1/NH2Decomposition reaction is carried out under the action of-N-rGO catalyst, mass spectrum test is carried out under Ar atmosphere, and the result of figure 12b proves that formic acid is completely decomposed into H2And CO2Hydrogen selectivity behavior is 100%.
Example 4:
1. Preparing a high-efficiency catalyst:
Dispersing 30mg of GO in 20mL of ultrapure water, carrying out ultrasonic treatment for 15min, adding 0.4mL of APTS, and uniformly stirring; respectively taking 0.025mmol HAuCl4Solution, 0.05mmol of Na2PdCl4Solution and 0.025mmol of IrCl3·xH2Dissolving the O solution in an aqueous solution of APTS + GO, and stirring for 3 min; at 25 deg.C, 30mg of NaBH is added4Uniformly stirring the mixed solution by magnetic force until no bubbles are generated, and completely reducing; centrifuging, washing to obtain Au0.25Pd0.5Ir0.25/NH2-N-rGO catalyst.
2. Sample detection:
(1) The prepared Au layer0.25Pd0.5Ir0.25/NH2-diluting the N-rGO catalyst, dropping on a carbon support membrane, and drying; referring to FIG. 13, Transmission Electron Microscope (TEM) results show that Au0.25Pd0.5Ir0.25/NH2the-N-rGO samples had ultra-fine particle size and uniform dispersibility.
(2) the prepared Au layer0.25Pd0.5Ir0.25/NH2-N-rGO catalyst and GO vacuum drying; referring to fig. 14, raman results show that GO was successfully reduced to rGO.
(3) The prepared Au is0.25Pd0.5Ir0.25/NH2-N-rGO catalyst vacuum drying; referring to FIG. 15, X-ray diffraction (XRD) resultsThe experiment method shows that the functionalized graphene-loaded AuPdIr trimetal catalyst is successfully synthesized, wherein the AuPdIr is in an alloy structure.
3. Catalyzing formic acid hydrolysis to prepare hydrogen:
Mixing Au0.25Pd0.5Ir0.25/NH2-N-rGO catalyst was dispersed in water, 5mmol of formic acid was added and the hydrogen produced was measured by a gas burette. Au coating0.25Pd0.5Ir0.25/NH2the hydrogen production amount (mL) and time (min) of the hydrogen production process by catalyzing formic acid aqueous solution by the N-rGO catalyst is shown in a graph in FIG. 16a, and the amount of the gas produced by catalyzing the hydrogen production by hydrolyzing formic acid at room temperature is 245mL in 1.11 min. In addition, 5mmol of formic acid in Au was taken0.25Pd0.5Ir0.25/NH2decomposition reaction is carried out under the action of-N-rGO catalyst, mass spectrum test is carried out under Ar atmosphere, and the result of FIG. 16b proves that formic acid is completely decomposed into H2and CO2Hydrogen selectivity behavior is 100%.
example 5:
1. preparing a high-efficiency catalyst:
dispersing 30mg of GO in 20mL of ultrapure water, carrying out ultrasonic treatment for 15min, adding 0.4mL of APTS, and uniformly stirring; 0.0357mmol of HAuCl is respectively taken4Solution, 0.05mmol of Na2PdCl4Solution and 0.0143mmol of IrCl3·xH2Dissolving the O solution in an aqueous solution of APTS + GO, and stirring for 3 min; at 25 deg.C, 30mg of NaBH is added4Uniformly stirring the mixed solution by magnetic force until no bubbles are generated, and completely reducing; centrifuging, washing to obtain Au0.25Pd0.35Ir0.1/NH2-N-rGO catalyst.
2. sample detection:
(1) The prepared Au layer0.25Pd0.35Ir0.1/NH2-diluting the N-rGO catalyst, dropping on a carbon support membrane, and drying; referring to FIG. 17, Transmission Electron Microscope (TEM) results show that Au0.25Pd0.35Ir0.1/NH2the-N-rGO samples had ultra-fine particle size and uniform dispersibility.
(2) The prepared Au layer0.25Pd0.35Ir0.1/NH2-N-rGO catalyst and GO vacuum drying; referring to fig. 18, raman results show that GO was successfully reduced to rGO.
(3) The prepared Au is0.25Pd0.35Ir0.1/NH2-N-rGO catalyst vacuum drying; referring to fig. 19, the X-ray diffraction (XRD) result shows that the experimental method successfully synthesizes the functionalized graphene-supported AuPdIr trimetallic catalyst, wherein AuPdIr has an alloy structure.
3. catalyzing formic acid hydrolysis to prepare hydrogen:
Mixing Au0.25Pd0.35Ir0.1/NH2-N-rGO catalyst was dispersed in water, 5mmol of formic acid was added and the hydrogen produced was measured by a gas burette. Au coating0.25Pd0.35Ir0.1/NH2The hydrogen production amount (mL) and time (min) graph of the hydrogen production process by catalyzing the formic acid aqueous solution by the N-rGO catalyst is shown in FIG. 20a, and the amount of the gas produced by catalyzing the hydrogen production by hydrolyzing the formic acid at room temperature is 245mL in 0.77 min. In addition, 5mmol of formic acid in Au was taken0.25Pd0.35Ir0.1/NH2The decomposition reaction is carried out under the action of-N-rGO catalyst, and mass spectrometry is carried out under Ar atmosphere, and the result of figure 20b proves that formic acid is completely decomposed into H2And CO2Hydrogen selectivity behavior is 100%.
Comparative example: (example 1 of application No. 201810620905.2)
1. Preparing a catalyst:
Adding 0.033mmol of HAuCl4and 0.067mmol of Na2PdCl4Dissolving in APTS + GO water solution, and stirring uniformly; 30mg of NaBH4Dissolving in 1mL of distilled water, adding the solution into the mixed solution at 25 ℃, uniformly stirring by magnetic force, and stirring until complete reduction; centrifuging, washing to obtain AuPd/NH2-N-rGO catalyst.
2. Sample detection:
(1) The prepared AuPd/NH2-diluting the N-rGO catalyst, dropping on a carbon support membrane, and drying; referring to FIGS. 21a and 21b, electrons are transmittedThe results of the microscope (TEM) show that AuPd/NH2the N-rGO sample had an ultra-fine particle size (1.5nm) and uniform dispersion, and as can be seen from the high resolution picture of the sample, the sample formed AuPd alloy structure;
(2) The prepared AuPd/NH2-N-rGO catalyst and GO vacuum drying; referring to FIG. 22a, Raman results show that GO was successfully reduced to rGO, indicating that the method successfully synthesized AuPd/NH2-an N-rGO sample;
(3) The prepared AuPd/NH2-N-rGO catalyst vacuum drying; referring to fig. 22b, X-ray diffraction (XRD) results show that this experimental method successfully synthesizes the functionalized graphene-supported AuPd bimetallic catalyst, wherein AuPd is an alloy structure.
3. catalyzing formic acid aqueous solution to prepare hydrogen:
Mixing AuPd/NH2-N-rGO catalyst was dispersed in water, 5mmol of formic acid was added and the hydrogen produced was measured by a gas burette. AuPd/NH2A graph of hydrogen production amount (mL) and time (min) in the hydrogen production process by catalyzing formic acid aqueous solution with the N-rGO catalyst is shown in FIG. 23a, the amount of gas generated in 1.65 min by catalyzing hydrogen production by hydrolyzing formic acid at room temperature is 245mL, and the conversion rate reaches 100%. The gas composition is H as shown in FIG. 23b2And CO2No CO is produced.
example 6
preparing a high-efficiency catalyst:
Dispersing 30mg of GO in 30mL of ultrapure water, performing ultrasonic treatment for 20min, adding 0.4mL of APTS, and uniformly stirring; 0.035mmol HAuCl was respectively taken4Solution, 0.05mmol of Na2PdCl4Solution and 0.015mmol of IrCl3·xH2dissolving the O solution in an aqueous solution of APTS + GO, and stirring for 3 min; at 25 deg.C, 100mg of NaBH is added4Uniformly stirring the mixed solution by magnetic force until no bubbles are generated, and completely reducing; centrifuging, washing to obtain Au0.35Pd0.5Ir0.15/NH2-N-rGO catalyst.
Example 7
Preparing a high-efficiency catalyst:
Dispersing 30mg of GO in 6mL of ultrapure water, carrying out ultrasonic treatment for 30min, adding 0.4mL of APTS, and uniformly stirring; 0.035mmol HAuCl was respectively taken4Solution, 0.05mmol of Na2PdCl4Solution and 0.015mmol of IrCl3·xH2Dissolving the O solution in an aqueous solution of APTS + GO, and stirring for 3 min; at 25 deg.C, 60mg of NaBH is added4Uniformly stirring the mixed solution by magnetic force until no bubbles are generated, and completely reducing; centrifuging, washing to obtain Au0.35Pd0.5Ir0.15/NH2-N-rGO catalyst.
the above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and all simple modifications and equivalent variations of the above embodiment according to the present invention are within the scope of the present invention.

Claims (9)

1. The high-efficiency catalyst for preparing hydrogen by hydrolyzing formic acid is characterized in that the high-efficiency catalyst is prepared by passing-NH2-N bifunctional group modified graphene carrier NH2AuPdIr/NH obtained by doping gold-palladium-iridium nano particles on-N-rGO2-N-rGO high efficiency catalyst.
2. the preparation method of the high-efficiency catalyst for hydrogen production by formic acid hydrolysis, which is characterized by comprising the following steps:
(1) preparing graphene oxide GO in advance by adopting a Hummer's method, adding the prepared GO into a certain amount of water, and preparing a GO aqueous solution with the concentration of 1-5 mg/mL; carrying out ultrasonic treatment for 15-30 min to obtain a uniformly dispersed GO aqueous solution;
(2) Adding a proper amount of 3-aminopropyl-3-ethoxysilane APTS into the GO aqueous solution obtained in the step (1), continuing ultrasonic treatment for 5-15 min, and uniformly stirring to obtain a mixed solution A;
(3) PdCl with a molar ratio of 1:22Dissolving NaCl and NaCl in certain amount of distilled water, and stirring to obtain brown yellow Na2PdCl4An aqueous solution;
(4) the prepared Na2PdCl4Aqueous solution, HAuCl4Aqueous solution and IrCl3·xH2Adding a proper amount of O aqueous solution into the mixed solution A in the step (2), and continuously stirring to obtain a mixed solution B;
(5) 30-100 mg of sodium borohydride NaBH4Adding the reducing agent into the mixed solution B obtained in the step (4), and stirring and reducing to obtain a mixed solution C;
(6) At room temperature, stirring and reducing the mixed solution C in the step (5) in the air, centrifuging at 8000-10000 rpm for 3-5 min after bubbles completely disappear, and washing with water for 3-5 times to obtain the AuPdIr/NH2-N-rGO high efficiency catalyst.
3. The method according to claim 2, wherein in the step (4), Na is added2PdCl4Aqueous solution, HAuCl4Aqueous solution and IrCl3·xH2The concentration of the O aqueous solution was 0.02M.
4. the method according to claim 2, wherein in the step (4), the molar ratio of Pd (Au + Ir) is 1:1, wherein Au: the Ir molar ratio is 1-5: 1.
5. the method according to claim 4, wherein the optimal molar ratio of Au to Pd to Ir is 7:10: 3.
6. The preparation method according to claim 2, wherein the stirring reduction in the step (5) is performed at room temperature for 10-20 min.
7. The method according to claim 2, wherein the AuPdIr/NH used in step (6) is2the-N-rGO high-efficiency catalyst is characterized in that AuPdIR nano particles are uniformly distributed in a-NH passing process2-N bifunctional group modified graphene carrier NH2-N-rGO.
8. The use of the high-efficiency catalyst for hydrogen production by formic acid hydrolysis according to claim 1,The method is characterized in that the concentration of a formic acid aqueous solution is 0.5-5M, and the AuPdIr/NH2The mol ratio of the-N-rGO high-efficiency catalyst to the formic acid is 0.01-0.5.
9. the use according to claim 8, wherein said AuPdIr/NH is administered2the-N-rGO high-efficiency catalyst is used for hydrogen production reaction by the decomposition of aqueous solution of formic acid at room temperature; when AuPdIr/NH2when the actual dosage of the-N-rGO high-efficiency catalyst is 0.06mmol, 245mL of gas is generated within 0.75min, the gas is a 1:1 mixed gas of hydrogen and carbon dioxide generated by the formic acid dehydrogenation reaction, the formic acid conversion rate is 100%, and the hydrogen selectivity is 100%.
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