CN114606535B - CO used for electrocatalytic reduction 2 Ni-S-C composite catalyst and preparation method thereof - Google Patents
CO used for electrocatalytic reduction 2 Ni-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 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000009467 reduction Effects 0.000 title abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 37
- 238000000197 pyrolysis Methods 0.000 claims abstract description 17
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 34
- 229910052799 carbon Inorganic materials 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 11
- 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
- 238000011068 loading method Methods 0.000 claims description 9
- 229920000557 Nafion® Polymers 0.000 claims description 8
- 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
- 239000012798 spherical particle Substances 0.000 claims description 6
- 150000003852 triazoles Chemical class 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 8
- 238000005868 electrolysis reaction Methods 0.000 abstract description 6
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000011258 core-shell material Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 13
- 239000011148 porous material Substances 0.000 description 12
- 229910021607 Silver chloride Inorganic materials 0.000 description 7
- 239000010411 electrocatalyst Substances 0.000 description 7
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000007605 air drying Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229910001339 C alloy Inorganic materials 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 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
- 230000008901 benefit Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000002349 favourable effect Effects 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
- 239000003575 carbonaceous material Substances 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
- 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
- 238000012546 transfer Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000080590 Niso Species 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 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
- 230000008569 process Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- -1 NiS Chemical compound 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 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
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 230000007847 structural defect Effects 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
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
- C25B11/091—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
-
- 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
-
- 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
-
- 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
Abstract
The invention discloses a catalyst for electrocatalytic reduction of CO 2 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 Ni 3 S 2 The shell layer is C; the preparation method comprises the steps of synthesizing a Ni-tri precursor by a hydrothermal method, and then performing pyrolysis treatment on the Ni-tri precursor to obtain a Ni-S-C composite catalyst; the Ni-tri precursor with a porous structure is synthesized by adopting a simple hydrothermal method, and the Ni-S-C composite catalyst material is further prepared by high-temperature pyrolysis treatment; the Ni-S-C composite catalyst provided by the invention has good electrocatalytic activity and higher conversion efficiency, and the highest CO Faraday efficiency is 66.6%; and the catalyst can be recycled, only 9% of the catalyst is reduced after the 5 th electrolysis, the stability is good, and the efficient recycling of the catalyst is realized.
Description
Technical Field
The invention relates to the technical field of catalyst electrode preparation, in particular to a catalyst for electrocatalytic reduction of CO 2 The Ni-S-C composite catalyst and the preparation method thereof.
Background
The massive consumption of fossil fuels results in CO 2 And brings about a series of problems such as greenhouse effect. Electrochemical reduction of CO 2 (CO 2 RR) use of renewable energy power to convert CO 2 The electroreduction to value-added products is a mild and clean method for solving the environmental and energy problems. Although noble metal-based electrocatalysts, such as Ag, au and Pd electrodes, in electrochemical CO 2 The reduction aspect shows a high degree of selectivity, but the high cost and limited reserves prevent their commercialization. Therefore, there is an urgent need to develop efficient and robust catalysts based on earth-rich elementsTo realize low-cost and high-benefit CO 2 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 very promising CO 2 RR electrocatalyst. Their partially closed d-orbitals approach the fermi level, which allows optimization of the electronic structure from a chemical point of view, which increases the kinetics of the reaction and thus promotes the formation of intermediates (Xin-yue Wang, qi-dong Zhao, bin Yang, et al emerging nanostructured carbon-based nonprecious metal electrocatalysts for selective electrochemical CO 2 reduction to CO[J]Journal of Materials Chemistry A,2019,7,25191-25202). In addition, studies have shown that in the metal of M-N-C electrocatalysts (M represents a metal), CO is converted 2 The general selectivity sequence for CO is Ni>Fe > Co, and the active order is Ni, fe > Co (Xin-Ming Hu, halvor)Hval,Emil Tveden Bjerglund,et al.Selective CO 2 reduction to CO in water using earth-abundant metal and nitrogen-doped carbon electrocatalysts[J]ACS Catalysis,2018,8,6255-6264). Therefore, transition metal Ni is the first choice for general research into transition metal heteroatom co-doped carbon materials, and a great deal of research effort has been devoted to developing high-performance nickel-based materials as alternatives to noble metals. Wherein nickel sulfide (such as NiS, niS 2 And Ni 3 S 2 ) Attention is paid to the low cost and convenient preparation, in particular to Ni 3 S 2 Has inherent metal behavior and high conductivity, and is an important property of electrocatalyst (Geng Zhang, yu-Shuo Feng, wang-Ting Lu, et al advanced catalysis of electrochemical overall water splitting in alkaline media by Fe doping in Ni) 3 S 2 nanosheet arrays[J]ACS Catalysis,2018,8,5431-5441). However, the related research is limited to the full water dissolution, but is performed on CO 2 The RR aspect is not involved.
In conclusion, the existing CO 2 RR electrocatalyst cannot be prepared at cost and choiceBoth performance and energy utilization efficiency.
Disclosure of Invention
The invention aims to: the invention aims to provide a catalyst for electrocatalytic reduction of CO, which has low cost, high selectivity and high energy efficiency 2 The Ni-S-C composite catalyst in the (B); 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 CO 2 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 Ni 3 S 2 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 dissolution, adjusting pH, fully reacting at constant temperature, and cleaning and drying the product to obtain a Ni-tri precursor
(2) The Ni-tri precursor is subjected to high-temperature pyrolysis treatment to obtain the Ni-S-C composite catalyst.
Further, in the step (1), the molar ratio of the nickel sulfate to the triazole is 1:1.5-1; adjusting the pH value by using hydrofluoric acid, wherein the volume ratio of the hydrofluoric acid to deionized water is 1:70-80; the constant temperature is 180-200 ℃, and the reaction time is 40-60 h; the conditions are favorable for the growth of a crystal structure, the crystallinity is improved, and the Ni-tri precursor is in a regular octahedral morphology, 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 favorable for volatilization of deionized water, and does 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 a hydrogen atom 2 Heating to 800-1000 ℃ under atmosphere, keeping constant temperature for at least 1h, in particular, in N 2 Respectively adding at a temperature rising rate of 5 ℃/min from 30 ℃ under atmosphereHeating to 800, 900 and 1000 ℃; the conditions are favorable for preparing the transition metal heteroatom co-doped carbon material.
On the other hand, the invention provides a Ni-S-C composite catalyst prepared by the method for electrocatalytically reducing CO 2 Is used in the field of applications.
Ni-S-C composite catalyst for electrocatalytic reduction of CO 2 Wherein S has a larger atomic size and polarizability than C, S doping provides edge strain, charge delocalization and higher spin density to the carbon structure, so the doping of S element is improving CO 2 The effect of RR catalytic activity is particularly remarkable. On the one hand, since the electronegativity of the S element is very similar to that of C, S doping does not produce significant charge redistribution in the carbon structure; in contrast, because the element has larger size, the regulation of S in the carbon structure causes obvious structural defects, the specific surface area of the material is further increased, new active sites are exposed, and the activity of the catalyst is improved; on the other hand S-doping promotes the CO pathway while inhibiting the HER pathway; in addition, 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, the Ni-S-C composite catalyst and the conductive carbon black are mixed, stirred and dispersed in Nafion ethanol solution to form uniform catalyst suspension, the catalyst suspension is coated on the surface of the carbon paper electrode, and the carbon paper electrode loaded by the Ni-S-C composite catalyst is obtained by air drying at room temperature.
Further, mixing the Ni-S-C composite catalyst with conductive carbon black, stirring and dispersing in Nafion ethanol solution with mass fraction of 0.5% for 12-24 hours to form uniform catalyst suspension; the mass ratio of the 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/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The condition is favorable for uniform dispersion of the catalyst and increases the catalytic activity area.
The invention synthesizes the Ni-tri precursor with porous structure by adopting a simple hydrothermal methodAnd preparing the Ni-S-C composite catalyst material by high-temperature pyrolysis treatment. The catalyst has the characteristics of retaining the porous structure of the precursor, improving the specific surface area and the pore volume, and bringing the benefits of high conductivity, multiple active sites and good mass transfer effect. Then, taking carbon paper with good stability, corrosion resistance, good permeability and high conductivity as a base electrode, and loading the Ni-S-C composite catalyst on the carbon paper to obtain CO thereof 2 RR performance exertion provides good conditions. The electrochemical performance test is carried out in a three-electrode system, and the prepared electrode is found to have good electrocatalytic activity, higher conversion efficiency and better stability and can be recycled with high efficiency.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable advantages:
(1) Synthesizing Ni-tri precursor by a hydrothermal method, wherein raw materials are cheap and easy to obtain, equipment requirements are simple, 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 maintains the porous structure of the precursor, but also improves the specific surface area and the pore volume, thereby bringing the benefits of high conductivity, more active sites and good mass transfer effect;
(3) The Ni-S-C composite catalyst has good electrocatalytic activity and higher conversion efficiency, and the highest Faraday efficiency of CO is 66.6%; and the catalyst can be recycled, only 9% of the catalyst is reduced after the 5 th electrolysis, 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 to obtain CO thereof 2 RR performance exertion provides good conditions.
Drawings
FIG. 1 is a simulated and synthesized X-ray diffraction pattern of Ni-tri precursors prepared in examples 1-3 of the present invention;
FIG. 2 shows Ni-S-C as prepared in examples 1-3 of the present invention 800 、Ni-S-C 900 、Ni-S-C 1000 An X-ray diffraction pattern of the composite catalyst;
FIG. 3 is a Scanning Electron Microscope (SEM) picture of the Ni-tri precursor prepared in examples 1-3 of the present invention, scale 200 μm;
FIG. 4 is a Ni-S-C film prepared in example 1 of the present invention 800 Scanning Electron Microscope (SEM) pictures of the composite catalyst, and the scale is 10 mu m;
FIG. 5 is a Ni-S-C film prepared in example 2 of the present invention 900 Scanning Electron Microscope (SEM) pictures of the composite catalyst, and the scale is 10 mu m;
FIG. 6 is a Ni-S-C alloy of example 3 of the present invention 1000 Scanning Electron Microscope (SEM) pictures of the composite catalyst, and the scale is 10 mu m;
FIG. 7 is a Ni-S-C alloy of example 3 of the present invention 1000 A Transmission Electron Microscope (TEM) picture of the composite catalyst, with a scale of 1 μm;
FIG. 8 is a Ni-S-C alloy of example 3 of the present invention 1000 High Resolution Transmission Electron Microscope (HRTEM) pictures of the composite catalyst are respectively provided with a scale of 200nm and a scale of 50nm;
FIG. 9 is a graph showing the nitrogen adsorption and desorption curves and pore size distribution of the Ni-S-C composite catalyst prepared in examples 1-3 of the present invention;
FIG. 10 is a Linear Sweep Voltammogram (LSV) of the Ni-S-C composite catalyst prepared in examples 1-3 of this invention;
FIG. 11 is a Faraday efficiency chart of CO obtained by electrolyzing the Ni-S-C composite catalyst prepared in the embodiment 1-3 of the invention for 2 hours under the potential of-1.3V to-1.7V vs. Ag/AgCl;
FIG. 12 is a Ni-S-C alloy of example 3 of the present invention 1000 A time current curve graph and a corresponding Faraday efficiency graph are obtained by electrolyzing the composite catalyst for 24 hours under the potential of-1.5V vs. Ag/AgCl;
FIG. 13 is a Ni-S-C alloy of example 3 of the present invention 1000 The composite catalyst is circularly electrolyzed for 5 times under the potential of minus 1.5V vs. Ag/AgCl to obtain Faraday efficiency graph.
Detailed Description
The technical scheme of the invention is further described below with reference to the accompanying drawings.
Example 1
The preparation method of the Ni-S-C composite catalyst comprises the following steps:
(1) Synthesizing a Ni-tri precursor: at 15mL H 2 Adding 315mg of NiSO to O 4 ·6H 2 O,166mg1,2, 4-triazole, and magnetically stirring for 1h to obtain a dark blue clear solution. To the solution was added 0.2mL HF and stirred briefly for half a minute, the solution was transferred to a 25mL teflon reactor and heated at 200 ℃ for 48h. After the reaction kettle is cooled to room temperature, cleaning a product by deionized water, and drying in a drying oven at 80 ℃ to obtain deep blue crystal powder;
(2) Preparing a Ni-S-C composite catalyst material: the Ni-tri precursor prepared above is poured into an alumina porcelain boat, and is heated to 800 ℃ at a speed of 5 ℃/min in a tube furnace under nitrogen atmosphere, and the temperature is kept for 1h. Cooling to room temperature to obtain black solid powder, named Ni-S-C 800 。
The method for preparing the electrode by using the Ni-S-C composite catalyst comprises the following steps:
Ni-S-C 800 Mixing with conductive carbon black at a ratio of 1:2, adding 1mL of 0.5% (mass fraction) Nafion ethanol solution, magnetically stirring for 12 hr to form uniform catalyst suspension, and coating on the surface of carbon paper electrode to ensure coverage area of 1×1cm 2 X 2, catalyst loading of 2.5mg/cm 2 Air-drying at room temperature to obtain Ni-S-C 800 A loaded carbon paper electrode.
Example 2
The preparation method of the Ni-S-C composite catalyst comprises the following steps:
(1) The method for synthesizing the Ni-tri precursor is the same as in example 1;
(2) Preparing a Ni-S-C composite catalyst material: the Ni-tri precursor prepared above is poured into an alumina porcelain boat, and is heated to 900 ℃ at a speed of 5 ℃/min in a tube furnace under nitrogen atmosphere, and the temperature is kept for 1h. Cooling to room temperature to obtain black solid powder, named Ni-S-C 900 。
The method for preparing the electrode by using the Ni-S-C composite catalyst comprises the following steps:
Ni-S-C 900 Mixing with conductive carbon black in a ratio of 1:2Adding 1mL of 0.5% (mass fraction) Nafion ethanol solution, magnetically stirring for 12 hr to form uniform catalyst suspension, and coating on the surface of carbon paper electrode to ensure coverage area of 1×1cm 2 X 2, catalyst loading of 2.5mg/cm 2 Air-drying at room temperature to obtain Ni-S-C 900 A loaded 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: at 15mL H 2 Adding 315mg of NiSO to O 4 ·6H 2 O, 336 mg of 1,2, 4-triazole was magnetically stirred for 1h to give a dark blue clear solution. To the solution was added 0.23mL HF and stirred briefly for half a minute, the solution was transferred to a 25mL teflon reactor and heated at 200 ℃ for 48h. After the reaction kettle is cooled to room temperature, cleaning a product by deionized water, and drying in a drying oven at 80 ℃ to obtain deep blue crystal powder;
(2) Preparing a Ni-S-C composite catalyst material: the Ni-tri precursor prepared above is poured into an alumina porcelain boat, and is heated to 1000 ℃ at a speed of 5 ℃/min in a tube furnace under nitrogen atmosphere, and the temperature is kept for 1h. Cooling to room temperature to obtain black solid powder, named Ni-S-C 1000 。
The method for preparing the electrode by using the Ni-S-C composite catalyst comprises the following steps:
Ni-S-C 1000 Mixing with conductive carbon black at a ratio of 1:2, adding 1mL of 0.5% (mass fraction) Nafion ethanol solution, magnetically stirring for 12 hr to form uniform catalyst suspension, and coating on the surface of carbon paper electrode to ensure coverage area of 1×1cm 2 X 2, catalyst loading of 2.5mg/cm 2 Air-drying at room temperature to obtain Ni-S-C 1000 A loaded carbon paper electrode.
Example 4
The preparation method of the Ni-S-C composite catalyst comprises the following steps:
(1) The method for synthesizing the Ni-tri precursor is the same as in example 1, except that: the molar ratio of nickel sulfate to triazole is 1:1.5; the volume ratio of hydrofluoric acid to deionized water is 1:70; the constant temperature reaction temperature is 180 ℃ and the reaction time is 60h.
(2) Preparing a Ni-S-C composite catalyst material: the 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 at 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 1X 1cm 2 X 2, catalyst loading of 2mg/cm 2 And (3) 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 for synthesizing the Ni-tri precursor is the same as in example 1, except that: the molar ratio of nickel sulfate to triazole is 1:3; the volume ratio of hydrofluoric acid to deionized water is 1:80; the constant temperature reaction temperature is 200 ℃ and the reaction time is 40h.
(2) Preparing a Ni-S-C composite catalyst material: the 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 at 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 1X 1cm 2 X 2 catalyst loading of 3mg/cm 2 And (3) air-drying at room temperature to obtain the Ni-S-C loaded carbon paper electrode.
Product properties of examples 1-3:
as can be seen from the X-ray diffraction patterns of FIGS. 1 and 2, the diffraction peaks obtained by testing the synthesized Ni-tri precursor of the present invention are similar to the simulated diffraction peaks, which indicates that the synthesized substance is the target product and has higher purity. The Ni-S-C composite catalyst prepared by pyrolysis of Ni-tri precursor at 800-1000 ℃ does not show diffraction peaks of the precursor, as can be seen in FIG. 2, the Ni-S-C composite catalyst has a diffraction peak at an angle of 21.8 DEG, 31.1 DEG and 37.8 DEGThe Ni is stronger at 38.3 degrees, 49.7 degrees, 50.1 degrees, 54.6 degrees and 55.2 degrees 3 S 2 Diffraction peaks at an angle of 44.5 degrees, 51.8 degrees and 76.4 degrees correspond to the peaks of Ni, which indicates that the structure of the Ni-tri precursor is destroyed after high-temperature pyrolysis, and a new composite product is obtained through derivatization.
As shown in FIG. 3, the Ni-tri precursor synthesized in examples 1-3 was a regular octahedral-shaped crystal, partially unformed. The Ni-S-C composite catalyst after pyrolysis is spherical particles with nonuniform sizes, and the spherical particles are Ni in combination with analysis of an X-ray diffraction pattern 3 S 2 。
The transmission electron microscope of FIG. 7 and the high resolution transmission electron microscope of FIG. 8 show Ni 3 S 2 The spherical particle surface is covered by a thin, nonuniform carbon shell outer layer, and the carbon element is used as a substrate. Illustrating that Ni-tri precursor is obtained after high temperature pyrolysis with Ni 3 S 2 Ni-S-C composite catalyst with main body and carbon element as substrate.
FIG. 9 Ni-S-C composite catalyst vs. N at 77K 2 The adsorption and desorption isotherm diagram shows an H4 type hysteresis loop formed by compounding type I isotherms and type II isotherms, 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 increasing pyrolysis temperature. The differentiation of the pore volume with respect to the pore diameter, i.e., the pore volume variation per unit pore diameter, was calculated according to the BJH method, and the pore diameter distribution curves of all the obtained samples had similar shapes, which means that the Ni-S-C composite catalyst had similar uniform pore diameters. The Ni-S-C composite catalyst has maximum intensity peak value about 0.88nm and 1.91nm, and Ni-S-C 1000 Is larger than the other samples. These results indicate that pyrolysis collapses the mesoporous structure of the precursor, forming micropores, thus forming a broad pore distribution, and that an increase in pyrolysis temperature leads to an increase in pore size.
TABLE 1
TestingElectrochemical reduction of CO by Ni-S-C composite catalyst 2 Performance:
the test is carried out in a closed H-type 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 CO 2 Saturated 0.1mol/LKHCO 3 An aqueous solution. The electrochemical performance correlation is characterized by linear sweep voltammetry and time-current curve test, and the gas phase product is qualitatively and quantitatively analyzed by a gas chromatograph.
FIG. 10 is a linear sweep voltammogram obtained from the test of Ni-S-C composite catalyst supported carbon paper electrodes prepared in examples 1-3. Ni-S-C under the same potential 1000 Shows the highest current density, ni-S-C 900 Next, ni-S-C 800 Is the lowest current density. This initially demonstrates that Ni-S-C among the three composite catalysts 1000 Electrochemical reduction of CO 2 The performance is best.
FIG. 11 is a Faraday chart of CO obtained by electrolyzing the Ni-S-C composite catalyst-supported carbon paper electrode prepared in example 1-3 at a potential of-1.3V to-1.7V vs. Ag/AgCl for 2 h. The CO Faraday efficiencies of the three Ni-S-C composite catalysts all show a trend of increasing and then decreasing along with the change of the potential, and reach the highest CO Faraday efficiency under the potential of-1.5 Vvs. Wherein Ni-S-C prepared in example 3 1000 Has the highest Faraday efficiency of 66.6% for CO and Ni-S-C 800 The Faraday efficiency of CO was 40.2%, ni-S-C 900 The CO faraday efficiency of (c) was 47.4%.
Ni-S-C prepared in example 3 1000 With better electrochemical reduction of CO 2 Performance, therefore its stability at-1.5 v vs. ag/AgCl potential was further tested. Fig. 12 shows that the current density has a tendency to drop slowly over the first 10 hours, then reaches a plateau and is relatively stable. The inset shows the Faraday efficiencies of the products at electrolysis times of 2,4, 6, 8, 10, 24h, ni-S-C within 24h of electrolysis 1000 The CO faraday efficiency of (c) was maintained at 55%, indicating better catalyst stability.
FIG. 13 further illustrates Ni prepared in example 3-S-C 1000 A cyclicity test was performed. The same electrode is repeatedly electrolyzed for 5 times under the potential of minus 1.5V vs. Ag/AgCl, the Faraday efficiency of CO after each electrolysis is reduced by a small amount, and the Faraday efficiency is reduced by 9% after the 5 th electrolysis, thereby realizing the efficient recycling of the catalyst.
Claims (9)
1. A preparation method of a Ni-S-C composite catalyst is characterized in that,
the method comprises the following steps:
(1) Synthesizing a Ni-tri precursor by a hydrothermal method: adding nickel sulfate and triazole into deionized water for dissolution, adjusting pH, fully reacting at constant temperature, and cleaning and drying the product to obtain a Ni-tri precursor
(2) The Ni-tri precursor is subjected to high-temperature pyrolysis treatment to obtain a Ni-S-C composite catalyst;
wherein, the Ni-S-C composite catalyst after pyrolysis is spherical particles with nonuniform size, and the spherical particles are Ni 3 S 2 ；Ni 3 S 2 The surface of the spherical particles is covered by a thin and uneven carbon shell outer layer, and the carbon element is taken as a substrate; after high temperature pyrolysis of the Ni-tri precursor, ni is obtained 3 S 2 Ni-S-C composite catalyst with main body and carbon element as substrate.
2. The method for producing a Ni-S-C composite catalyst according to claim 1, wherein in the step (1), the molar ratio of nickel sulfate to triazole is 1.5 to 3.
3. The method for preparing a Ni-S-C composite catalyst according to claim 1, wherein in the step (1), hydrofluoric acid is used for adjusting pH, and the volume ratio of the hydrofluoric acid to deionized water is 1:70-80.
4. The method for producing a Ni-S-C composite catalyst according to claim 1, wherein in the step (1), the constant temperature is 180 to 200 ℃ and the reaction time is 40 to 60h.
5.The method for producing a 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 a high temperature, and N 2 Heating to 800-1000 ℃ in the atmosphere, and keeping the constant temperature to at least 1h.
6. An electrode comprising the Ni-S-C composite catalyst prepared by the method for preparing a Ni-S-C composite catalyst according to claim 1.
7. The method for preparing an electrode according to claim 6, wherein the Ni-S-C composite catalyst is mixed with conductive carbon black, stirred and dispersed in Nafion ethanol solution to form a uniform catalyst suspension, and coated on the surface of the carbon paper electrode, and dried at room temperature to obtain the Ni-S-C composite catalyst-supported carbon paper electrode.
8. The method for preparing an electrode according to claim 7, wherein the mass ratio of the Ni-S-C composite catalyst to the conductive carbon black is 1.5 to 2.5.
9. The method for preparing an electrode according to claim 7, wherein the loading amount of the Ni-S-C composite catalyst on the carbon paper electrode is 2-3 mg/cm 2 。
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| "Nitrogen-, Oxygen- and Sulfur-Doped Carbon-Encapsulated Ni3S2 and NiS Core–Shell Architectures: Bifunctional Electrocatalysts for Hydrogen Evolution and Oxygen Reduction Reactions";Yangfei Cao et al.;ACS SUSTAINABLE CHEMISTRY & ENGINEERING》;第6卷(第11期);第15582-15590页 * |
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