CN114606535A - For electrocatalytic reduction of CO2Ni-S-C composite catalyst and preparation method thereof - Google Patents
For electrocatalytic reduction of CO2Ni-S-C composite catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 108
- 239000002131 composite material Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 230000009467 reduction Effects 0.000 title claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000000197 pyrolysis Methods 0.000 claims abstract description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 6
- 239000011258 core-shell material Substances 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 30
- 229910052799 carbon Inorganic materials 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 229920000557 Nafion® Polymers 0.000 claims description 8
- 238000011068 loading method Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 6
- 150000003852 triazoles Chemical class 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 12
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- 238000002156 mixing Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 7
- 229910021607 Silver chloride Inorganic materials 0.000 description 6
- 238000007605 air drying Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000010411 electrocatalyst Substances 0.000 description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000003624 transition metals Chemical group 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
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- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
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- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- YGHCWPXPAHSSNA-UHFFFAOYSA-N nickel subsulfide Chemical compound [Ni].[Ni]=S.[Ni]=S YGHCWPXPAHSSNA-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000037361 pathway Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- 229910052783 alkali metal Inorganic materials 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000013329 compounding Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
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- 239000003895 organic fertilizer Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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- 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
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- 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
- C25B1/23—Carbon monoxide or syngas
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- 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
- C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a method for electrocatalytic reduction of CO2The Ni-S-C composite catalyst is in a core-shell structure and comprises a core body and a shell layer coated outside the core body, wherein the core body is Ni3S2The shell layer is C; the preparation method comprises the steps of synthesizing a Ni-tri precursor by a hydrothermal method, and then carrying out high-temperature pyrolysis treatment on the Ni-tri precursor to obtain a Ni-S-C composite catalyst; the method adopts a simple hydrothermal method to synthesize a Ni-tri precursor with a porous structure, and further prepares the Ni-S-C composite catalyst material through high-temperature pyrolysis treatment; the Ni-S-C composite catalyst shows good electrocatalytic activity and higher conversion efficiency, and the highest CO Faraday efficiency can reach 66.6%; and the catalyst can be recycledAfter 5 th electrolysis, the catalyst is reduced by only 9%, the stability is good, and the efficient reuse of the catalyst is realized.
Description
Technical Field
The invention relates to the technical field of catalyst electrode preparation, in particular to a method for electrocatalytic reduction of CO2The Ni-S-C composite catalyst and the preparation method thereof.
Background
Large consumption of fossil fuelsResult in CO2The excessive emission of the organic fertilizer brings a series of problems of greenhouse effect and the like. Electrochemical reduction of CO2(CO2RR) CO conversion from renewable energy power2The electroreduction is a value-added product, and is a mild and clean method for solving the problems of environment and energy. In spite of noble metal-based electrocatalysts, such as Ag, Au and Pd electrodes, in electrochemical CO2The reduction aspect shows a high degree of selectivity, but their commercialization is hampered by the high cost and limited reserves. Therefore, there is an urgent need to develop efficient and robust catalysts based on earth-rich elements to achieve cost-effective CO2And (5) carrying out a conversion process.
In recent years, the advantages of low cost, high selectivity and high energy efficiency make the transition metal heteroatom CO-doped carbon material a promising CO2An RR electrocatalyst. Their partially closed d-orbitals close to the Fermi level, allowing the electronic structure to be optimized chemically, which improves the reaction kinetics and thus promotes the formation of intermediates (Xin-yue Wang, Qi-dong ZHao, Bin Yang, et al2reduction to CO[J]Journal of Materials Chemistry A,2019,7, 25191-. In addition, it has been shown that, among the metals of the M-N-C electrocatalyst (M represents a metal), CO is converted2General selectivity sequence for CO is Ni>Fe > Co and the order of activity is Ni, Fe > Co (Xin-Ming Hu, Halvor)
Hval,Emil Tveden Bjerglund,et al.Selective CO2 reduction to CO in water using earth-abundant metal and nitrogen-doped carbon electrocatalysts[J]ACS Catalysis,2018,8, 6255-. Therefore, the transition metal Ni becomes the first choice for the general research on the transition metal heteroatom co-doped carbon material, and a great deal of research work is invested to develop a high-performance nickel-based material as a substitute for noble metals. Wherein the nickel sulfide (e.g. NiS, NiS)2And Ni3S2) Is of great interest due to its low cost and ease of preparation, especially Ni3S2Has inherent metal behavior and high conductivity, and is an important property of the electrocatalyst (Geng Zhang, Yu-Shuo Feng, Wang-Ting Lu, et al. enhanced catalysis of electrochemical over water splitting in alkali metal media by Fe doping in Ni3S2 nanosheet arrays[J]ACS Catalysis,2018,8, 5431-. However, the related research is limited to the full hydrolysis, and is only related to CO2The RR aspect is not involved.
As can be seen from the above, the existing CO2RR electrocatalysts cannot compromise on preparation cost, selectivity, and energy utilization efficiency.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a catalyst for electrocatalytic reduction of CO with low cost, high selectivity and high energy efficiency2The Ni-S-C composite catalyst; another object of the present invention is to provide a method for preparing a Ni-S-C composite catalyst; it is another object of the present invention to provide an electrode; another object of the present invention is to provide a method for preparing an electrode.
The technical scheme is as follows: the invention is used for electrocatalytic reduction of CO2The Ni-S-C composite catalyst is in a core-shell structure and comprises a core body and a shell layer coated outside the core body, wherein the core body is Ni3S2And the shell layer is C.
In another aspect, the present invention provides a method for preparing a Ni-S-C composite catalyst, comprising the steps of:
(1) synthesizing a Ni-tri precursor by a hydrothermal method: adding nickel sulfate and triazole into deionized water for dissolving, adjusting pH, fully reacting at constant temperature, cleaning and drying the product to obtain Ni-tri precursor
(2) And carrying out high-temperature pyrolysis treatment on the Ni-tri precursor to obtain the Ni-S-C composite catalyst.
Further, in the step (1), the molar ratio of nickel sulfate to triazole is 1: 1.5-1; adjusting the pH value by using hydrofluoric acid, wherein the volume ratio of the hydrofluoric acid to the deionized water is 1: 70-80; the constant temperature is 180-200 ℃, and the reaction time is 40-60 h; the above conditions are favorable for crystal structure growth, the crystallinity is improved, and the Ni-tri precursor is in the shape of an octahedron and has a porous structure and higher stability.
Further, in the step (1), the drying step is drying in a drying oven at 80 ℃, which is beneficial to the volatilization of deionized water and can not remove crystal water in the Ni-tri precursor structure.
Further, in the step (2), the Ni-tri precursor is put into a tube furnace for high-temperature pyrolysis, and N is used for pyrolysis2Heating to 800-1000 ℃ in the atmosphere, keeping the temperature for at least 1h, specifically, in N2Heating to 800, 900 and 1000 ℃ respectively at the heating rate of 5 ℃/min from 30 ℃ in the atmosphere; the above conditions are favorable for preparing the transition metal heteroatom co-doped carbon material.
In another aspect, the invention provides a method for preparing the Ni-S-C composite catalyst by the method for electrocatalytic reduction of CO2The use of (1).
Electrocatalytic reduction of CO by Ni-S-C composite catalyst2The catalytic efficiency is obviously improved, wherein S has larger atomic size and polarizability than C, and S doping provides edge strain, charge delocalization characteristics and higher spin density for a carbon structure, so that the doping of S element improves CO2The effect on the catalytic activity of RR is particularly significant. On one hand, S is doped in a carbon structure without obvious charge redistribution because the electronegativity of the S element is very similar to that of C; on the contrary, because the element has larger size, the adjustment of S in a carbon structure causes remarkable structural defects, further increases the specific surface area of the material, exposes new active sites and improves the activity of the catalyst; on the other hand, S doping promotes the CO pathway and inhibits the HER pathway; furthermore, in terms of kinetics, S doping increases the electrochemically active surface area, improving charge transfer.
In another aspect, the present invention provides an electrode comprising the Ni-S-C composite catalyst prepared by the above-described preparation method.
Further, mixing the Ni-S-C composite catalyst with conductive carbon black, stirring and dispersing in a Nafion ethanol solution to form uniform catalyst suspension, coating the catalyst suspension on the surface of the carbon paper electrode, and air-drying at room temperature to obtain the carbon paper electrode loaded with the Ni-S-C composite catalyst.
Further, mixing the Ni-S-C composite catalyst with conductive carbon black, stirring and dispersing in a Nafion ethanol solution with the mass fraction of 0.5% for 12-24 hours to form uniform catalyst suspension; the mass ratio of the mixed Ni-S-C composite catalyst to the conductive carbon black is 1: 1.5-2.5; the loading capacity of the Ni-S-C composite catalyst on the carbon paper electrode is 2-3 mg/cm2(ii) a The condition is favorable for uniform dispersion of the catalyst and increases the catalytic activity area.
The invention adopts a simple hydrothermal method to synthesize a Ni-tri precursor with a porous structure, and further prepares the Ni-S-C composite catalyst material through high-temperature pyrolysis treatment. The catalyst has the characteristics that the catalyst not only keeps the porous structure of a precursor, but also improves the specific surface area and the pore volume, and brings the benefits of high conductivity, more active sites and good mass transfer effect. Then carbon paper with good stability, corrosion resistance, good permeability and high conductivity is used as a substrate electrode, and Ni-S-C composite catalyst is loaded on the carbon paper to obtain CO2RR performance offers good conditions. Electrochemical performance tests are carried out in a three-electrode system, and the electrode prepared by the method is found to show good electrocatalytic activity, high conversion efficiency and good stability, and can be efficiently recycled.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages:
(1) the Ni-tri precursor is synthesized by a hydrothermal method, the raw materials are cheap and easy to obtain, the equipment requirement is simple, the operation is convenient, the process is pollution-free and harmless, and the obtained precursor crystal has a porous structure;
(2) the Ni-S-C composite catalyst derived from the high-temperature pyrolysis Ni-tri precursor not only keeps the porous structure of the precursor, but also improves the specific surface area and the pore volume, and brings the benefits of high conductivity, many active sites and good mass transfer effect;
(3) the Ni-S-C composite catalyst shows good electrocatalytic activity and higher conversion efficiency, and the highest CO Faraday efficiency can reach 66.6%; the catalyst can be recycled, the reduction of the catalyst by only 9% after the 5 th electrolysis is realized, the stability is good, and the efficient recycling of the catalyst is realized.
(4) The carbon paper electrode has good stability, corrosion resistance, porous permeability, good conductivity, high cost performance and low manufacturing cost; loading Ni-S-C composite catalyst on carbon paper as CO2RR performance offers good conditions.
Drawings
FIG. 1 is a simulated and synthetic X-ray diffraction pattern of Ni-tri precursor prepared in examples 1-3 of the present invention;
FIG. 2 shows Ni-S-C prepared according to examples 1-3 of the present invention800、Ni-S-C900、Ni-S-C1000An X-ray diffraction pattern of the composite catalyst;
FIG. 3 is a Scanning Electron Microscope (SEM) picture of Ni-tri precursor prepared in examples 1-3 of the present invention, with a scale bar of 200 μm;
FIG. 4 shows Ni-S-C prepared in example 1 of the present invention800Scanning Electron Microscope (SEM) picture of the composite catalyst, the scale is 10 μm;
FIG. 5 shows Ni-S-C prepared in example 2 of the present invention900Scanning Electron Microscope (SEM) picture of the composite catalyst, the scale is 10 μm;
FIG. 6 shows Ni-S-C prepared in example 3 of the present invention1000Scanning Electron Microscope (SEM) picture of the composite catalyst, the scale is 10 μm;
FIG. 7 shows Ni-S-C prepared in example 3 of the present invention1000A Transmission Electron Microscope (TEM) picture of the composite catalyst, wherein a ruler is 1 mu m;
FIG. 8 shows Ni-S-C prepared in example 3 of the present invention1000High Resolution Transmission Electron Microscopy (HRTEM) pictures of the composite catalyst with a scale of 200nm and 50nm respectively;
FIG. 9 is a nitrogen adsorption/desorption curve and a pore size distribution diagram of Ni-S-C composite catalysts prepared in examples 1 to 3 of the present invention;
FIG. 10 is a Linear Sweep Voltammogram (LSV) of Ni-S-C composite catalysts prepared in examples 1-3 of the present invention;
FIG. 11 is a graph showing the Faraday efficiencies of CO obtained by electrolyzing the Ni-S-C composite catalyst prepared in examples 1 to 3 of the present invention at a potential of-1.3V to-1.7V vs. Ag/AgCl for 2 hours;
FIG. 12 shows Ni-S prepared in example 3 of the present invention-C1000The time current curve diagram and the corresponding Faraday efficiency chart are obtained by electrolyzing the composite catalyst for 24 hours under the potential of-1.5V vs. Ag/AgCl;
FIG. 13 shows Ni-S-C prepared in example 3 of the present invention1000And (3) performing cyclic electrolysis on the composite catalyst for 5 times under the potential of-1.5V vs.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings.
Example 1
The preparation method of the Ni-S-C composite catalyst comprises the following steps:
(1) synthesizing a Ni-tri precursor: in 15mL of H2Adding 315mg of NiSO into O4·6H2O, 166mg1,2, 4-triazole, was magnetically stirred for 1h to give a dark blue clear solution. To the solution was added 0.2mL of HF and stirred briefly for half a minute, and the solution was transferred to a 25mL Teflon reactor and heated at 200 ℃ for 48 h. When the reaction kettle is cooled to room temperature, washing the product with deionized water, and drying in a drying oven at 80 ℃ to obtain dark blue crystal powder;
(2) preparing a Ni-S-C composite catalyst material: pouring the prepared Ni-tri precursor into an alumina porcelain boat, heating to 800 ℃ at the speed of 5 ℃/min in a tubular furnace under the nitrogen atmosphere, and keeping the temperature for 1 h. Cooling to room temperature to obtain black solid powder named Ni-S-C800。
The method for preparing the electrode by using the Ni-S-C composite catalyst comprises the following steps:
mixing Ni-S-C800Mixing with conductive carbon black at a ratio of 1:2, adding 1mL 0.5% (mass fraction) Nafion ethanol solution, magnetically stirring for 12h to form uniform catalyst suspension, and coating the suspension on the surface of carbon paper electrode to ensure coverage area of 1 × 1cm2X 2, catalyst loading 2.5mg/cm2Air-drying at room temperature to obtain Ni-S-C800A supported carbon paper electrode.
Example 2
The preparation method of the Ni-S-C composite catalyst comprises the following steps:
(1) the method of synthesizing the Ni-tri precursor was the same as in example 1;
(2) preparing a Ni-S-C composite catalyst material: pouring the prepared Ni-tri precursor into an alumina porcelain boat, heating to 900 ℃ at the speed of 5 ℃/min in a tubular furnace under the nitrogen atmosphere, and keeping the temperature for 1 h. Cooling to room temperature to obtain black solid powder named Ni-S-C900。
The method for preparing the electrode by using the Ni-S-C composite catalyst comprises the following steps:
mixing Ni-S-C900Mixing with conductive carbon black at a ratio of 1:2, adding 1mL 0.5% (mass fraction) Nafion ethanol solution, magnetically stirring for 12h to form uniform catalyst suspension, and coating the suspension on the surface of carbon paper electrode to ensure coverage area of 1 × 1cm2X 2, catalyst loading 2.5mg/cm2Air-drying at room temperature to obtain Ni-S-C900A supported carbon paper electrode.
Example 3
The preparation method of the Ni-S-C composite catalyst comprises the following steps:
(1) synthesizing a Ni-tri precursor: in 15mL of H2Adding 315mg of NiSO into O4·6H2O, 332mg1,2, 4-triazole, was magnetically stirred for 1h to give a dark blue clear solution. To the solution was added 0.23mL of HF and stirred briefly for half a minute, and the solution was transferred to a 25mL Teflon reactor and heated at 200 ℃ for 48 h. When the reaction kettle is cooled to room temperature, washing the product with deionized water, and drying in a drying oven at 80 ℃ to obtain dark blue crystal powder;
(2) preparing a Ni-S-C composite catalyst material: pouring the prepared Ni-tri precursor into an alumina porcelain boat, heating to 1000 ℃ at the speed of 5 ℃/min in a tubular furnace under the nitrogen atmosphere, and keeping the temperature for 1 h. Cooling to room temperature to obtain black solid powder named Ni-S-C1000。
The method for preparing the electrode by using the Ni-S-C composite catalyst comprises the following steps:
mixing Ni-S-C1000Mixing with conductive carbon black at a ratio of 1:2, adding 1mL of 0.5% (mass fraction) Nafion ethanol solution, magnetically stirring for 12h to form uniform catalyst suspension, and coating the suspension on carbon paperThe surface of the electrode is covered with a cover area of 1 × 1cm2X 2, catalyst loading 2.5mg/cm2Air-drying at room temperature to obtain Ni-S-C1000A supported carbon paper electrode.
Example 4
The preparation method of the Ni-S-C composite catalyst comprises the following steps:
(1) the method of synthesis of Ni-tri precursor was the same as in example 1, except that: the molar ratio of the nickel sulfate to the triazole is 1: 1.5; the volume ratio of the hydrofluoric acid to the deionized water is 1: 70; the constant temperature reaction temperature is 180 ℃, and the reaction time is 60 h.
(2) Preparing a Ni-S-C composite catalyst material: same as in example 1.
The method for preparing the electrode by using the Ni-S-C composite catalyst comprises the following steps:
mixing Ni-S-C and conductive carbon black in a ratio of 1:1.5, adding 1mL of 0.5% (mass fraction) Nafion ethanol solution, magnetically stirring for 12h to form uniform catalyst suspension, and coating the catalyst suspension on the surface of a carbon paper electrode to ensure that the coverage area is 1 × 1cm2X 2, catalyst loading 2mg/cm2And air-drying at room temperature to obtain the Ni-S-C loaded carbon paper electrode.
Example 5
The preparation method of the Ni-S-C composite catalyst comprises the following steps:
(1) the method of synthesis of Ni-tri precursor was the same as in example 1, except that: the molar ratio of the nickel sulfate to the triazole is 1: 3; the volume ratio of the hydrofluoric acid to the deionized water is 1: 80; the constant temperature reaction temperature is 200 ℃, and the reaction time is 40 h.
(2) Preparing a Ni-S-C composite catalyst material: same as in example 1.
The method for preparing the electrode by using the Ni-S-C composite catalyst comprises the following steps:
mixing Ni-S-C and conductive carbon black in a ratio of 1:2.5, adding 1mL of 0.5% (mass fraction) Nafion ethanol solution, magnetically stirring for 12h to form uniform catalyst suspension, and coating the catalyst suspension on the surface of a carbon paper electrode to ensure that the coverage area is 1 × 1cm2X 2, catalyst loading of 3mg/cm2And air-drying at room temperature to obtain the Ni-S-C loaded carbon paper electrode.
Product characterization for examples 1-3:
as can be seen from the X-ray diffraction patterns of FIG. 1 and FIG. 2, the diffraction peak obtained by testing the synthesized Ni-tri precursor of the present invention is similar to the simulated diffraction peak, indicating that the synthesized substance is the target product and has higher purity. The Ni-S-C composite catalyst prepared by high-temperature pyrolysis of the Ni-tri precursor at 800-1000 ℃ does not show the diffraction peak of the precursor, and as can be seen from figure 2, the Ni-S-C composite catalyst has stronger Ni at the angles of 21.8 degrees, 31.1 degrees, 37.8 degrees, 38.3 degrees, 49.7 degrees, 50.1 degrees, 54.6 degrees and 55.2 degrees3S2Diffraction peaks, corresponding to the peaks of Ni at angles of 44.5 degrees, 51.8 degrees and 76.4 degrees, indicate that the structure of the Ni-tri precursor is destroyed after high-temperature pyrolysis, and a new composite product is derived.
As shown in FIG. 3, the Ni-tri precursors synthesized in examples 1 to 3 were regular octahedral crystals, and were partially unformed. The Ni-S-C composite catalyst after high-temperature pyrolysis is spherical particles with uneven sizes, and the spherical particles are Ni by combining the analysis of an X-ray diffraction pattern3S2。
The TEM image of FIG. 7 and the TEM image of FIG. 8 show that Ni is present in the sample3S2The surface of the spherical particles is covered by a thin and uneven carbon shell outer layer, and carbon element is used as a substrate. Shows that Ni is obtained after the high-temperature pyrolysis of the Ni-tri precursor3S2The Ni-S-C composite catalyst takes a main body and carbon as a substrate.
Ni-S-C composite catalyst of FIG. 9 vs. N at 77K2The adsorption and desorption isotherm graphs show an H4 type hysteresis loop formed by compounding the type I isotherm and the type II isotherm, and the material has a micropore and mesopore structure. As shown in table 1, the specific surface area and pore volume of the material gradually increased with the increase in pyrolysis temperature. The pore size distribution curves for all samples obtained by calculating the differential of pore volume with respect to pore diameter, i.e., the amount of pore volume change per unit pore diameter, according to the BJH method have similar shapes, which means that the Ni — S — C composite catalyst has similar uniform pore diameters. Ni-S-C composite catalyst at 0.88nm andabout 1.91nm having a maximum intensity peak, Ni-S-C1000Is larger than the pore volume of the other samples. These results indicate that pyrolysis collapses the mesostructure of the precursor, forms micropores, thereby forming a broad pore distribution, and that an increase in pyrolysis temperature leads to an increase in pore size.
TABLE 1
Testing of electrochemical reduction of CO with Ni-S-C composite catalyst2Performance:
the test is carried out in a closed H-shaped electrolytic cell device, a carbon paper electrode loaded by a Ni-S-C composite catalyst is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a platinum sheet electrode is used as a counter electrode, and an electrolyte is CO2Saturated 0.1mol/LKHCO3An aqueous solution. The electrochemical performance correlation characterization is linear sweep voltammetry and time-current curve test, and the qualitative and quantitative analysis is carried out on the gas phase product through a gas chromatograph.
FIG. 10 is a linear sweep voltammogram measured for Ni-S-C composite catalyst-supported carbon paper electrodes prepared in examples 1-3. At the same potential, Ni-S-C1000Showing the highest current density, Ni-S-C900Second, Ni-S-C800The lowest current density. This preliminary demonstrates that of the three composite catalysts, Ni-S-C1000Electrochemical reduction of CO2The performance is the best.
FIG. 11 is a graph of the Faraday efficiencies of CO obtained from the Ni-S-C composite catalyst-supported carbon paper electrodes prepared in examples 1-3 by electrolysis at potentials of-1.3V to-1.7V vs. Ag/AgCl for 2 h. The CO Faraday efficiencies of the three Ni-S-C composite catalysts show a trend of increasing and then decreasing along with the change of the potential, and the highest CO Faraday efficiency is achieved at the potential of-1.5 Vvs. Wherein Ni-S-C prepared in example 31000Has the highest CO Faraday efficiency of 66.6 percent, and Ni-S-C800The Faraday efficiency of CO of (1) is 40.2%, and that of Ni-S-C900The faradaic efficiency of CO was 47.4%.
Ni-S-C prepared in example 31000Has better electrochemical reduction of CO2Performance, and therefore their stability at-1.5V vs. ag/AgCl potential was further tested. Fig. 12 shows that the current density had a tendency to slowly decrease during the first 10 hours, and then reached a plateau, which was relatively stable. The inset shows the faradaic efficiency of the products at electrolysis times of 2,4, 6, 8, 10, 24h, within 24h of electrolysis, Ni-S-C1000The faradaic efficiency of the catalyst is maintained at 55%, which shows that the stability of the catalyst is better.
FIG. 13 further illustrates Ni-S-C prepared in example 31000A cyclicity test was performed. The same electrode is repeatedly electrolyzed for 5 times under the potential of-1.5V vs. Ag/AgCl, the CO Faraday efficiency is reduced a little after each electrolysis, and is reduced by only 9% after the 5 th electrolysis, thereby realizing the high-efficiency reutilization of the catalyst.
Claims (10)
1. For electrocatalytic reduction of CO2The Ni-S-C composite catalyst is characterized in that the Ni-S-C composite catalyst is of a core-shell structure and comprises a core body and a shell layer coated outside the core body, wherein the core body is Ni3S2And the shell layer is C.
2. A preparation method of a Ni-S-C composite catalyst is characterized by comprising the following steps:
(1) synthesizing a Ni-tri precursor by a hydrothermal method: adding nickel sulfate and triazole into deionized water for dissolving, adjusting pH, fully reacting at constant temperature, cleaning and drying the product to obtain Ni-tri precursor
(2) And carrying out high-temperature pyrolysis treatment on the Ni-tri precursor to obtain the Ni-S-C composite catalyst.
3. The method for preparing the Ni-S-C composite catalyst according to claim 1, wherein in the step (1), the molar ratio of the nickel sulfate to the triazole is 1: 1.5-3.
4. The preparation method of the Ni-S-C composite catalyst according to claim 1, wherein in the step (1), hydrofluoric acid is used for adjusting the pH, and the volume ratio of the hydrofluoric acid to the deionized water is 1: 70-80.
5. The preparation method of the Ni-S-C composite catalyst according to claim 1, wherein in the step (1), the constant temperature is 180-200 ℃ and the reaction time is 40-60 h.
6. The method for preparing the Ni-S-C composite catalyst according to claim 1, wherein in the step (2), the Ni-tri precursor is subjected to pyrolysis in a tube furnace at high temperature, and N is used2Heating to 800-1000 ℃ in the atmosphere, and keeping the temperature for at least 1 h.
7. An electrode comprising the Ni-S-C composite catalyst according to claim 1.
8. The preparation method of the electrode according to claim 1, wherein the Ni-S-C composite catalyst is mixed with conductive carbon black, stirred and dispersed in Nafion ethanol solution to form uniform catalyst suspension, and the catalyst suspension is coated on the surface of the carbon paper electrode and dried at room temperature to obtain the carbon paper electrode loaded with the Ni-S-C composite catalyst.
9. The method for preparing the electrode according to claim 8, wherein the mass ratio of the Ni-S-C composite catalyst to the conductive carbon black is 1:1.5 to 2.5.
10. The method for preparing the electrode according to claim 8, wherein the loading amount of the Ni-S-C composite catalyst on the carbon paper electrode is 2-3 mg/cm2。
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| YANGFEI CAO ET AL.: ""Nitrogen-, Oxygen- and Sulfur-Doped Carbon-Encapsulated Ni3S2 and NiS Core–Shell Architectures: Bifunctional Electrocatalysts for Hydrogen Evolution and Oxygen Reduction Reactions"", ACS SUSTAINABLE CHEMISTRY & ENGINEERING》, vol. 6, no. 11, pages 15582 - 15590 * |
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