CN117403262A - Catalytic material for producing hydrogen by water electrolysis and preparation method and application thereof - Google Patents
Catalytic material for producing hydrogen by water electrolysis and preparation method and application thereof Download PDFInfo
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- CN117403262A CN117403262A CN202311312119.8A CN202311312119A CN117403262A CN 117403262 A CN117403262 A CN 117403262A CN 202311312119 A CN202311312119 A CN 202311312119A CN 117403262 A CN117403262 A CN 117403262A
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 50
- 239000001257 hydrogen Substances 0.000 title claims abstract description 50
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000000463 material Substances 0.000 title claims abstract description 37
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 35
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 27
- 239000008103 glucose Substances 0.000 claims abstract description 27
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 24
- 230000003647 oxidation Effects 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 235000019253 formic acid Nutrition 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 30
- 238000004070 electrodeposition Methods 0.000 claims description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 11
- 239000003792 electrolyte Substances 0.000 claims description 11
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 11
- 230000001590 oxidative effect Effects 0.000 claims description 10
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 239000006260 foam Substances 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 150000001720 carbohydrates Chemical class 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 150000001299 aldehydes Chemical class 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 claims description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 4
- 239000002028 Biomass Substances 0.000 abstract description 2
- 239000010949 copper Substances 0.000 description 16
- 229910002520 CoCu Inorganic materials 0.000 description 12
- 238000012360 testing method Methods 0.000 description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 229910018916 CoOOH Inorganic materials 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 238000006056 electrooxidation reaction Methods 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- OUDFNZMQXZILJD-UHFFFAOYSA-N 5-methyl-2-furaldehyde Chemical compound CC1=CC=C(C=O)O1 OUDFNZMQXZILJD-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000002362 energy-dispersive X-ray chemical map Methods 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 238000002186 photoelectron spectrum Methods 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/077—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the compound being a non-noble metal oxide
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/23—Oxidation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses a catalytic material for hydrogen production by water electrolysis and a preparation method and application thereof, belonging to the field of solar hydrogen production. The invention provides a catalytic material for producing hydrogen by water electrolysis, which has the chemical composition of AB x OOH；0<x<0.1 wherein A is any one of Fe, co and Ni, and B is any one of Mn, fe, ni, cu and Zn. The invention utilizes biomass-based raw materials, such as glucose and the like, as an oxidation substrate, and is coupled with the reaction of reduced water at the same timeThe efficiency of water electrolysis is up to 94.2% when the water electrolysis is matched with the high-efficiency catalytic material, and the efficiency of solar hydrogen production at room temperature exceeds 30%; meanwhile, glucose can be efficiently converted into formic acid which is a high value-added product, and the yield is over 80 percent; the technical scheme of the invention can reduce the cost of hydrogen produced by decomposing water of the solar cell by about 4.6 dollars per kilogram of hydrogen.
Description
Technical Field
The invention relates to the field of solar hydrogen production, in particular to a catalytic material for water electrolysis hydrogen production, a preparation method and application thereof.
Background
Solar hydrogen production is a very promising technical scheme for solving the energy and environmental problems. The approaches of solar hydrogen production mainly comprise photocatalytic water splitting hydrogen production, photoelectrochemical water splitting hydrogen production, direct water splitting hydrogen production of solar cells and the like. The solar cell directly decomposes water to prepare hydrogen, so that the conversion efficiency of hydrogen production by solar energy is relatively high and can exceed 20%. However, the oxidation reaction of water decomposition has a higher overpotential, resulting in lower efficiency of solar hydrogen production and low economic value of the produced oxygen. Aiming at the problem, a scheme of coupling glycerol, chitosan and 5-methylfurfural oxidation with water reduction to produce hydrogen is proposed in the prior art, so that the hydrogen production efficiency is improved, however, the current research is mainly focused on the problem of selectivity of oxidation products, and the hydrogen production efficiency is not subjected to systematic and deep analysis, so that the hydrogen production efficiency still needs to be improved. It is therefore necessary to find a suitable oxidation substrate and develop a high efficiency catalytic material that matches it.
Disclosure of Invention
The invention provides a catalytic material for producing hydrogen by water electrolysis, a preparation method and application thereof.
The invention firstly provides a catalytic material for producing hydrogen by water electrolysis, which has the chemical composition of AB x OOH；0<x<0.1 wherein A is any one of Fe, co and Ni, and B is any one of Mn, fe, ni, cu and Zn.
In the catalytic material, x is more than or equal to 0.03 and less than or equal to 0.09, and preferably, x=0.05;
a is Co, B is Cu, fe or Ni; preferably, B is Cu.
The invention also provides a preparation method of the catalytic material, which comprises the following steps: weighing a source A and a source B according to stoichiometric ratio, and dissolving the sources A and the sources B in water to obtain electrolyte; and then carrying out electrochemical deposition reaction, and oxidizing the anode after the reaction to obtain the catalytic material.
In the preparation method, the source A is nitrate and/or sulfate of corresponding metal elements; specifically, cobalt nitrate;
the source B is nitrate of corresponding metal elements; specifically, copper nitrate, manganese nitrate, ferric nitrate, nickel nitrate or zinc nitrate;
in the electrolyte, the concentration of A is 0.05-0.3 mol/L; specifically, the concentration may be 0.1mol/L.
In the preparation method, the electrochemical deposition reaction adopts a three-electrode system, and the cathode is a platinum sheet, platinum carbon or carbon paper; the anode is foam nickel, foam iron or carbon cloth; the reference electrode is an Ag/AgCl or saturated calomel electrode.
In the preparation method, the electrochemical deposition reaction adopts a constant pressure mode; applying a voltage of-0.8 to-1.2V relative to the reference electrode at the anode; specifically, -1.0V; the electrodeposition time is 1-10 min; specifically, the time period may be 5min.
In the preparation method, the oxidation is carried out by taking an anode electrode after electrochemical deposition reaction as an anode, taking potassium hydroxide solution as electrolyte, and applying constant voltage to the anode for oxidation reaction;
preferably, the oxidation employs a three-electrode system; applying a voltage of 0.1 to 0.5V to the anode with respect to the reference electrode; specifically, the voltage can be 0.3V; the oxidation time is 1-10 min; specifically, the time period may be 5min.
The concentration of the potassium hydroxide solution is 0.1-2 mol/L, and specifically can be 1mol/L.
Finally, the invention also provides the use of the catalytic material described above in any of the following;
(1) Application in hydrogen production by water electrolysis;
(2) The application of the combination of oxidizing alcohols, saccharides or aldehydes in the hydrogen production by the electrolysis of water.
In the above application, the saccharide is glucose;
the oxidizing alcohols, saccharides or aldehydes produce formic acid.
In the application, the power source is used for generating electricity by solar energy;
preferably, the power source is a solar cell.
The invention uses biomass-based raw materials, such as glucose and the like, as an oxidation substrate, and is simultaneously coupled with the reaction of reduced water and matched with a high-efficiency catalytic material, the water electrolysis efficiency is up to 94.2%, and the hydrogen production efficiency by solar energy is over 30%; meanwhile, glucose can be efficiently converted into formic acid which is a high value-added product, and the yield is over 80 percent; the technical scheme of the invention can reduce the cost of hydrogen produced by decomposing water of the solar cell by about 4.6 dollars per kilogram of hydrogen.
Drawings
FIG. 1 shows the preparation of electrocatalytic material CoCu by electrochemical deposition x Physical maps before and after electrochemical oxidation in OOH (x=0.05); in fig. 1, a is a physical diagram before electrochemical oxidation, and b is a physical diagram after electrochemical oxidation.
FIG. 2 shows the electrocatalytic material CoCu prepared in example 1 x X-ray diffraction patterns of OOH (x=0.05) and CoOOH; the blue dotted line is the diffraction peak of the base foam nickel.
FIG. 3 shows the electrocatalytic material CoCu prepared in example 1 x OOH (x=0.05).
FIG. 4 shows the electrocatalytic material CoCu prepared in example 1 x Composition analysis of OOH (x=0.05); a in fig. 4 is X-ray selective energy spectrum analysis; b is Co element distribution; c is Cu element analysis; d is EDX map; and e is the element composition ratio.
FIG. 5 shows the electrocatalytic material CoCu prepared in example 1 x X-ray surface photoelectron spectroscopy of OOH (x=0.05).
FIG. 6 is a schematic diagram of a device for glucose oxidation testing.
FIG. 7 is a graph of voltage versus current for glucose oxidation.
FIG. 8 is a graph of current versus time for oxidation of 20mmol/L glucose in 1mol/L KOH aqueous solution at 0.3V.
FIG. 9 is a nuclear magnetic resonance 1H spectrum of a product obtained by oxidizing 20mmol/L glucose in 1mol/L KOH aqueous solution at 0.3V.
FIG. 10 is a graph showing the effect of Cu doping concentration on formate yield.
FIG. 11 is a schematic diagram of an apparatus for oxidizing glucose and producing hydrogen from a single cell driven by a solar cell.
Fig. 12 is a comparison of the current-voltage curves of commercial solar cells InGaP/GaAs/Ge (5 mm x 5mm, hgsc-a 50B) for electrolysis of water at 1 sunlight (green line) and 14 sunlight (blue line) intensities and 1 (orange line) and 2 (red) cells.
Fig. 13 is a schematic diagram of a solar cell driving 2 cells to oxidize glucose and reduce water to produce hydrogen under the application of an external voltage.
Fig. 14 shows hydrogen production efficiency at different temperatures.
Detailed Description
The following detailed description of the invention is provided in connection with the accompanying drawings that are presented to illustrate the invention and not to limit the scope thereof.
The experimental methods in the following examples are conventional methods unless otherwise specified.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Example 1 electrocatalytic Material CoCu x Preparation of OOH (x=0.05)
The electrocatalytic material CoCu of the invention x OOH (x=0.05) was synthesized by electrochemical deposition reactions at room temperature as follows: with Co (NO) 3 ) 2 ·6H 2 O was used as a raw material, and 30mL of an aqueous Co solution of 0.1mol/L was prepared. Stirring uniformly, adding Cu (NO) 3 ) 2 ·3H 2 The concentration of O and Cu is 5mol% of Co, and the electrolyte required by electrochemical deposition is obtained by stirring uniformly. The electrochemical deposition adopts a three-electrode system, wherein the anode is foam nickel (thickness is 0.5mm, area is 2cm multiplied by 3 cm), the cathode is platinum sheet (area is 1cm multiplied by 2 cm), and the reference electrode is Ag/AgCl. The electrodeposition was carried out in a constant pressure mode using an electrochemical workstation, and a voltage of-1.0V was applied to the anode with respect to the reference electrode Ag/AgCl, and the electrodeposition time was 5 minutes. After the electrodeposition was completed, a green electrode was obtained by rinsing with deionized water, which is shown as a in fig. 1.
Oxidizing the obtained electrode in electrolyte of 1mol/L KOH, taking the electrode as an anode, a platinum sheet as a cathode and Ag/AgCl as a reference electrode, applying voltage of 0.3V relative to the reference electrode Ag/AgCl on the anode through a constant pressure mode of an electrochemical workstation for 5 minutes, and flushing with deionized water after the end to obtain a black electrode, namely the electrocatalytic material CoCu x OOH (x=0.05), which is shown as b in fig. 1.
The electrocatalytic material CoCu prepared by the invention x OOH (x=0.05) has a hydroxyl group oxidizedThe same crystal structure as CoOOH (see fig. 2), cu doping did not change its phase composition. Electrocatalytic material CoCu x The morphology of OOH (x=0.05) is lamellar structure, see fig. 3.EDX spectra showed a uniform distribution of Cu and Co elements, with a Cu to Co ratio of 5.32% as measured by the spectra (see fig. 4). After dissolution of the samples with hydrochloric acid, the Cu to Co ratios in the two duplicate samples were measured to be 6.3% and 6.6% using inductively coupled plasma spectroscopy. The surface photoelectron spectrum proves that the hydroxyl exists in the material, the valence state of Co is a mixed valence state of +2 and +3, and Cu is +2 (see figure 5).
The preparation method of the CoOOH comprises the following steps: with Co (NO) 3 ) 2 ·6H 2 O was used as a raw material, and 30mL of an aqueous Co solution of 0.1mol/L was prepared. Stirring uniformly to obtain the electrolyte required by electrochemical deposition. The electrochemical deposition adopts a three-electrode system, wherein the anode is foam nickel (thickness is 0.5mm, area is 2cm multiplied by 3 cm), the cathode is platinum sheet (area is 1cm multiplied by 2 cm), and the reference electrode is Ag/AgCl. The electrodeposition was carried out in a constant pressure mode using an electrochemical workstation, and a voltage of-1.0V was applied to the anode with respect to the reference electrode Ag/AgCl, and the electrodeposition time was 5 minutes. After the electrodeposition is completed, the substrate is rinsed with deionized water.
Oxidizing the obtained electrode in electrolyte of 1mol/L KOH, taking the electrode as an anode, a platinum sheet as a cathode and Ag/AgCl as a reference electrode, applying voltage of 0.3V relative to the reference electrode Ag/AgCl on the anode through a constant pressure mode of an electrochemical workstation for 5 minutes, and flushing with deionized water after the end to obtain a black electrode, namely the electrocatalytic material CoOOH.
TABLE 1 CoCu measured by inductively coupled plasma emission spectroscopy x Co and Cu content in OOH (x=0.05)
Example 2 glucose Oxidation test
The three-electrode system was used, the anode was the electrode material prepared in example 1, the cathode was a platinum sheet (area 1 cm. Times.2 cm), and the reference electrode was Ag/AgCl. The test device is an H-type electrochemical device with an anion exchange membraneThe electrolytic cells, the exchange membrane separates the cathode and anode cells, each cell containing 20mL of 1mol/L KOH aqueous solution, and the anode cell was charged with 72mg glucose. The anode electrolytic cell is prepared electrode material and reference electrode, and the cathode electrolytic cell is platinum sheet electrode. The device is shown in fig. 6. The voltage-current relationship test for glucose oxidation was performed using a linear scan mode of the electrochemical workstation at a scan rate of 2mV/s (FIG. 7). The test for complete oxidation of glucose to formic acid uses a constant voltage mode with a voltage of 0.3V applied at the anode with respect to the reference electrode until the current decays to approximately 0mA (fig. 8). Nuclear magnetic resonance gave the product as formate (8.38 ppm) in 80.9% yield (FIG. 9). The formate yield was quantitatively calculated by adding the internal standard tert-valeric acid (Pivalic acid) with a peak position of 1.03ppm. The doping concentration of Cu had an important effect on formate yield, and about 5% was optimal (FIG. 10, the preparation method of the anode used in this figure was the same as that of example 1, except that the concentration of Cu added was different, and the concentration of Cu added was 1mol%, 3mol%, 5mol%, 7mol%, 9mol% in this order). Furthermore, coOOH doped with other elements also had similar functions, but different yields, see table 2. The electrocatalytic materials used in Table 2 were prepared in the same manner as in example 1, except that the added element was different, and the specific added substance was Mn (NO 3 ) 2 ·4H 2 O、Fe(NO 3 ) 3 ·9H 2 O、Ni(NO 3 ) 2 ·6H 2 O、Cu(NO 3 ) 2 ·3H 2 O and Zn (NO) 3 ) 2 ·6H 2 O。
TABLE 2 formate yield of glucose oxidized by electrocatalytic material doped with 5mol% different elements in 1M KOH aqueous solution
| Doping element | Formate yield (%) |
| Without any means for | 50 |
| Mn | 58 |
| Fe | 63 |
| Ni | 60 |
| Cu | 80 |
| Zn | 32 |
Example 3 solar cell-driven glucose oxidation and Water reduction Hydrogen production test
Glucose oxidation and water reduction are driven by solar cells. The solar cell used in this example was a commercial InGaP/GaAs/Ge solar cell (5 mm×5mm, hgsc-a50B, shenzhen huashang. Cathode reduction of water to hydrogen material Ni 4 Mo, methods for its preparation are described in the literature (chem electrophoresis chem 1,1138-1144 (2014)). The material of the anodic oxidation glucose is CoCu x OOH (x=0.05). The test device is a single electrolytic cell, and the electrolyte is an aqueous solution of 1mol/L KOH and 0.02mol/L glucose. Under the test condition of one sun, when one electrolytic cell is driven to reduce water and oxidized glucose, the solar cell is directly connected with the cathode and the anode of the electrolytic cell, the schematic diagram is shown in fig. 11, the hydrogen production efficiency is 16.7 percent (fig. 12), and the hydrogen production efficiency is 25.9 percent when two electrolytic cells are driven (fig. 12). When the condensing lens is used for condensing 14 solar rays, the open-circuit voltage and the short-circuit current of the solar cell are both improvedThe battery efficiency also increased to 34.9% (fig. 12). At this time, the hydrogen production efficiency of one cell is 17.2% (fig. 12), and when two cells are driven, the voltage of the solar cell is insufficient to support the concentrated large current, so the hydrogen production efficiency is only 10.6% (fig. 12), and the solar cell cannot exert the maximum efficiency. Thus, an applied voltage of 0.3V was applied during the experiment through the electrochemical workstation (which could also be replaced by other power sources), as shown in fig. 13. At this time, the hydrogen production efficiency at room temperature may reach 30%, and heating may further improve the hydrogen production efficiency, as shown in fig. 14. The hydrogen production efficiency at 80 ℃ can reach 32.9 percent. In addition, the scheme of driving a plurality of electrolytic cells by a plurality of solar cells can be adopted to fully utilize the efficiency of the solar cells or customize the solar cells with required open-circuit voltage according to the requirement.
Example 4 solar cell-driven glucose oxidation and Water reduction to Hydrogen production benefits
According to some recent analysis, it is assumed that the conventional green hydrogen production with electrolyzed water can cost up to $5.90 per kilogram or less (Sustainable Energy Fuels, 1085-1094 (2021)) with a solar to hydrogen efficiency of 28%.
According to formula (1), 1kg of H is produced per production 2 49kg of potassium formate (calculated as 80% yield) can be produced. While consuming 15kg of glucose. Industrial glucose has a price of about $0.45-0.65/kg calculated from the estimated price of the April commodity chemical market in 2023 in China
(https:// www.alibaba.com/product-detail/Dextrose-raw-Gum-Bases 99-1600746592695. Htmlspm=a2700.bulletyoffferlist. Normal_offer. D_title.77a4413 aBLahEC) KOH costs about $0.95-1.35/kg
(https:// www.alibaba.com/product-detail/High-Purity-Potasium-Hydroxide-KOH-sodium_1600746995331. Htmls = p), potassium formate is about $1.05-1.25/kg
(https:// www.alibaba.com/product-detail/High-Quality-Best-Price-Potasium-format_6082324746. Htmlspm=a2700.bulletyofferlist.0.0.3 c 1040c6qcpsf7). According to the average value of market prices of the raw materials and the products (glucose: $0.55/kg, KOH: $1.15/kg, potassium formate: $1.15/kg, and yield of 80%), the material of the invention can be obtained by calculation according to the formula (1) to oxidize glucose and produce hydrogen at the same time, and each time, 1kg of H is produced 2 Additional benefits of about $4.63/kg may be achieved. Therefore, the production cost of green hydrogen is hopefully reduced to below $2.0/kg, and can be compared with the traditional methane reforming hydrogen production cost or even lower.
Claims (10)
1. A catalytic material for preparing hydrogen by electrolyzing water has chemical composition AB x OOH；0<x<0.1 wherein A is any one of Fe, co and Ni, and B is any one of Mn, fe, ni, cu and Zn.
2. Catalytic material according to claim 1, characterized in that: x is more than or equal to 0.03 and less than or equal to 0.09, preferably, x=0.05;
a is Co, B is Cu, fe or Ni; preferably, B is Cu.
3. A method of preparing a catalytic material as claimed in claim 1 or 2, comprising the steps of: weighing a source A and a source B according to stoichiometric ratio, and dissolving the sources A and the sources B in water to obtain electrolyte; and then carrying out electrochemical deposition reaction, and oxidizing the anode after the reaction to obtain the catalytic material.
4. A method of preparation according to claim 3, characterized in that: the source A is nitrate and/or sulfate of corresponding metal elements;
the source B is nitrate of corresponding metal elements;
in the electrolyte, the concentration of A is 0.05-0.3 mol/L.
5. The method according to claim 3 or 4, wherein: the electrochemical deposition reaction adopts a three-electrode system, and the cathode is a platinum sheet, platinum carbon or carbon paper; the anode is foam nickel, foam iron or carbon cloth; the reference electrode is an Ag/AgCl or saturated calomel electrode.
6. The method of any one of claims 3-5, wherein: the electrochemical deposition reaction adopts a constant pressure mode; applying a voltage of-0.8 to-1.2V relative to the reference electrode at the anode; the electrodeposition time is 1-10 min.
7. The production method according to any one of claims 3 to 6, characterized in that: the oxidation is carried out by taking an anode electrode after electrochemical deposition reaction as an anode, taking potassium hydroxide solution as electrolyte, and applying constant voltage to the anode to carry out oxidation reaction;
preferably, the oxidation employs a three-electrode system; applying a voltage of 0.1 to 0.5V to the anode with respect to the reference electrode; the oxidation time is 1-10 min.
8. Use of a catalytic material according to claim 1 or 2 in any of the following;
(1) Application in hydrogen production by water electrolysis;
(2) The application of the combination of oxidizing alcohols, saccharides or aldehydes in the hydrogen production by the electrolysis of water.
9. The use according to claim 8, characterized in that: the saccharide is glucose;
the oxidizing alcohols, saccharides or aldehydes produce formic acid.
10. Use according to claim 8 or 9, characterized in that: the power used in the application is generated by solar energy;
preferably, the power source used in the application is a solar cell.
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