CN115584522A - Three-dimensional porous electrode, preparation method and application of acidic electrocatalytic carbon dioxide reduction to formic acid - Google Patents
Three-dimensional porous electrode, preparation method and application of acidic electrocatalytic carbon dioxide reduction to formic acid Download PDFInfo
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 title claims abstract description 134
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 235000019253 formic acid Nutrition 0.000 title claims abstract description 67
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 36
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 27
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 26
- 230000009467 reduction Effects 0.000 title abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 229920000642 polymer Polymers 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000011148 porous material Substances 0.000 claims abstract description 21
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- 239000002002 slurry Substances 0.000 claims abstract description 19
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
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- 239000004744 fabric Substances 0.000 claims abstract description 10
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- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 7
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- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 8
- 239000004332 silver Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 229920002492 poly(sulfone) Polymers 0.000 claims description 5
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 5
- 229920012287 polyphenylene sulfone Polymers 0.000 claims description 5
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- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 3
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 2
- 229910052708 sodium Inorganic materials 0.000 claims 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 19
- 230000008859 change Effects 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
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- 229910052753 mercury Inorganic materials 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
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- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 150000004675 formic acid derivatives Chemical class 0.000 description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 3
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
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- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
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- 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
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- 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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- 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
- C25B11/095—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 at least one of the compounds being organic
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Abstract
The invention provides a three-dimensional porous electrode, a preparation method thereof and application of acidic electrocatalytic carbon dioxide reduction to formic acid; the three-dimensional porous electrode comprises a conductive support substrate and a porous composite catalyst layer, wherein the conductive support substrate is carbon cloth, the porous composite catalyst layer contains inorganic catalyst bismuth nano particles and polymers, the thickness of the electrode is in a micron scale, and the electrode has communicated and fluffy pore structures; uniformly mixing a catalyst, a polymer and an organic solvent, and stirring and ultrasonically degassing to obtain uniform and viscous slurry; uniformly coating the paste on carbon cloth by using a scraper with a fixed height to obtain an unformed blank; and transferring the unformed blank into a coagulating bath, taking out after completely curing, and drying to obtain the three-dimensional porous electrode. The two-chamber acid flow electrolytic system is provided for the first time to directly synthesize formic acid, the Faraday effect of formic acid can reach 89.2% under the condition of pH value-2.7, the aim of preparing formic acid by direct electroreduction is achieved, and the method has industrial application potential.
Description
Technical Field
The invention belongs to the field of electrocatalytic synthesis; in particular to a three-dimensional porous electrode, a preparation method and application of acidic electrocatalysis carbon dioxide reduction to prepare formic acid.
Background
Electrocatalytic carbon dioxide reduction (CO) 2 RR) technology is to couple CO with renewable energy 2 One of the potential methods of industrial stream exploitation and conversion to valuable chemicals helps achieve the goal of net zero emission. In contrast to current fossil-based thermal synthesis methods, there are a number of COs 2 In RR reduction products, only carbon monoxide and formic acid can be used for remarkably reducing CO through electrosynthesis 2 Emission (1-2 million tons of carbon dioxide per year) [2] 。
Although at present electrocatalytic CO 2 The field of the preparation of C1 products (carbon monoxide, formic acid) from RR has made a remarkable development, especially in terms of catalyst structure and flowing electrolysis system, but the progress of the industrial development is still far and heavy. Currently, electrolysis systems in the industry, in order to suppress the occurrence of hydrogen evolution reactions to increase the selectivity of C1 products, generally utilize neutral or alkaline electrolytes, which results in obtaining products that are formate salts rather than formic acid. If the product is used as a feedstock by a subsequent process, it needs to be separated from the salt solution and further acidified, which obviously increases capital investment. In addition, neutral or alkaline electrolytes can capture CO 2 Converting it to carbonate or bicarbonate, so-called "carbonate problem", the part being converted not being electrocatalytic for CO 2 RR utilization, even because of the existence of a large amount of salt, blocks a reaction flow channel, and reduces the catalytic efficiency. Apparently, CO in such systems 2 The utilization of (a) is also relatively low. The existence of these problems limits electrocatalytic CO 2 And 4, industrial development process of synthesizing formic acid by RR. According to the Pourbaix diagram, the turning point of the material morphology of formic acid and formate is located at pH 3.77, corresponding to the pKa of formic acid. The formic acid can be directly generated by using the acidic electrolyte with the pH value lower than 3.77, so that the subsequent separation and acidification processes of formate are avoided, and the problem of carbonate is also solved. But when the pH of the electrolyte is lowThe hydrogen evolution reaction is significantly amplified due to kinetic advantages, so that the faradaic efficiency of formic acid is reduced. Therefore, designing a large-surface-area electrode capable of inhibiting the hydrogen evolution reaction and improving the selectivity of formic acid under an acidic condition is of great significance for promoting the industrial development of the electrosynthesis of formic acid.
Aiming at the problems, a novel three-dimensional porous electrode in the field of electrocatalysis and a method for preparing the electrode are provided. The electrode structure integrating the catalyst and gas-liquid diffusion is obtained by utilizing the communicated pore structure, high porosity and proper wettability of the electrode, the purposes of promoting mass transfer and morphology confinement effect are achieved, and CO is selectively introduced under the acidic condition that the pH value of the electrolyte is less than 3.77 2 Reducing to formic acid. In addition, the electrode realizes the sustainable formic acid synthesis target in an acidic flowing electrolysis system, and has potential industrial development prospect.
Reference to the literature
[1]R.K.Pachauri,M.R.Allen,V.R.Barros,J.Broome,W.Cramer,R.Christ,J.A.Church,L.Clarke,Q.Dahe and P.Dasgupta,Climate change 2014:synthesis report.Contribution of Working Groups I,II and III to the fifth assessment report of the Intergovernmental Panel on Climate Change,IPCC,2014..
[2]M.Rahimi,A.Khurram,T.A.Hatton,B.Gallant,Electrochemical carbon capture processes for mitigation of CO2 emissions,Chem.Soc.Rev.,2022.
Disclosure of Invention
The invention aims to provide a three-dimensional porous electrode to overcome the defects that the preparation of the current large-scale electrode is difficult, the problem of hydrogen evolution in an acidic environment is serious and the like.
The second purpose of the invention is to provide a preparation method of the three-dimensional porous electrode.
The third current invention is to provide the above three-dimensional porous electrode for acidic electrocatalysis of CO 2 Application of reduction to the preparation of formic acid.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a three-dimensional porous electrode; the electrode comprises a conductive support substrate and a porous composite catalysis layer, wherein the conductive support substrate is carbon cloth, the porous composite catalysis layer comprises inorganic catalyst bismuth nanoparticles and polymers, the thickness of the electrode is in a micron scale, and the electrode has a fluffy pore structure which is communicated with each other; the polymer is water insoluble polymer compound, including polyphenylene sulfone, polyacrylonitrile, polysulfone or polyvinylidene fluoride, as shown in FIG. 1.
The average thickness of the three-dimensional porous electrode is 300-800 mu m, the water contact angle is 32-111 degrees, and the porosity is 54-72 percent.
The preparation method of the three-dimensional porous electrode comprises the following steps:
1) Preparing composite slurry: uniformly mixing a catalyst, a polymer and an organic solvent, and stirring and ultrasonically degassing to obtain uniform and viscous slurry;
2) Preparing a blank of the three-dimensional porous electrode: uniformly coating the paste on carbon cloth by using a scraper with a fixed height to obtain an unformed blank;
3) Curing into a three-dimensional porous electrode: and transferring the unformed blank into a coagulating bath, taking out after complete solidification, and drying to obtain the three-dimensional porous electrode.
In the method, the mass ratio of the catalyst to the polymer in the composite slurry is 2:1 to 1:2, the mass ratio of the total mass of the catalyst and the polymer to the organic solvent is 0.15 to 0.5, and the polymer is a water-insoluble high molecular compound and comprises polyphenylene sulfone, polyacrylonitrile, polysulfone or polyvinylidene fluoride; the organic solvent in the composite slurry is a polar solvent, comprises N-methyl pyrrolidone, N-dimethyl formamide or N, N-diethyl formamide, meets the requirement of fully dissolving the polymer and completely dissolving the polymer with the coagulating bath, and the coagulating bath is water, ethanol and the like and is required to be completely dissolved with the organic solvent and not dissolve the polymer.
The three-dimensional porous electrode is applied to electrocatalysis of CO 2 Reducing to prepare formic acid; the three-dimensional porous electrode is arranged in the acidic/neutral H-shaped electrolytic cell; the three-dimensional porous electrode is used as a cathode, the platinum sheet is used as an anode, the silver/silver chloride is used as a reference electrode, and the three-electrode sealing system is adopted.
The application voltage range is 0 to-1.4V vs RHE, preferably-0.6 to-1.0V RHE, the electrolyte is a non-volatile acid solution, a soluble sodium salt or a soluble potassium salt, and the pH range is 1.2 to 7.2.
The three-dimensional porous electrode is applied to electrocatalysis of CO 2 Reducing to prepare formic acid; the three-dimensional porous electrode is applied to an acidic two-electrode flowing electrolytic tank; the three-dimensional porous electrode is used as a cathode, the proton exchange membrane is used as a separation membrane, the water oxidation catalyst is used as an anode, and carbon dioxide and electrolyte in a cathode area are mixed and introduced according to a certain gas-liquid ratio.
The range of the applied electrolytic voltage is 2.4-3.6V, preferably 2.7-3.2V; CO 2 2 The volume ratio range of the raw material gas to the electrolyte is 8:1-0 2 A saturated electrolyte. The electrolyte pH is preferably in the range of 1.8 to 3.7.
In the method, in the step (1), the mass ratio of the catalyst to the polymer in the composite slurry is 2:1 to 1: and 2, the mass ratio of the total mass of the catalyst and the polymer to the organic solvent is 0.15-0.5.
The invention has the beneficial effects that:
(1) The invention provides a three-dimensional porous electrode, which comprises a conductive support substrate and a porous composite catalyst layer, wherein the conductive support substrate is carbon cloth, the porous composite catalyst layer contains an inorganic catalyst and a polymer, the thickness of the porous composite catalyst layer is in a micron scale, the porous composite catalyst layer has mutually communicated and fluffy pore structures, and due to the fact that the pore structures are mutually communicated, the porosity is high, and the wettability is proper, the three-dimensional porous electrode not only improves the mass transport, but also amplifies H inside the electrode + The diffusion effect causes a locally higher pH around the active site to promote formic acid synthesis.
(2) The invention provides a preparation method of a three-dimensional porous electrode, which is used for preparing the three-dimensional porous electrode by using a phase transfer method based on a solvent diffusion principle to obtain a high-porosity and three-dimensional electrode structure.
(3) The invention firstly provides a two-chamber acid flow electrolytic system for directly synthesizing formic acid, the Faraday effect of the formic acid can reach 89.2 percent under the condition of pH-2.7, the tank pressure is 3.0V, and the system can stably run for 12 hours, thereby realizing the purpose of preparing the formic acid by direct electroreduction, avoiding the subsequent separation and acidification steps and having industrial application potential.
Drawings
FIG. 1: schematic structural diagram of three-dimensional porous electrode.
FIG. 2: scanning electron micrographs of the three-dimensional porous electrode obtained in example 1.
FIG. 3: example 2 scanning electron micrographs of the resulting three-dimensional porous electrode.
FIG. 4: scanning electron micrographs of the three-dimensional porous electrode obtained in example 3.
FIG. 5: the pore structure and pore size distribution of the three-dimensional porous electrodes obtained in example 1, example 2 and example 3.
FIG. 6: water contact angle graphs of the three-dimensional porous electrodes obtained in example 1, example 2 and example 3.
FIG. 7: formate Faraday efficiency plots of the three-dimensional porous electrodes obtained in examples 1, 2 and 3 at different potentials in a neutral electrolyte (neutral pH 7.2).
FIG. 8: faradaic efficiency plots of formate or formic acid in pH electrolyte for the three-dimensional porous electrode obtained in example 1.
FIG. 9: graph of the faradaic efficiency and local current density of formic acid for the three-dimensional porous electrode obtained in example 1 at different cell pressures in an acidic (pH-2.7) flow cell.
FIG. 10: the stability test chart of the three-dimensional porous electrode obtained in the example 1 in an electrolysis system with anolyte of pH-2 sulfuric acid and catholyte of pH-2.7 sodium sulfate flow.
FIG. 11: the three-dimensional porous electrode obtained in example 2 catalyzes CO in an acidic H-type electrolytic cell with pH of 3.7 2 Faraday efficiency diagram of reduction to formic acid.
FIG. 12: the three-dimensional porous electrode obtained in example 2 is used for electrically reducing CO in a two-chamber flow electrolysis device under the condition of gas-liquid ratio 4:1 2 And (4) preparing a formate Faraday efficiency graph.
FIG. 13: the three-dimensional porous electrode obtained in example 3 is catalyzed in an acidic H-type electrolytic cell with pH of 1.2CO 2 Faraday efficiency graph of reduction formic acid preparation.
FIG. 14: three-dimensional porous electrolysis obtained in example 3 electro-reduction of CO at gas-liquid ratio 0:1 in acidic two-chamber flow electrolysis device 2 Faraday efficiency graph for formic acid production.
Detailed description of the preferred embodiments
The present invention is described in detail below with reference to embodiments and drawings, and the following embodiments can facilitate those skilled in the art to more fully understand the present invention. But not to limit the invention in any way.
Example 1
The preparation process of the three-dimensional porous electrode comprises the following steps:
(1) Preparing composite slurry: 0.1g of amorphous bismuth nanoparticles, 0.2g of polyphenylene sulfone (at this time the mass ratio of catalyst to polymer is 1:2) were ultrasonically dispersed in 1g N-methylpyrrolidone solvent (at this time the mass ratio of the total mass of catalyst and polymer to organic solvent is 0.3.
(2) Preparing a blank of the three-dimensional porous electrode: pouring the slurry on carbon cloth, setting the height to be 500 mu m by using a height-fixing scraper, and scraping and coating uniform slurry to obtain an unformed blank;
(3) Curing into a three-dimensional porous electrode: and soaking the unformed blank in deionized water at room temperature overnight, taking out after complete curing, and drying to form the three-dimensional porous electrode.
FIG. 2 is a scanning electron microscope picture of the three-dimensional porous electrode obtained in example 1, the overall morphology of which is composed of a dense layer and a porous support layer. Clearly, the dense layer (polymer-rich phase) has a smooth porous surface with a uniform distribution of visible mesopores and macropores (fig. 2 b); the porous support layer (polymer lean phase) is bonded by a layered structure of honeycomb pores to form an interconnected lofty scaffold-like structure (fig. 2 c), further forming visible, continuous micron-scale finger-like pore channels (fig. 2 a) providing a large number of channels for mass transport. The active component bismuth nanoparticles were distributed homogeneously over the three-dimensional porous electrolysis (fig. 2 d). Fig. 5 is a graph showing the pore structure and pore size distribution obtained by the mercury intrusion test method. Under medium pressure, the accumulated mercury intrusion amount is increased sharply, which shows that the electrode obtained in example 1 has medium-sized pores, the pore diameter is mainly concentrated in the micron-sized range, the distribution is strongest around 2.5 μm, and the porosity reaches 64.2%. Fig. 7 shows the water contact angle, 78 °, for a three-dimensional porous electrode.
The three-dimensional porous electrode prepared in example 1 was used in H-type and two-electrode flow electrolyzers for the electroreduction synthesis of formic acid or formate from neutral/acidic carbon dioxide.
The three-dimensional porous electrode prepared in example 1 was used as a cathode, a platinum sheet as an anode, a silver/silver chloride electrode as a reference electrode, and 0.5M KHCO 3 Neutral electrocatalytic carbon dioxide reduction was performed in an H-cell as the electrolyte. FIG. 7 shows that the three-dimensional porous electrode prepared in example 1 catalyzes CO in a neutral (pH 7.2) H-type electrolytic cell 2 The graph of the faradaic efficiency of reduced formate mainly describes the change of the faradaic efficiency of formate with the increase of the electrode potential. As can be seen from the figure, the three-dimensional porous electrode prepared in example 1 has higher electrochemical reduction of CO 2 Faradaic efficiency of formate production. In a test potential window of-0.68 to-1.0V vs RHE, the Faraday efficiencies of the formates reach more than 92 percent and reach as high as 96.2 percent, which shows that the formate has the advantages in the aspect of preparing formic acid by electrocatalysis of carbon dioxide reduction.
The three-dimensional porous electrode prepared in example 1 was used as a cathode, a platinum sheet as an anode, a silver/silver chloride electrode as a reference electrode, and sulfuric acid was added in an amount of 0.25mol/LNa 2 SO 4 The pH test range is 1.2-7.2 for electrolyte, and the acidic electrocatalytic carbon dioxide reduction is carried out in an H-type electrolytic cell. FIG. 8 shows that the three-dimensional porous electrode obtained in example 1 catalyzes CO in an acidic H-type electrolytic cell 2 The faradaic efficiency of reducing formic acid is mainly described as the change of the faradaic efficiency of formic acid along with the pH value of the electrolyte. The Faraday efficiency of formic acid is reduced along with the reduction of the pH value of the electrolyte, the Faraday efficiency of formic acid is more than 20 percent within the test range of pH 1.2-7.2, and the Faraday efficiency of formic acid can still reach 85.2 percent when the pH is 1.8. The three-dimensional porous electrode overcomes the mass transmission limitation, inhibits the hydrogen evolution reaction through the shape confinement effect to form a local higher pH value around the active site, and promotes the electrode to be capable of being positioned on an acid stripAnd electrically reducing the carbon dioxide under the condition of one piece to prepare the formic acid.
The three-dimensional porous electrode prepared in example 1 was used as a cathode, a Nafion115 proton exchange membrane was used as a diaphragm, and an iridium black mesh was used as an anode, and electrocatalytic carbon dioxide reduction was performed using an acidic two-chamber flow electrolyzer. In the cathode region, CO, in the acid electrolysis process 2 The raw material gas and the catholyte are mixed and introduced according to the volume ratio of 8:1, and the pH of the catholyte is between 2.7 and 1mol/L Na 2 SO 4 The pH of the anolyte is Na with the concentration of 2.7 to 1mol/L 2 SO4 and pH 2H 2 SO 4 。
FIG. 9 is the electro-reduction of CO in an acidic two-compartment flow electrolyzer from three-dimensional porous electrolysis obtained in example 1 2 The Faraday efficiency chart of the formic acid preparation is that the electrolytes of the cathode and the anode are all Na with the pH value of 2.7 1mol/L 2 SO 4 The change of the Faraday efficiency of formic acid with the tank pressure is mainly described. At a pH of 2.7, a Faraday effect of 89.2% formic acid was achieved at 3.0V and exceeded 40% or more at a voltage of 2.7-3.2V. The highest local current density of 54.0mA/cm is obtained under the voltage of 3.1V 2 。
FIG. 10 is the electro-reduction of CO in an acidic two-compartment flow electrolyzer from three-dimensional porous electrolysis obtained in example 1 2 The stability test chart of the prepared formic acid shows that the cathode electrolyte is Na with the pH value of 2.7 1mol/L 2 SO 4 The anolyte is pH-2H 2 SO 4 The change in catholyte pH and formic acid concentration with electrolysis time is mainly described. The formic acid concentration steadily increases after the continuous acidic electrolysis test of 12h is carried out under the pressure of a 3.0V tank, and the three-dimensional porous electrolysis obtained in the example 1 is proved to be capable of maintaining the pH of the continuous reaction, and the total concentration of the formic acid reaches 0.1mol/L. The excellent electrocatalytic carbon dioxide reduction capability of the three-dimensional porous electrolysis obtained in the embodiment 1 proves the possibility of continuously generating formic acid under an acidic condition, avoids the subsequent separation and acidification steps, and has potential application prospects.
Example 2
The preparation process of the three-dimensional porous electrode comprises the following steps:
(1) Preparing composite slurry: 0.1g of amorphous bismuth nanoparticles, 0.1g of polysulfone (at this time the mass ratio of catalyst to polymer is 1:1) were ultrasonically dispersed in 0.4g of N, N-dimethylformamide (at this time the mass ratio of the total mass of catalyst and polymer to the organic solvent is 0.5.
(2) Preparing a blank of the three-dimensional porous electrode: pouring the slurry on carbon cloth, setting the height to be 800 mu m by using a height-setting scraper, and scraping and coating uniform slurry to obtain an unformed blank;
(3) Curing into a three-dimensional porous electrode: and soaking the unformed blank in deionized water at room temperature overnight, taking out after complete curing, and drying to form the three-dimensional porous electrode.
FIG. 3 is a scanning electron micrograph of the three-dimensional porous electrode obtained in example 2. The cross-sectional topography presents distinct finger-like pore transmission channels, and the pore channels are formed by numerous fine pores connected to each other. Figure 5 reflects the pore distribution of the three-dimensional porous structure, with only a small amount of mercury invading the channels at pressures less than 10psia, indicating a smaller macroporous structure, with an increase in cumulative invasion of mercury with increasing pressure, but a smaller overall invasion relative to example 1, indicating the presence of a small amount of mesopores with a porosity of 54.5%. Fig. 6 shows the water contact angle, 111.3 °, of the three-dimensional porous electrode obtained in example 2, which is relatively hydrophobic.
The three-dimensional porous electrode prepared in example 2 was used in H-type and two-electrode flow electrolyzers for the electroreduction synthesis of formic acid or formate from neutral/acidic carbon dioxide.
The three-dimensional porous electrode prepared in example 2 was used as a cathode, a platinum sheet as an anode, a silver/silver chloride electrode as a reference electrode, and 0.5M KHCO 3 Neutral electrocatalytic carbon dioxide reduction was performed in an H-cell as the electrolyte. FIG. 7 reflects that the three-dimensional porous electrode prepared in example 2 catalyzes CO in a neutral (pH 7.2) H-type electrolytic cell 2 The graph of the faradaic efficiency of reduced formate mainly describes the change of the faradaic efficiency of formate with the increase of the electrode potential. As can be seen from the figure, the three-dimensional porous electrode prepared in example 2 has higher electrochemical reduction of CO 2 Faradaic efficiency of formate production. The Faraday efficiencies of formate are all up to more than 48% and the maximum value at a test potential window of-0.68 to-1.0V vs RHECan reach 92 percent.
The three-dimensional porous electrode prepared in example 2 was used as a cathode, a platinum sheet as an anode, a silver/silver chloride electrode as a reference electrode, and 0.25mol/L Na acidified with sulfuric acid 2 SO 4 Is used as electrolyte, pH is 3.7, and acidic electrocatalytic carbon dioxide reduction is carried out in an H-shaped electrolytic tank. FIG. 11 shows that the three-dimensional porous electrode obtained in example 2 catalyzes CO in an acidic H-type electrolytic cell 2 The Faraday efficiency graph of reducing formic acid mainly describes the change of the Faraday efficiency of formic acid with the potential of an electrode. The three-dimensional porous electrode prepared in example 2 can be used for electrically reducing carbon dioxide into formic acid under the condition of pH value of 3.7, and the faradaic efficiency of the formic acid is over 45 percent and is maximum 86 percent.
The three-dimensional porous electrode prepared in example 2 was used as a cathode, a Nafion115 proton exchange membrane was used as a diaphragm, and an iridium black mesh was used as an anode, and electrocatalytic carbon dioxide reduction was performed using an acidic two-chamber flow electrolyzer. In the cathode region, CO, in the acid electrolysis process 2 The raw material gas and the catholyte are mixed and introduced in a volume ratio of 4:1, and the pH of the catholyte and the anolyte is 3.7 1mol/L Na 2 SO 4 The pH value of the anolyte is 3.7 1mol/LNa 2 SO 4 。
FIG. 12 is a schematic diagram of the three-dimensional porous electrolysis obtained in example 2 for the electro-reduction of CO in an acidic two-chamber flow electrolyzer 2 The Faraday efficiency chart of formic acid preparation, and the electrolytes of the cathode and the anode are all pH-3.7 1mol/L Na 2 SO 4 The change of the Faraday efficiency of formic acid with the tank pressure is mainly described. When the voltage is more than 2.7V, the formic acid Faraday effect is more than 25 percent and reaches more than 50 percent under the voltage of 2.9V.
Example 3
The preparation process of the three-dimensional porous electrode comprises the following steps:
(1) Preparing composite slurry: 0.1g of amorphous bismuth nanoparticles, 0.05g of polyacrylonitrile (here, the mass ratio of the catalyst to the polymer is 2:1) were ultrasonically dispersed in 0.5g of n, n-dimethylacetamide solvent (here, the mass ratio of the total mass of the catalyst and the polymer to the organic solvent is 0.15.
(2) Preparing a blank of the three-dimensional porous electrode: pouring the slurry on carbon cloth, setting the height to be 300 mu m by using a height-setting scraper, and scraping and coating uniform slurry to obtain an unformed blank;
(3) Curing into a three-dimensional porous electrode: and soaking the unformed blank in deionized water at room temperature overnight, taking out after complete curing, and drying to form the three-dimensional porous electrode.
FIG. 4 is a scanning electron micrograph of the three-dimensional porous electrode obtained in example 3, and it can be seen that finger-shaped pore channels exist in the appearance thereof, but the interior of the channel structure is relatively compact. FIG. 5 is a graph of the pore structure distribution of the three-dimensional porous electrode obtained in example 3, showing that there are relatively more large and small pore structures, the mesopore content is less, there are two most probable distributions in the ranges of 0.1-0.8 μm and 6-40 μm, and the porosity is 72%. Figure 5 shows that example 3 has a water contact angle of 32.4 deg., relatively hydrophilic.
The three-dimensional porous electrode prepared in example 3 was used in H-type and two-electrode flow electrolyzers for the electroreduction synthesis of formic acid or formate from neutral/acidic carbon dioxide.
The three-dimensional porous electrode prepared in example 3 was used as a cathode, a platinum sheet as an anode, a silver/silver chloride electrode as a reference electrode, and 0.5M KHCO 3 As an electrolyte, a neutral electrocatalytic carbon dioxide reduction was performed in an H-type electrolytic cell. FIG. 7A three-dimensional porous electrode prepared in example 3 catalyzes CO in a neutral (pH 7.2) H-type cell 2 The graph of the faradaic efficiency of reduced formate mainly describes the change of the faradaic efficiency of formate with the increase of the electrode potential. As can be seen from the figure, the three-dimensional porous electrode prepared in example 3 has higher electrochemical reduction of CO 2 Faradaic efficiency of formate production. In a test potential window of-0.68 to-1.0V vs RHE, the Faraday efficiencies of the formates are all more than 30 percent and maximally 72 percent.
The three-dimensional porous electrode prepared in example 3 was used as a cathode, a platinum sheet as an anode, a silver/silver chloride electrode as a reference electrode, and 0.25mol/L Na acidified with sulfuric acid 2 SO 4 The pH of the electrolyte solution is 1.2, and the acidic electrocatalytic carbon dioxide reduction is carried out in an H-shaped electrolytic cell. FIG. 13 shows pH 1.2 of the three-dimensional porous electrode obtained in example 3Catalyzing CO in sex H-type electrolytic cell 2 The Faraday efficiency graph of reduction to formic acid mainly describes the change of the Faraday efficiency of formic acid with the potential of an electrode. The three-dimensional porous electrode prepared in example 3 can be used for electrically reducing carbon dioxide into formic acid under the condition of pH value of 1.2, and the Faraday efficiency of the formic acid is more than 20%.
The three-dimensional porous electrode prepared in example 3 was used as a cathode, a Nafion115 proton exchange membrane was used as a membrane, and an iridium black mesh was used as an anode, and electrocatalytic carbon dioxide reduction was performed using an acidic two-chamber flow electrolysis apparatus. In the cathode region, CO, in the acid electrolysis process 2 The volume ratio of the raw material gas to the cathode liquid is 0:1 is mixed and introduced, and the pH of the electrolyte of the cathode and the anode is 1.8 to 1mol/L Na 2 SO 4 The pH value of the anolyte is 1.8 1mol/LNa 2 SO 4 。
FIG. 14 is the electro-reduction of CO in an acidic two-compartment flow electrolyzer from three-dimensional porous electrolysis obtained in example 3 2 The Faraday efficiency chart of the formic acid preparation is that the electrolytes of the cathode and the anode are all Na with the pH value of 1.8 1mol/L 2 SO 4 The change of the formic acid Faraday efficiency with the tank pressure is mainly described. As can be seen from the figure, the three-dimensional porous electrode prepared in example 3 can be used for electrically reducing carbon dioxide into formic acid under the condition of pH value of 1.8, and the faradaic efficiency of the formic acid is more than 10%.
The three-dimensional porous electrode for preparing formic acid by acidic electrosynthesis, the preparation method and the design of the acidic flowing electrolysis system disclosed and proposed by the invention have been described by the field preferred embodiments, and it is obvious for those skilled in the art to implement the technology of the present invention by modifying or appropriately changing and combining the methods without departing from the content, spirit and scope of the invention. It is expressly intended that all such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and content of the invention.
Claims (10)
1. A three-dimensional porous electrode; the electrode is characterized by comprising a conductive support substrate and a porous composite catalyst layer, wherein the conductive support substrate is carbon cloth, the porous composite catalyst layer contains inorganic catalyst bismuth nano particles and polymers, the thickness of the electrode is in a micron scale, and the electrode has communicated and fluffy pore structures; the polymer is water insoluble polymer compound, including polyphenylene sulfone, polyacrylonitrile, polysulfone or polyvinylidene fluoride.
2. The three-dimensional porous electrode according to claim 1, wherein the average thickness is 300 to 800 μm, and the water contact angle is 32 ° (mm °)
-111 ° and a porosity of 54-72%.
3. The method for preparing a three-dimensional porous electrode according to any one of claims 1 to 2, comprising the steps of:
(1) Preparing composite slurry: uniformly mixing a catalyst, a polymer and an organic solvent, and stirring and ultrasonically degassing to obtain uniform and viscous slurry;
(2) Preparing a blank of the three-dimensional porous electrode: uniformly coating the paste on carbon cloth by using a scraper with a fixed height to obtain an unformed blank;
(3) Curing into a three-dimensional porous electrode: and transferring the unformed blank into a coagulating bath, taking out after completely curing, and drying to obtain the three-dimensional porous electrode.
4. The method of claim 3, wherein the mass ratio of catalyst to polymer in the composite slurry is from 2:1 to 1: and 2, the mass ratio of the total mass of the catalyst and the polymer to the organic solvent is 0.15-0.5, the polymer is a water-insoluble high molecular compound, such as polyphenylene sulfone, polyacrylonitrile, polysulfone, polyvinylidene fluoride and the like, the organic solvent in the composite slurry is a polar solvent, such as N-methyl pyrrolidone, N-dimethylformamide, N-diethylformamide and the like, and the requirements of fully dissolving the polymer and fully mutually dissolving the polymer with a coagulating bath are met.
5. The three-dimensional porous electrode of claim 1 applied to electrocatalytic CO 2 Reducing to prepare formic acid in an acidic/neutral H-type electrolytic cell; it is characterized in that a three-dimensional porous electrode is used as a cathode, a platinum sheet is used as an anode, and silver/chloride is addedSilver is used as a reference electrode, and a three-electrode sealing system is adopted.
6. A method according to claim 5, characterized in that the voltage is in the range of 0 to-1.4V vs RHE, preferably-0.6 to-1.0V RHE, the electrolyte is a non-volatile acid solution, a soluble sodium or potassium salt and the pH is in the range of 1.2 to 7.2.
7. The three-dimensional porous electrode of claim 1 applied to electrocatalytic CO 2 Reducing the acid in an acid two-electrode flowing electrolytic tank for preparing formic acid; the method is characterized in that a three-dimensional porous electrode is used as a cathode, a proton exchange membrane is used as a separation membrane, a water oxidation catalyst is used as an anode, and carbon dioxide and electrolyte in a cathode area are mixed and introduced according to a certain gas-liquid ratio.
8. The method as claimed in claim 7, wherein the electrolysis voltage is in the range of 2.4 to 3.6V, preferably 2.7 to 3.2V.
9. The method of claim 7, wherein the CO is 2 The volume ratio range of the raw material gas to the electrolyte is 8:1-0 2 A saturated electrolyte.
10. The method of claim 7, wherein the electrolyte is a non-volatile acid solution, soluble sodium or potassium salt, and has a pH in the range of 1.8 to 3.7.
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| CN110402303A (en) * | 2017-03-13 | 2019-11-01 | 西门子股份公司 | By CO2It is electrochemically reduced to the preparation of the gas-diffusion electrode with ion transmission resin of chemical utility |
| CN112144076A (en) * | 2020-09-18 | 2020-12-29 | 碳能科技（北京）有限公司 | Integrated membrane electrode and preparation method and application thereof |
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| CN110402303A (en) * | 2017-03-13 | 2019-11-01 | 西门子股份公司 | By CO2It is electrochemically reduced to the preparation of the gas-diffusion electrode with ion transmission resin of chemical utility |
| CN109518222A (en) * | 2019-01-28 | 2019-03-26 | 苏州大学 | For electro-catalysis CO2It is restored to the bismuth-based catalysts and its preparation method and application of formic acid |
| CN112144076A (en) * | 2020-09-18 | 2020-12-29 | 碳能科技（北京）有限公司 | Integrated membrane electrode and preparation method and application thereof |
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