CN112481656B - Bifunctional catalyst for high-selectivity electrocatalysis of glycerin oxidation conversion to produce formic acid and high-efficiency electrolysis of water to produce hydrogen, preparation method and application thereof - Google Patents

Bifunctional catalyst for high-selectivity electrocatalysis of glycerin oxidation conversion to produce formic acid and high-efficiency electrolysis of water to produce hydrogen, preparation method and application thereof Download PDF

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CN112481656B
CN112481656B CN202011377241.XA CN202011377241A CN112481656B CN 112481656 B CN112481656 B CN 112481656B CN 202011377241 A CN202011377241 A CN 202011377241A CN 112481656 B CN112481656 B CN 112481656B
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glycerol
formic acid
water
hydrogen
selectivity
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陈燕
何祖韵
刘秋宇
宫志恒
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South China University of Technology SCUT
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Abstract

The invention discloses a bifunctional catalyst for high-selectivity electrocatalysis of glycerin oxidation conversion to produce formic acid and high-efficiency electrolysis of water to produce hydrogen, and a preparation method and application thereof. The method comprises the following steps: electrodeposition of Ni/Ni (OH) on conductive three-dimensional substrates2(ii) a Then soaking the catalyst in cobalt acetate solution for cation exchange, and taking out the catalyst to obtain the bifunctional catalyst. The method adopts an electrodeposition technology and a cation exchange strategy, and the preparation process is simple and feasible. The electrocatalyst provided by the invention has the performance of high-selectivity electrocatalysis of glycerol oxidation conversion to produce formic acid and the activity of efficiently electrolyzing water to produce hydrogen, and the hydrogen concentration is 100mA/cm in the glycerol oxidation reaction2The potential at the current density of (a) was 1.349V, the formic acid selectivity was 94.3%, and the current density was 100mA/cm2The electrolysis was continued for 90 hours with almost no potential decay. In the hydrogen evolution reaction, at 100mA/cm2The potential at the current density of (2) was-0.206V.

Description

Bifunctional catalyst for high-selectivity electrocatalysis of glycerin oxidation conversion to produce formic acid and high-efficiency electrolysis of water to produce hydrogen, preparation method and application thereof
Technical Field
The invention belongs to the technical field of electrocatalysis materials, and particularly relates to a bifunctional catalyst for producing formic acid by high-selectivity electrocatalysis of glycerol oxidation conversion and high-efficiency hydrogen production by electrolysis of water, and a preparation method and application thereof.
Background
The preparation of high value-added chemicals by using an electro-catalytic technology is an effective way for efficiently utilizing biomass resources. Conventional heatThe catalytic oxidation method is carried out under the condition of oxygen, oxygen is used as an oxidant, and the catalytic oxidation method is usually carried out under higher oxygen partial pressure and higher temperature, and has strict requirements on equipment. Otherwise, additional chemical oxidants, such as H, need to be added2O2And the like, which have low selectivity for the target product from the oxidation process, and produce large amounts of undesirable chemical waste. In this context, electrocatalytic oxidation is a promising alternative, with several advantages compared to the traditional thermal catalytic oxidation methods: 1. the oxidation reaction can be carried out at normal temperature and normal pressure, so that the energy consumption in the production process is effectively reduced; 2. the electrochemical oxidation does not need to use an additional chemical oxidant, so that the cost is reduced and the environmental pollution is avoided; 3. can be effectively coupled with Hydrogen Evolution Reaction (HER), and H with high added value is prepared at the cathode2The economic value of the whole electrochemical process is increased; 4. the electrochemical oxidation can be conveniently carried out in a small reactor arranged near the distribution of the biomass source, large-scale equipment is not needed, and the installation and the use are more convenient and flexible; 5. renewable energy sources (such as solar energy, wind energy and the like) can be effectively utilized to provide power required by electrochemical oxidation, the power cost is reduced, and the production period is more green and environment-friendly. However, the catalysts currently studied for electrochemical oxidation are mostly limited to noble metals (Zhang, Z.; Xin, L.; Li, W.; electrochemical oxidation of glycerol on Pt/C in an-exchange membrane fuel cell: Cogeneration of electric and effective chemical. applied catalysts B: Environmental 2012,119-120,40-48.) and their alloy catalysts (Kim, H.J.; Choi, S.M.; Seo, M.H.; Green, S.; Huber, G.W.; Kim, W.B., electrochemical oxidation of biological-derived glycerol over a Ptene-grafted catalyst), and their high cost further application (890 ). And, the oxidation process of biomass is complex, resulting in various products. Therefore, the development of a biomass resource oxidation catalyst which is low in price, excellent in catalytic activity and high in selectivity is one of the problems to be solved.
The rapid development of the biodiesel industry over the last several decades has resulted in a large excess in glycerol production (as a by-product of biodiesel production), making glycerol a low-cost, useable chemical. ($ 0.11 per kg or $ 0.010 per mole of raw glycerol). Indeed, glycerol is listed by the U.S. department of energy as one of ten large biomass-derived platform molecules for the production of high-value chemicals. Thus, inexpensive glycerol can be used as a raw material for the production of various high-value chemicals such as glyceraldehyde, dihydroxyacetone, glyceric acid, glycolic acid, oxalic acid, formic acid and the like. Among the various high value chemicals derived from the oxidation of glycerol, formic acid has practical prospects and high added value ($ 0.40/kg or $ 0.018/mole). Formic acid can be used as a fuel for Direct Formic Acid Fuel Cells (DFAFCs), which has attracted increased attention due to its high power density, limited fuel exchange, and convenient power system integration. In addition, the liquid nature and low toxicity of formic acid make it more convenient, easier to store, transport and handle than hydrogen. Formic acid is therefore an alternative hydrogen energy carrier with high capacity. With the development and deployment of direct or indirect applications for formic acid, the future demand for formic acid may increase rapidly, while the current global formic acid production capacity (72 ten thousand tons per year 2013) may not meet the demand. Thus, the selective production of 3 equivalents of formic acid from 1 equivalent of glycerol may be a promising approach.
As mentioned above, coupling the catalytic Hydrogen Evolution Reaction (HER) with the biomass oxidation reaction (BOER) can further improve its economic value. Therefore, the development of the bifunctional catalyst with HER and BOER activities can effectively simplify an electrolysis device, reduce equipment cost and improve product value. However, most of the electrocatalysis reported at present only have single activity of hydrogen evolution reaction/biomass oxidation reaction. Interface engineering is considered an effective method to design efficient electrocatalysts, since electrocatalytic reactions typically occur at the interface. Research shows that the interface engineering heterojunction can promote electron transfer and influence the adsorption/desorption energy of active species in electrocatalytic reaction, thereby regulating catalytic activity. Bifunctional HER/BEOR electrocatalysts may be prepared by integrating HER and BEOR active materials to construct a heterostructure catalyst. Furthermore, the interaction promotion of the two components may also be beneficial to further improve the catalytic activity and stability of the heterostructure.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a bifunctional catalyst for producing formic acid by high-selectivity electrocatalysis of glycerol oxidation conversion and high-efficiency electrolysis of water to produce hydrogen, and a preparation method and application thereof.
Aiming at the defects and shortcomings of the prior art, the invention aims to provide a preparation method of a bifunctional catalyst for high-selectivity electrocatalysis of glycerin oxidation conversion to produce formic acid and high-efficiency electrolysis of water to produce hydrogen.
It is another object of the present invention to provide the use of the above bifunctional catalyst in a fully electrolytic glycerol solution.
The purpose of the invention is realized by at least one of the following technical solutions.
A dual-function catalyst with high selectivity for preparing formic acid by electrocatalysis of glycerin oxidation conversion and high-efficiency hydrogen production by electrolysis of water is prepared by depositing Ni/Ni (OH) on conductive three-dimensional substrate by electrodeposition technology2Nanosheets, and electrodepositing the electrodeposited Ni/Ni (OH)2And soaking the nanosheets in a cobalt acetate solution for cation exchange, and taking out the nanosheets to obtain the high-efficiency bifunctional catalyst for glycerol oxidation and hydrogen production by water electrolysis.
The preparation method of the bifunctional catalyst for producing formic acid by high-selectivity electrocatalysis glycerol oxidation conversion and efficiently electrolyzing water to produce hydrogen, which comprises the following steps:
(1) electrodeposition of Ni/Ni (OH) on conductive three-dimensional substrates2Nanosheets, resulting in a deposit of Ni/Ni (OH)2A substrate after the nanosheet;
(2) depositing Ni/Ni (OH) in the step (1)2And soaking the substrate after the nano-sheets in a cobalt acetate solution, heating to perform cation exchange treatment, and taking out to obtain the high-selectivity bifunctional catalyst for producing formic acid and efficiently electrolyzing water to produce hydrogen by the oxidation conversion of the glycerol under the electrocatalysis.
Further, the conductive three-dimensional substrate in the step (1) is more than one of carbon cloth, carbon paper, foamed nickel, iron mesh and the like.
Preferably, the conductive three-dimensional substrate in the step (1) is carbon cloth.
Preferably, when the carbon cloth is selected as the conductive three-dimensional substrate in the step (1), the carbon cloth can be subjected to hydrophilic treatment in advance; the hydrophilic treatment comprises: soaking the carbon cloth in 37 wt% hydrochloric acid, heating at 90 deg.C for 2 hr, taking out, washing with water, and drying to complete hydrophilic treatment.
Further, the electrolyte used in the electrodeposition process in the step (1) is a nickel acetate solution; the concentration of the nickel acetate solution is 30-100 mM.
Preferably, the electrolyte used in the electrodeposition process in the step (1) is a nickel acetate solution; the concentration of the nickel acetate solution is 100 mM.
Further, the electrodeposition in the step (1) is deposition by using a cathode constant current chronopotentiometry method, and the current density of the electrodeposition is 5-15mA/cm2。
Preferably, the electrodeposition in the step (1) is deposition by using a cathodic constant current chronopotentiometry method, and the current density of the electrodeposition is 10mA/cm2。
Further, the time for the electrodeposition in the step (1) is 300-.
Preferably, the electrodeposition time in step (1) is 300 s.
In the step (1), after electrodeposition, Ni nano-sheets and Ni (OH) are generated on the conductive three-dimensional substrate2Nanosheets.
Further, the concentration of the cobalt acetate solution in the step (2) is 30-100 mM.
Preferably, the concentration of the cobalt acetate solution in the step (2) is 100 mM.
Further, the temperature of the cation exchange treatment in the step (2) is 60-80 ℃.
Preferably, the temperature of the cation exchange in step (2) is 80 ℃.
Further, the time of the cation exchange treatment in the step (2) is 2h-10 h.
Preferably, the time of the cation exchange treatment in the step (2) is 2 h.
The invention provides the bifunctional catalyst which is prepared by the preparation method and has the functions of high selectivity, electrocatalysis of glycerin oxidation conversion to produce formic acid and high efficiency of electrolysis of water to produce hydrogen.
The bifunctional catalyst prepared by the invention has the advantages of simple preparation process, energy-saving preparation process, low preparation cost, strong universality of the preparation method, flexible and controllable preparation process, easy adjustment of the components of the obtained catalyst and the like, and has the performance of producing formic acid by high-selectivity electrocatalysis of glycerol oxidation conversion and high-efficiency electrolysis of water to produce hydrogen.
The bifunctional catalyst with high selectivity for producing formic acid by electrocatalysis glycerol oxidation conversion and high-efficiency hydrogen production by electrolysis of water can be applied to hydrogen production reaction by coupling full electrolysis glycerol oxidation and electrolysis.
The obtained catalyst is used as an anode and a cathode to be assembled into a full electrolytic cell for simultaneously carrying out glycerol oxidation to prepare formic acid and electrolyzing water to produce hydrogen, and 100mA/cm can be generated under the voltage of 1.581V2The voltage drops by only 27.5mV when the electrolysis is continued for 110 hours at the current density, and the stability is excellent.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) in the preparation method provided by the invention, the adopted raw materials are low in price, high-temperature sintering is not needed, the energy consumption in the production process is less, and the production cost is low;
(2) in the preparation method provided by the invention, a cation exchange strategy is adopted, the preparation process is simple, and the preparation method is suitable for large-scale production;
(3) in the preparation method provided by the invention, the adopted conductive three-dimensional substrate has wide selection, such as carbon cloth, carbon paper, iron net, foam nickel and the like, and has wide application range;
(4) in the preparation method provided by the invention, a cation exchange strategy is adopted, the ion species selectivity is high, various transition metal compound composite catalysts can be easily prepared according to different reaction requirements, and the preparation method has universality;
(5) in the preparation method provided by the invention, the cation exchange strategy is adopted, so that the composite catalysts with different doping amounts can be easily prepared by controlling the reaction temperature, the solution concentration and the reaction time, and the application range is wide;
(6) the electrocatalyst provided by the invention has the performance of high-selectivity electrocatalysis of glycerol oxidation conversion to produce formic acid and the activity of efficiently electrolyzing water to produce hydrogen, and the hydrogen concentration is 100mA/cm in the glycerol oxidation reaction2The potential at the current density of (a) was 1.349V, the formic acid selectivity was 94.3%, and the current density was 100mA/cm2The electrolysis is continued for 90 hours, and the potential is almost not attenuated; in the hydrogen evolution reaction, at 100mA/cm2The potential at the current density of (a) is-0.206V; the obtained catalyst is used as an anode and a cathode to be assembled into a full electrolytic cell for simultaneously carrying out glycerol oxidation to prepare formic acid and electrolyzing water to produce hydrogen, and 100mA/cm can be generated under the voltage of 1.581V2The voltage drops by only 27.5mV when the electrolysis is continued for 110 hours at the current density, and the stability is excellent.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of the bifunctional catalyst for efficient electrolytic oxidation of glycerol and production of hydrogen by electrolysis of water obtained in example 1;
FIG. 2 is an X-ray spectral imaging (EDS) diagram of the bifunctional catalyst for efficient electrolytic glycerol oxidation and electrolytic water hydrogen production obtained in example 1;
FIG. 3 is a High Resolution Transmission Electron Microscope (HRTEM) image and a corresponding Fast Fourier Transform (FFT) image of the bifunctional catalyst for efficient electrolytic glycerol oxidation and electrolytic water hydrogen production obtained in example 1;
FIG. 4 is the cyclic voltammogram of the bifunctional catalyst for efficient electrolytic glycerol oxidation and hydrogen production from water obtained in example 1 for the catalytic test of the glycerol oxidation reaction;
FIG. 5 is the linear sweep voltammogram of the bifunctional catalyst for efficient electrolytic glycerol oxidation and electrolytic water hydrogen production obtained in example 1 for the catalytic test of hydrogen evolution reaction;
FIG. 6 is a High Performance Liquid Chromatogram (HPLC) and corresponding glycerol conversion and glyceric acid, glycolic acid and formic acid yield plots of the bifunctional catalyst for high performance electrolytic glycerol oxidation and hydrogen production by electrolysis of water obtained in example 1 after 0-10h electrolysis in 0.1M glycerol solution;
FIG. 7 is a graph showing the results of the selectivity of glyceric acid, glycolic acid and formic acid when the bifunctional catalyst for efficient electrolytic oxidation of glycerol and hydrogen production by electrolysis of water obtained in example 1 is electrolyzed in a 0.1M glycerol solution for 10 hours;
FIG. 8 shows Faraday efficiencies of glyceric acid, glycolic acid and formic acid when the bifunctional catalyst for efficient electrolytic oxidation of glycerol and hydrogen production by electrolysis of water obtained in example 1 was electrolyzed at 1000 ℃ in a 0.1M glycerol solution at different potentials;
FIG. 9 shows the hydrogen production by the dual-function catalyst for high efficiency electrolytic oxidation of glycerin and electrolysis of water obtained in example 1 at 100mA/cm in the glycerin oxidation reaction2Constant current chronopotentiometric diagram of continuous electrolysis for 90h under current density;
FIG. 10 is a linear sweep voltammogram of the full electrolysis hydrogen production of the glycerol solution in the two-electrode system of the bifunctional catalyst for efficient electrolytic glycerol oxidation and electrolytic water hydrogen production obtained in example 1;
FIG. 11 is the full electrolysis of the glycerol solution to produce hydrogen in the two-electrode system of the bifunctional catalyst for efficient electrolytic oxidation of glycerol and hydrogen production by electrolysis of water obtained in example 1 at 100mA/cm2A constant current chronopotentiometry graph of continuous electrolysis for 110h under current density and linear sweep voltammograms before and after the electrolysis;
FIG. 12 shows the deposit Ni/Ni (OH) obtained in comparative example 12Scanning Electron Microscope (SEM) images of the carbon cloth substrate of the nanoplatelets;
FIG. 13 shows the deposit Ni/Ni (OH) obtained in comparative example 12A transmission electron microscope (HRTEM) image and a corresponding selected area electron diffraction pattern (SAED) of the carbon cloth substrate of the nanoplatelets, and a corresponding Fast Fourier Transform (FFT) image of a High Resolution Transmission Electron Microscope (HRTEM) image;
FIG. 14 shows the deposit Ni/Ni (OH) obtained in comparative example 12The carbon cloth substrate of the nano sheet is used for a cyclic voltammetry curve chart of a glycerin oxidation reaction catalysis test;
FIG. 15 shows the deposit Ni/Ni (OH) obtained in comparative example 12The carbon cloth substrate of the nano-sheet is used for a linear scanning voltammetry curve chart of a hydrogen evolution reaction catalysis test;
FIG. 1 shows a schematic view of a6 is the deposit Ni/Ni (OH) obtained in comparative example 12Performing High Performance Liquid Chromatogram (HPLC) of the carbon cloth substrate of the nano sheet after 0-10h of electrolysis in 0.1M glycerol solution, and corresponding glycerol conversion rate and glyceric acid, glycolic acid and formic acid yield maps;
FIG. 17 shows the deposit Ni/Ni (OH) obtained in comparative example 12Glyceric acid, glycolic acid and formic acid selectivity result graphs when the carbon cloth substrate of the nano sheet is electrolyzed in 0.1M glycerol solution for 10 h;
FIG. 18 shows the deposit Ni/Ni (OH) obtained in comparative example 12A linear scanning voltammetry curve graph of the carbon cloth substrate of the nanosheet in a two-electrode system for full-electrolysis hydrogen production of glycerol solution;
FIG. 19 is a cyclic voltammogram of the bifunctional catalyst for efficient electrolytic oxidation of glycerol and hydrogen production by electrolysis of water obtained in example 2, used in a catalytic test of a glycerol oxidation reaction.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Example 1
A preparation method of a bifunctional catalyst for high-selectivity electrocatalysis of glycerin oxidation conversion to produce formic acid and high-efficiency electrolysis of water to produce hydrogen comprises the following steps:
(1) carrying out hydrophilic treatment on the carbon cloth, soaking the carbon cloth in 37 wt% hydrochloric acid, and heating for 2h at 90 ℃;
(2) washing the carbon cloth obtained in the step (1) with pure water, and putting the carbon cloth into a vacuum drying chamber at 60 ℃ for 5 hours;
(3) depositing Ni/Ni (OH) on the carbon cloth substrate obtained in the step (2) by an electrodeposition technology in a three-electrode system2The nano-sheet is prepared by using carbon cloth as a working electrode, an Ag/AgCl electrode as a reference electrode, a Pt net as a counter electrode, a nickel acetate solution with the concentration of 100mM as an electrolyte and applying 10mA/cm to the working electrode by using a constant current time-measuring potential method2For 300s, obtaining a deposit of Ni/Ni (OH)2A substrate after the nanosheet;
(4) depositing Ni/Ni (OH) obtained in the step (3)2The substrate with the nano-sheets is soaked in a 100mM cobalt acetate solution to obtain a mixture, and the mixture is placed in an oven at 80 ℃ to be heated for 2 hours to obtain the bifunctional catalyst (NiCo LDH) for high-selectivity electrocatalytic oxidation conversion of glycerol to formic acid and high-efficiency electrolysis of water to hydrogen.
In the embodiment, a Scanning Electron Microscope (SEM) image of the obtained bifunctional catalyst for producing formic acid by oxidation and conversion of high-selectivity electrocatalytic glycerol and efficiently electrolyzing water to produce hydrogen is shown in fig. 1, and the obtained sample has a nanosheet three-dimensional structure.
The X-ray energy spectrum (EDS) image of the bifunctional catalyst for producing formic acid by oxidation and conversion of high-selectivity electrocatalytic glycerol and for producing hydrogen by high-efficiency electrolysis of water is shown in fig. 2, and the Ni, Co and O elements in the obtained sample are uniformly distributed.
The High Resolution Transmission Electron Microscope (HRTEM) and the corresponding Fast Fourier Transform (FFT) of the obtained bifunctional catalyst for high selectivity electrocatalytic oxidation conversion of glycerol to formic acid and efficient electrolysis of water to hydrogen are shown in fig. 3, and the lattice spacing of the obtained sample is 0.26nm, which is consistent with NiCo LDH reported in the literature (j. mater.chem.a, 2018, 6, 15040).
In this example, the obtained bifunctional catalyst for efficient glycerol oxidation and hydrogen production by electrolysis of water was subjected to catalytic activity tests for glycerol oxidation and hydrogen evolution. Glycerol oxidation catalytic activity test conditions: a standard three-electrode system is adopted as a test system, the obtained catalyst material is used as a working electrode, saturated Ag/AgCl is used as a reference electrode, a platinum net is used as a counter electrode, a 1M KOH and 0.1M glycerol mixed solution is used as an electrolyte (a 1M KOH solution is used as a contrast), and a test instrument is a Shanghai Hua 660E electrochemical workstation. The cyclic voltammograms were tested at room temperature at 25 ℃. The cyclic voltammetry curve of the glycerol oxidation of the obtained bifunctional catalyst for producing formic acid by high-selectivity electrocatalytic oxidation conversion of glycerol and efficiently electrolyzing water to produce hydrogen is shown as a solid line in figure 4. Hydrogen evolution activity test conditions: a standard three-electrode system is adopted as a test system, the obtained catalyst material is used as a working electrode, saturated Ag/AgCl is used as a reference electrode, a graphite rod is used as a counter electrode, 1M KOH solution is used as electrolyte, and a test instrument is a Shanghai Hua 660E electrochemical workstation. The linear voltammetric sweep curves were tested at room temperature at 25 ℃. The linear sweep voltammetry curve of hydrogen evolution of the obtained bifunctional catalyst for high-selectivity electrocatalysis of glycerol oxidation conversion to formic acid and high-efficiency electrolysis of water to produce hydrogen is shown in figure 5.
In this example, as shown in fig. 6, the High Performance Liquid Chromatography (HPLC) of the electrolyte after electrolysis for different time (2-10h) of the obtained bifunctional catalyst for high selectivity electrocatalytic oxidation conversion of glycerol to formic acid and high efficiency electrolysis of water to produce hydrogen shows that the glycerol conversion rate after 10h electrolysis is 89%, the yield of glyceric acid is 0.68%, the yield of glycolic acid is 4.33%, and the yield of formic acid is 84.1%.
In this example, the selectivities of the obtained bifunctional catalyst for producing formic acid by electrocatalytic oxidation and conversion of glycerol with high selectivity and for producing hydrogen by electrolyzing water with high efficiency in the oxidation of glycerol are shown in fig. 7, in which the selectivity for glyceric acid is 0.76%, the selectivity for glycolic acid is 4.86%, and the selectivity for formic acid is 94.27%.
In this example, the faradaic efficiencies of the obtained bifunctional catalyst for producing formic acid by electrocatalytic oxidation and conversion of glycerol with high selectivity and for producing hydrogen by electrolyzing water with high efficiency when oxidizing glycerol are shown in fig. 8, and at 1000C under 0.6V electrolysis, the faradaic efficiency for glyceric acid is 4.15%, the faradaic efficiency for glycolic acid is 2.95%, and the faradaic efficiency for formic acid is 97.25%.
The stability of the obtained bifunctional catalyst for high selectivity electrocatalysis of glycerol oxidation conversion to formic acid and efficient electrolysis of water to produce hydrogen when glycerol oxidation is carried out is shown in FIG. 9, wherein 100mA/cm2The potential hardly decays when the electrolysis is carried out for 90 hours under the current density.
In this example, the linear sweep voltammetry curve of the obtained bifunctional catalyst for high selectivity electrocatalysis of glycerol oxidation conversion to formic acid and efficient electrolysis of water to produce hydrogen when the full electrolysis of glycerol solution to produce hydrogen is shown in fig. 10, where 10mA/cm2The voltage at the current density was 1.33V, 100mA/cm2Voltage at current density 1.58V。
In this example, the potentiostatic graph of the obtained bifunctional catalyst for high-selectivity electrocatalysis of oxidation conversion of glycerol to formic acid and efficient electrolysis of water to produce hydrogen when the full-electrolysis of glycerol solution to produce hydrogen and the linear sweep voltammetry before and after long-time electrolysis are shown in fig. 11, where 100mA/cm is shown2The potential drops by 27.5mV when the electrolysis is carried out for 110h under the current density.
Example 2
A preparation method of a bifunctional catalyst for high-selectivity electrocatalysis of glycerin oxidation conversion to produce formic acid and high-efficiency electrolysis of water to produce hydrogen comprises the following steps:
(1) carrying out hydrophilic treatment on the carbon cloth, soaking the carbon cloth in 37 wt% hydrochloric acid, and heating for 2h at 90 ℃;
(2) washing the carbon cloth obtained in the step (1) with pure water, and putting the carbon cloth into a vacuum drying chamber at 60 ℃ for 5 hours;
(3) depositing Ni/Ni (OH) on the carbon cloth substrate obtained in the step (2) by an electrodeposition technology in a three-electrode system2The nano-sheet is prepared by using carbon cloth as a working electrode, an Ag/AgCl electrode as a reference electrode, a Pt net as a counter electrode, a nickel acetate solution with the concentration of 100mM as an electrolyte and applying 15mA/cm to the working electrode by using a constant current time-measuring potential method2For 300s, obtaining a deposit of Ni/Ni (OH)2A substrate after the nanosheet;
(4) depositing Ni/Ni (OH) obtained in the step (3)2The substrate is soaked in 30mM cobalt acetate solution to obtain a mixture, and the mixture is placed in an oven at 80 ℃ to be heated for 2 hours to obtain the bifunctional catalyst (NiCo LDH) for high-selectivity electrocatalytic oxidation conversion of glycerol to formic acid and high-efficiency electrolysis of water to hydrogen.
The obtained bifunctional catalyst for high-selectivity electrocatalytic oxidation conversion of glycerol to formic acid and high-efficiency electrolysis of water to hydrogen is subjected to glycerol oxidation activity test. Glycerol oxidation catalytic activity test conditions: a standard three-electrode system is adopted as a test system, the obtained catalyst material is used as a working electrode, saturated Ag/AgCl is used as a reference electrode, a platinum net is used as a counter electrode, a 1M KOH and 0.1M glycerol mixed solution is used as an electrolyte (a 1M KOH solution is used as a contrast), and a test instrument is a Shanghai Hua 660E electrochemical workstation. The cyclic voltammograms were tested at room temperature at 25 ℃. The cyclic voltammogram of the obtained dual-function catalyst for efficient electrolytic glycerol oxidation and hydrogen production by electrolysis of water is shown as a solid line in fig. 19.
Comparative example 1
A deposited Ni/Ni (OH)2The preparation method of the carbon cloth substrate of the nanosheet comprises the following steps:
(1) carrying out hydrophilic treatment on the carbon cloth, soaking the carbon cloth in 37 wt% hydrochloric acid, and heating for 2h at 90 ℃;
(2) washing the carbon cloth obtained in the step (1) with pure water, and putting the carbon cloth into a vacuum drying chamber at 60 ℃ for 5 hours;
(3) depositing Ni/Ni (OH) on the carbon cloth substrate obtained in the step (2) by an electrodeposition technology in a three-electrode system2The nano-sheet is prepared by using carbon cloth as a working electrode, an Ag/AgCl electrode as a reference electrode, a Pt net as a counter electrode and 100mM nickel acetate solution as electrolyte, and applying 5mA/cm to the working electrode by using a constant current chronopotentiometry method2For 300s, obtaining a deposit of Ni/Ni (OH)2A carbon cloth substrate of the nano-sheet.
Comparative example 1 on the resulting deposit Ni/Ni (OH)2A Scanning Electron Microscope (SEM) image of the carbon cloth substrate of the nanoplatelets is shown in fig. 12, and the resulting sample exhibits a nanoplatelet three-dimensional structure.
Comparative example 1 on the resulting deposit Ni/Ni (OH)2Transmission Electron Microscopy (TEM) and corresponding selected electron diffraction patterns (SAED) and High Resolution Transmission Electron Microscopy (HRTEM) and corresponding Fast Fourier Transform (FFT) patterns of the nanosheet carbon cloth substrate are shown in fig. 13.
Comparative example 1 on the resulting deposit Ni/Ni (OH)2And (3) carrying out glycerol oxidation and hydrogen evolution catalytic activity tests on the carbon cloth substrate of the nanosheet. Glycerol oxidation catalytic activity test conditions: the resulting catalyst material (deposited Ni/Ni (OH) of comparative example 1) was tested using a standard three electrode system2Carbon cloth substrate of nanosheet) as working electrode, saturated Ag/AgCl as reference electrode, platinum mesh as counter electrode, and 1M KOH and 0.1M glycerol mixed solution as electrolyte (1M KOH solution as electrolysis solution)Liquid as a comparison), the test instrument was the Shanghai Hua 660E electrochemical workstation. The cyclic voltammograms were tested at room temperature at 25 ℃. Resulting deposit Ni/Ni (OH)2Cyclic voltammograms of glycerol oxidation of the carbon cloth substrates of the nanoplatelets are shown in solid lines in figure 14.
Hydrogen evolution activity test conditions: a standard three-electrode system is adopted as a test system, the obtained catalyst material is used as a working electrode, saturated Ag/AgCl is used as a reference electrode, a graphite rod is used as a counter electrode, 1M KOH solution is used as electrolyte, and a test instrument is a Shanghai Hua 660E electrochemical workstation. The linear voltammetric sweep curves were tested at room temperature at 25 ℃. Resulting deposit Ni/Ni (OH)2The linear sweep voltammograms for hydrogen evolution of the carbon cloth substrate of the nanoplatelets are shown in figure 15.
Comparative example 1 on the resulting deposit Ni/Ni (OH)2High Performance Liquid Chromatography (HPLC) of the electrolyte solution after electrolysis of the carbon cloth substrate of the nanosheet for different times (2-10h) is shown in fig. 16, and the conversion rate of glycerol after 10h of electrolysis is 82%, the yield of glyceric acid is 1.38%, the yield of glycolic acid is 2.69%, and the yield of formic acid is 74%.
Comparative example 1 on the resulting deposit Ni/Ni (OH)2As shown in fig. 17, the selectivity of the carbon cloth-based glycerol oxidation of the nanosheets was 1.68% for glyceric acid, 3.28% for glycolic acid, and 90.31% for formic acid.
Comparative example 1 on the resulting deposit Ni/Ni (OH)2The linear sweep voltammetry curve of the carbon cloth substrate of the nano-sheet when the hydrogen production is carried out by fully electrolyzing glycerol solution is shown in figure 18, and the linear sweep voltammetry curve is 10mA/cm2The voltage at the current density was 1.47V, 100mA/cm2The voltage at current density was 1.665V.
The results of fig. 12 and 13 show, in combination with fig. 1, fig. 2 and fig. 3, that hydroxide nanosheets can be successfully deposited on the carbon cloth, and the bifunctional catalyst for high-selectivity electrocatalytic oxidation and conversion of glycerol to formic acid and high-efficiency electrolysis of water to hydrogen production can be prepared.
The results shown in fig. 4, fig. 6, fig. 7, fig. 8, fig. 9, fig. 14, fig. 16, fig. 17 and fig. 19 show that the bifunctional catalyst for high-selectivity electrocatalytic oxidation and conversion of glycerol to formic acid and high-efficiency electrolysis of water to hydrogen, prepared in the example of the present invention, has excellent glycerol oxidation performance, high selectivity to formic acid and faradaic efficiency close to 100%, and has excellent long-term electrolytic stability under large current density conditions.
With reference to fig. 5, the results of fig. 15 show that the bifunctional catalyst for high selectivity electrocatalytic oxidation and conversion of glycerol to formic acid and high efficiency electrolysis of water to hydrogen prepared by the embodiment of the present invention has excellent hydrogen evolution activity, and can efficiently perform electrolysis of water to hydrogen under alkaline conditions.
The results of fig. 10, fig. 11 and fig. 18 show that the bifunctional catalyst for high-selectivity electrocatalysis of glycerol oxidation conversion to produce formic acid and high-efficiency electrolysis of water to produce hydrogen, which is prepared in the embodiment of the present invention, can simultaneously electrocatalysis of glycerol oxidation and electrolysis of water to produce hydrogen in a two-electrode electrolytic cell, and has long-term electrolytic stability under a large current density condition, and thus, the bifunctional catalyst has an excellent practical application prospect.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.

Claims (10)

1. A preparation method of a bifunctional catalyst for high-selectivity electrocatalysis of glycerin oxidation conversion to produce formic acid and high-efficiency electrolysis of water to produce hydrogen is characterized by comprising the following steps:
(1) electrodeposition of Ni/Ni (OH) on conductive three-dimensional substrates2Obtaining the deposit Ni/Ni (OH)2A rear substrate;
(2) depositing Ni/Ni (OH) in the step (1)2And soaking the substrate in cobalt acetate solution, heating to perform cation exchange treatment, and taking out to obtain the high-selectivity bifunctional catalyst for producing formic acid by electrocatalysis glycerol oxidation conversion and high-efficiency hydrogen production by electrolysis of water.
2. The preparation method of the bifunctional catalyst for high-selectivity electrocatalytic oxidation and conversion of glycerol to formic acid and high-efficiency electrolysis of water to hydrogen as claimed in claim 1, wherein the conductive three-dimensional substrate in the step (1) is one or more of carbon cloth, carbon paper, foamed nickel and iron mesh.
3. The preparation method of the bifunctional catalyst for high-selectivity electrocatalytic oxidation and conversion of glycerol to formic acid and high-efficiency electrolysis of water to hydrogen as claimed in claim 1, wherein the electrolyte used in the electrodeposition process in step (1) is nickel acetate solution; the concentration of the nickel acetate solution is 30-100 mM.
4. The method for preparing the bifunctional catalyst for high-selectivity electrocatalytic oxidation and conversion of glycerol to formic acid and high-efficiency electrolysis of water to hydrogen as claimed in claim 1, wherein the electrodeposition in the step (1) is performed by using a cathodic constant current chronopotentiometry method, and the current density of the electrodeposition is 5-15mA/cm2。
5. The method for preparing the bifunctional catalyst for high selectivity electrocatalytic oxidation and conversion of glycerol to formic acid and high efficiency electrolysis of water to hydrogen as claimed in claim 1, wherein the time of electrodeposition in step (1) is 300-600 s.
6. The preparation method of the bifunctional catalyst for high selectivity electrocatalytic oxidation and conversion of glycerol to formic acid and high efficiency electrolysis of water to hydrogen as claimed in claim 1, wherein the concentration of the cobalt acetate solution in the step (2) is 30-100 mM.
7. The preparation method of the bifunctional catalyst for high selectivity electrocatalytic oxidation and conversion of glycerol to formic acid and high efficiency electrolysis of water to hydrogen as claimed in claim 1, wherein the temperature of the cation exchange treatment in the step (2) is 60-80 ℃.
8. The preparation method of the bifunctional catalyst for high selectivity electrocatalytic oxidation and conversion of glycerol to formic acid and high efficiency electrolysis of water to hydrogen as claimed in claim 1, wherein the time of the cation exchange treatment in the step (2) is 2h-10 h.
9. The bifunctional catalyst for high-selectivity electrocatalytic oxidation conversion of glycerol to formic acid and high-efficiency electrolysis of water to hydrogen, which is prepared by the preparation method of any one of claims 1-8.
10. The use of the bifunctional catalyst of claim 9 for high selectivity electrocatalytic oxidation of glycerol to formic acid and high efficiency electrolysis of water to hydrogen for the oxidation of electrolytic glycerol and the reaction of electrolytic water.
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