CN116651456B - Biocompatible hydrogen evolution electrocatalyst and preparation method and application thereof - Google Patents
Biocompatible hydrogen evolution electrocatalyst and preparation method and application thereof Download PDFInfo
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- CN116651456B CN116651456B CN202310527298.0A CN202310527298A CN116651456B CN 116651456 B CN116651456 B CN 116651456B CN 202310527298 A CN202310527298 A CN 202310527298A CN 116651456 B CN116651456 B CN 116651456B
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- biocompatible
- hydrogen evolution
- terephthalic acid
- carbon dioxide
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- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 60
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000001257 hydrogen Substances 0.000 title claims abstract description 57
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- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 46
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 43
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- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- 229910004619 Na2MoO4 Inorganic materials 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
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- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 1
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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Abstract
The invention discloses a biocompatible hydrogen evolution electrocatalyst, a preparation method and application thereof, and belongs to the technical field of energy conversion and electrocatalysts, wherein the electrocatalyst comprises carbon nanotubes and metal nickel nanoparticles, and the metal nickel nanoparticles are wrapped in the carbon nanotubes with micropores and mesoporous structures; the preparation method comprises the following steps: respectively dissolving terephthalic acid and nickel acetate in N, N-dimethylformamide to obtain a terephthalic acid solution and a nickel acetate solution, dripping the nickel acetate solution into the terephthalic acid solution, heating, stirring, reacting, collecting a solid product, washing and drying to obtain the Ni-PTA metal organic framework; calcining the Ni-PTA metal organic framework at a high temperature under the inert gas atmosphere, cooling and then pickling to obtain the biocompatible hydrogen evolution electrocatalyst. The electrocatalyst has the advantages of low nickel ion dissolution and low active oxygen substance generation in neutral solution, has good biocompatibility, and can be applied to the electrocatalytic conversion of carbon dioxide by microorganisms.
Description
Technical Field
The invention relates to the technical field of energy conversion and electrocatalyst, in particular to a biocompatible hydrogen evolution electrocatalyst, a preparation method and application thereof.
Background
The microbial electrosynthesis is a process that microorganisms utilize electric energy as reducing power to reduce and synthesize CO 2, glucose or other substrates into various chemicals, and the system comprises an anode (counter electrode), a reference electrode and a cathode (working electrode), wherein the microbial electrosynthesis generates H 2 and O 2 by in-situ electrolysis of water, provides electrons and energy for the growth and metabolism of the microorganisms, and further utilizes the metabolic process of the microorganisms to realize the high-value conversion of CO 2. In recent years, the use of microbial electrosynthesis systems to immobilize CO 2 to produce poly-beta-hydroxybutyrate, biofuels, or a variety of complex multi-carbon products has become a current research hotspot. As a green sustainable biological carbon fixation technology, the technology not only can produce high added value chemicals, but also can realize fixation of greenhouse gas CO 2 at the same time, and provides a platform for converting CO 2 into multi-carbon compounds.
Wild-type copper pesticidal strain (Cupriavidus necator) has been extensively studied as a typical carbon-fixing hydroxide microorganism for the conversion of CO 2 to biomass or poly-beta-hydroxybutyrate. By using Cupriavidus necator as chassis cells and genetically modifying, the production of various biofuels such as isopropanol and isobutanol from CO 2 and the synthesis of high added value products such as lycopene and alpha-humulene can be realized.
In addition, chinese patent publication No. CN107354478a discloses a method for reducing carbon dioxide at a cathode using mixed anaerobic microorganisms including Proteobacteria, firmicutes and Bacteroidetes, which can achieve reduction of carbon dioxide to volatile fatty acids using common electrode materials, and produce substances with high added value using a domesticated and enriched mixed bacteria system.
In order to make in-situ electrolytic water reaction more efficient in microorganism culture solution environment and improve electric energy conversion efficiency, the hydrogen evolution electrocatalyst is applied to a cathode of a microorganism electrosynthesis system and used for reducing overpotential of hydrogen evolution reaction. However, dissolution and accumulation of metallic elements in hydrogen evolution catalysts during electrocatalytic processes can inhibit the activity of carbon-fixing microorganisms. 25 μmol L -1 of Co 2+ and Ni 2+ already have significant cytotoxicity. In addition, for aerobic microorganisms, by-product reactive oxygen species, including H 2O2 and HO, etc., produced by reduction of oxygen at the cathode, these ROS can destroy DNA, lipids and proteins, affecting metabolism and proliferation of the microorganism. Therefore, the biocompatibility of the cathodic hydrogen evolution electrocatalyst seriously affects the growth and metabolism of microorganisms in a microbial electrosynthesis system, thereby affecting the conversion of CO 2 to high value-added products. Therefore, designing a hydrogen evolution electrocatalyst capable of simultaneously reducing metal ion elution and ROS production with excellent biocompatibility is a problem that needs to be solved in the prior art.
Disclosure of Invention
The invention provides a biocompatible hydrogen evolution electrocatalyst, which comprises a carbon nano tube and metal nickel nano particles, wherein the metal nickel nano particles are wrapped in the carbon nano tube containing micropores and mesoporous structures; the electrocatalyst has a limited domain structure, can obviously reduce the dissolution of metallic nickel in the application process, reduces the generation of catalytic by-product Reactive Oxygen Species (ROS), and has excellent biocompatibility.
The technical scheme adopted is as follows:
A biocompatible hydrogen evolution electrocatalyst comprises 60-80wt% of carbon nanotubes and 20-40wt% of metallic nickel nanoparticles, wherein the metallic nickel nanoparticles are wrapped in the carbon nanotubes with micropores and mesoporous structures; preferably, the biocompatible hydrogen evolution electrocatalyst has micropores with a pore diameter of less than 3nm and mesopores with a pore diameter of 3-5 nm.
The biocompatible hydrogen evolution electrocatalyst provided by the invention has a specific structure, the metal nickel nano particles are wrapped in the carbon nano tubes, the electrocatalyst has a limited domain structure, the dissolution of metal nickel in the application process can be obviously reduced, the generation of catalytic by-product Reactive Oxygen Species (ROS) is reduced, the biocompatibility is excellent, and the electrocatalyst has a good application prospect in the electrocatalytic conversion of carbon dioxide by microorganisms.
The invention also provides a preparation method of the biocompatible hydrogen evolution electrocatalyst, which comprises the following steps:
(1) Respectively dissolving terephthalic acid and nickel acetate in N, N-dimethylformamide to obtain terephthalic acid solution and nickel acetate solution, dripping the nickel acetate solution into the terephthalic acid solution, heating, stirring, reacting, collecting solid products, washing and drying to obtain the Ni-PTA metal organic framework.
(2) Calcining the Ni-PTA metal organic frame obtained in the step (1) at a high temperature in an inert gas atmosphere, cooling to obtain black powder, and pickling to obtain the biocompatible hydrogen evolution electrocatalyst.
The invention takes nickel acetate as a nickel source and terephthalic acid as an organic ligand, firstly synthesizes a Ni-PTA metal organic framework, and further carries out calcination and acid washing operation on the framework to obtain the biocompatible hydrogen evolution electrocatalyst.
Preferably, in the step (1), the concentration of the terephthalic acid solution is 0.1 to 0.3mol L -1; the concentration of the nickel acetate solution is 0.1-0.3mol L -1; the volume ratio of the terephthalic acid solution to the nickel acetate solution is 1:1-2.
Preferably, the conditions of the heating and stirring reaction are 80-120 ℃ for 2-8 hours.
Preferably, in the step (2), the inert gas atmosphere is nitrogen atmosphere, the calcination temperature is 700-900 ℃, and the calcination time is 2-3 hours. The calcination atmosphere, temperature and time influence the conductivity, specific surface area and dispersibility of nickel metal nano particles of the catalyst product, and under the preferable conditions, the activity of the obtained product catalyst for catalyzing hydrogen evolution reaction is higher.
Further preferably, the rate of temperature rise in the high-temperature calcination is 5 to 10℃min -1. The rate of temperature rise is too fast and will affect the formation of carbon nanotubes.
Preferably, in step (2), sulfuric acid of 0.5mol L -1 is used for pickling for 12-24 hours. Under the above-mentioned preferable acid washing conditions, metallic nickel nanoparticles exposed outside the carbon nanotubes can be sufficiently removed.
The invention also discloses application of the biocompatible hydrogen evolution electrocatalyst in the electrocatalytic conversion of carbon dioxide by microorganisms, preferably, a microbial electrosynthesis system is used for loading the biocompatible hydrogen evolution electrocatalyst on a cathode, reducing the overpotential of the cathodic hydrogen evolution reaction, promoting aerobic microorganisms or anaerobic microorganisms to fix CO 2 and convert the CO 2 into high-added-value products such as poly beta-hydroxybutyrate and the like.
The invention also provides a method for converting carbon dioxide by using the microorganism electrocatalytic reaction, which comprises the following steps: constructing a three-electrode system, taking a carbon electrode carrying the biocompatible hydrogen evolution electrocatalyst as a cathode, taking Ag/AgCl as a reference electrode, taking a platinum electrode as an anode, forming a closed loop by the cathode, the reference electrode, the anode and an electrochemical workstation, taking an aerobic microorganism culture solution as an electrolyte, connecting the electrochemical workstation, inoculating aerobic microorganisms, controlling the OD 600 of the electrolyte at the initial inoculation to be 0.2-0.3, and operating at a cathode voltage of minus 0.9-minus 1.2V (relative to a saturated silver/silver chloride electrode) at room temperature to convert CO 2 into a high value-added product.
Preferably, the aerobic microorganism is copper-pesticidal bacterium (Cupriavidus necator), and the electrolyte is a liquid culture solution of the copper-pesticidal bacterium known to those skilled in the art; the high added value product is poly beta-hydroxybutyrate. Experiments prove that the biocompatible hydrogen evolution electrocatalyst can realize good coupling with Cupriavidus necator in a microbial electrosynthesis system, and realize high-value conversion from CO 2 to poly beta-hydroxybutyrate.
Compared with the prior art, the invention has the beneficial effects that:
(1) The biocompatible hydrogen evolution electrocatalyst provided by the invention has a specific structure, the biocompatible hydrogen evolution electrocatalyst comprises carbon nanotubes and metal nickel nanoparticles, the metal nickel nanoparticles are wrapped in the carbon nanotubes with micropores and mesoporous structures, and the limiting effect of the carbon nanotubes inhibits the dissolution of metal nickel, so that the electrocatalyst has the characteristic of low metal nickel ion dissolution, and further the cytotoxicity caused by metal ion dissolution is obviously reduced.
(2) When the biocompatible hydrogen evolution electrocatalyst is used for the electrocatalytic conversion of carbon dioxide by microorganisms, the biocompatible hydrogen evolution electrocatalyst has good catalytic hydrogen evolution performance in neutral microorganism culture solution, has good catalytic performance and stability for 160 hours, generates fewer by-product active oxygen substances (such as H 2O2, HO, and the like), shows excellent biocompatibility, and has wide application prospect in the field of the electrocatalytic conversion of carbon dioxide by microorganisms.
Drawings
FIG. 1 is a graph showing pore size distribution of the biocompatible hydrogen evolution electrocatalyst prepared in example 1.
FIG. 2 is an SEM image of a biocompatible hydrogen evolution electrocatalyst prepared according to example 1.
FIG. 3 is a TEM image of the biocompatible hydrogen evolution electrocatalyst prepared in example 1.
FIG. 4 is a graph showing the polarization of an electrolytic water hydrogen evolution reaction in a microbial broth for a biocompatible hydrogen evolution electrocatalyst prepared in example 1, at a scan rate of 2mV s -1.
FIG. 5 is a graph showing the accumulation of H 2O2 concentration with time during the operation of the microbial electro-synthesis system of application example 1.
FIG. 6 is a graph showing the accumulation of HO-concentration with time during the operation of the microbial electro-synthesis system of application example 1.
FIG. 7 is a graph showing the concentration of metal nickel ions eluted during the operation of the microbial electro-synthesis system of application example 2.
FIG. 8 is a graph showing the concentration of poly-beta-hydroxybutyrate produced from the electrocatalytic conversion of carbon dioxide by a microorganism in application example 3.
Detailed Description
The invention is further elucidated below in connection with the examples and the accompanying drawing. It is to be understood that these examples are for illustration of the invention only and are not intended to limit the scope of the invention. The methods of operation, under which specific conditions are not noted in the examples below, are generally in accordance with conventional conditions, or in accordance with the conditions recommended by the manufacturer.
The insecticidal copper bacteria (Cupriavidus necator) used in the examples were purchased from Beijing North Nakau Biotechnology institute under the product number BNCC137386.
Example 1
(1) 0.332G of terephthalic acid was added to 10mL of N, N-dimethylformamide and stirred at 500rpm in an oil bath at 120℃until dissolved; 0.75g of nickel acetate tetrahydrate is weighed and put into 15mL of N, N-dimethylformamide, and dispersed by ultrasonic for 30min until dissolved; obtaining terephthalic acid solution and nickel acetate solution with the concentration of 0.2mol L -1; slowly dripping nickel acetate solution into terephthalic acid solution, continuously stirring the obtained mixed solution at 120 ℃ in an oil bath, centrifugally collecting pale green solid products after reacting for 8 hours, repeatedly washing with N, N-dimethylformamide, and drying in a 60 ℃ oven to obtain the Ni-PTA metal organic framework.
(2) Placing the obtained Ni-PTA metal organic framework in a tube furnace, heating to 800 ℃ at a rate of -1 ℃ in a nitrogen atmosphere, calcining for 3 hours, and cooling to room temperature to obtain a black product; the black product is pickled for 24 hours by 0.5mol L -1 of sulfuric acid, and the biocompatible hydrogen evolution electrocatalyst is obtained.
Characterization of the biocompatible hydrogen evolution electrocatalyst shows that the content of metallic nickel in the biocompatible hydrogen evolution electrocatalyst is 30wt%, the average particle size of metallic nickel nano particles is 10-20nm, the specific surface area of the biocompatible hydrogen evolution electrocatalyst is 162m 2 g-1, and the pore volume is 0.53cm 3 g-1. The pore size distribution results are shown in FIG. 1, and micropores with a diameter of less than 3nm and mesopores with a diameter of 3-5nm exist in the electrocatalyst.
The microstructure of the biocompatible hydrogen evolution electrocatalyst was observed by Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM), respectively, as shown in fig. 2 and 3, it was seen that metallic nickel nanoparticles were encapsulated with carbon nanotubes. The metal nickel nano-particles regulate and control the electron cloud density of the carbon layer around the metal nickel nano-particles, and are used as active sites of the electrocatalyst for electrolytic water hydrogen evolution reaction in a neutral environment.
The hydrogen evolution performance of the electrocatalyst is measured by using a linear sweep voltammetry with a sweep rate of 2mV s -1 by taking a microbial culture solution as an electrolyte. As shown in the polarization graph of FIG. 4, the electrocatalyst had an overpotential of 444mV in the microorganism culture broth. Wherein, the overpotential is the difference between the measured potential and the theoretical potential when the current density is 10mA cm -2. This result shows that the electrocatalyst has better electrocatalytic hydrogen evolution performance in microbial culture solution.
Example 2
In this example, the preparation method of the biocompatible hydrogen evolution electrocatalyst is different from that of example 1 only in that the concentration of terephthalic acid solution is 0.1mol L -1 and the concentration of nickel acetate solution is 0.1mol L -1; the reaction conditions were 80℃with stirring for 6h.
Example 3
In this example, the preparation method of the biocompatible hydrogen evolution electrocatalyst is different from that in example 1 only in that the high-temperature calcination temperature is 700 ℃, the calcination time is 2 hours, the temperature rising rate is 10 ℃ min -1, and the pickling time is 12 hours.
Application example 1
The formula of the culture solution of the aerobic microorganism Cupriavidus necator is ：9g L-1Na2HPO4·12H2O,1.5g L-1KH2PO4,0.2g L-1(NH4)2SO4,80mg L-1MgSO4·7H2O,1mg L-1CaSO4·2H2O,50mg L-1 ferric citrate ,200mg L-1NaHCO3,1.5mg L-1NTA,0.3mg L-1H3BO3,0.2mg L-1CoCl2·6H2O,0.1mg L- 1ZnSO4·7H2O,0.03mg L-1MnCl2·4H2O,0.03mg L-1Na2MoO4·2H2O,0.02mg L-1NiCl2·6H2O,0.01mg L-1CuSO4·5H2O.
15Mg of the biocompatible hydrogen evolution electrocatalyst prepared in example 1 was weighed, mixed with 0.15mL of 0.5wt.% Nafion solution (obtained by diluting 5wt.% Nafion solution with absolute ethanol, 5wt.% Nafion solution purchased from dupont) and 1.35mL of absolute ethanol, and sonicated for 2 hours to obtain a mixed solution. Dropping the mixed solution on carbon paper to obtain a cathode of a microbial electrosynthesis system with the catalyst loading capacity of 1mg cm -2; a three-electrode system is constructed, a platinum mesh electrode with the thickness of 1cm is used as an anode, a reference electrode is a saturated silver/silver chloride electrode, and a closed loop is formed by a cathode, the reference electrode, the anode and an electrochemical workstation. And adding the microbial culture solution as electrolyte, and connecting an electrochemical workstation. The concentration of H 2O2 in the electrolyte was measured by controlling the cathode voltage to-0.9V at 30℃and sampling 1mL at 0, 10, 30, 60, 120min, and the concentration of H 2O2 as a by-product was only 7. Mu. Mol L -1 at the maximum as shown in FIG. 5.
As described above, under the above conditions, 1mL was sampled at 0min,10min,30min,1h,2h,3h,5h,24h,48h and 96h, and HO concentration in the electrolyte was measured, and as a result, as shown in FIG. 6, the cumulative HO concentration after 96h was found to be only 0.7. Mu. Mol L -1.
Since the microorganism itself has a certain resistance to active oxygen species, and part of the metabolic activity in the body also requires the participation of active oxygen species, and the descriptions of related experiments and literature can prove that the concentrations of H 2O2 and HO can not cause any cytotoxicity to the microorganism.
Application example 2
The method comprises the following steps of: one colony was taken from the agar plate, cultured in LB medium for about 12 hours, and then the bacterial solution was centrifuged (7000 rpm,10 minutes), and repeatedly washed three times with the microbial culture solution; the bacterial solution was redispersed in a microbial culture containing 10. Mu.g ml -1 gentamicin sulphate. After 48 hours of incubation with mixed gas (H 2：CO2：O2 =80:15:5), the incubated Cupriavidus necator was inoculated into a reactor containing 150 ml of microbial broth.
A three-electrode system microbial electrosynthesis system (same as in application example 1) was constructed, and the reaction apparatus was sterilized at high temperature for use. The culture solution Cupriavidus necator in application example 1 was used as an electrolyte, an electrochemical workstation was connected to inoculate Cupriavidus necator bacteria solution, the OD 600 of the electrolyte at the initial inoculation was controlled to be 0.2-0.3, and the cathode voltage was controlled to be-0.9V (relative to saturated silver/silver chloride electrode) at 30 ℃. CO 2 was bubbled for 15min every 24h and 2mL samples were taken. The concentration of metallic nickel in the supernatant was measured after centrifugation of the sample. As a result, as shown in FIG. 7, the concentration of metallic nickel ions was always lower than 0.1mg L -1.
Application example 3
A three-electrode system microbial electrosynthesis system (same as in application example 1) was constructed, and the reaction apparatus was sterilized at high temperature for use. The culture solution Cupriavidus necator in application example 1 was used as an electrolyte, an electrochemical workstation was connected, cupriavidus necator bacteria solution was inoculated, OD 600 of the electrolyte at the initial inoculation was controlled to be 0.2-0.3, cathode voltages were controlled to be-0.9V, -1.0V, -1.1V and-1.2V (relative to saturated silver/silver chloride electrode) at 30℃respectively, and the cells were operated under the above conditions, CO 2 min was introduced every 24 hours, and 2mL was sampled.
The concentration of poly-beta-hydroxybutyrate in the precipitate was measured after centrifugation of the sample and the results are shown in FIG. 8. The cathode voltage (absolute value) is increased, the hydrogen yield is increased, the accumulation speed of poly beta-hydroxybutyrate is increased, and the yield is obviously increased.
The above examples of application are only provided as possible ways of applying the biocompatible hydrogen evolution electrocatalyst, which may be used to construct a dual-chamber microbial electrosynthesis system in addition to the single-chamber microbial electrosynthesis system described above. The above is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto.
While the foregoing embodiments have been described in detail in connection with the embodiments of the invention, it should be understood that the foregoing embodiments are merely illustrative of the invention and are not intended to limit the invention, and any modifications, additions, substitutions and the like made within the principles of the invention are intended to be included within the scope of the invention.
Claims (7)
1. The biocompatible hydrogen evolution electrocatalyst for the electrocatalytic conversion of carbon dioxide by microorganisms is characterized by comprising 60-80 wt% of carbon nanotubes and 20-40-wt% of metal nickel nanoparticles, wherein the metal nickel nanoparticles are wrapped in the carbon nanotubes with micropores and mesoporous structures;
The preparation method of the biocompatible hydrogen evolution electrocatalyst for the microbial electrocatalytic conversion of carbon dioxide comprises the following steps:
(1) Respectively dissolving terephthalic acid and nickel acetate in N, N-dimethylformamide to obtain a terephthalic acid solution and a nickel acetate solution, dripping the nickel acetate solution into the terephthalic acid solution, heating, stirring, reacting, collecting a solid product, washing and drying to obtain the Ni-PTA metal organic framework;
(2) Calcining the Ni-PTA metal organic frame obtained in the step (1) at a high temperature in an inert gas atmosphere, cooling to obtain black powder, and pickling to obtain the biocompatible hydrogen evolution electrocatalyst for the electrocatalytic conversion of carbon dioxide by microorganisms;
in the step (1), the concentration of the terephthalic acid solution is 0.1-0.3 mol L -1; the concentration of the nickel acetate solution is 0.1-0.3 mol L -1; the volume ratio of the terephthalic acid solution to the nickel acetate solution is 1:1-2; heating and stirring to react at 80-120 deg.c and 2-8 h;
in the step (2), the inert gas atmosphere is nitrogen atmosphere, the calcining temperature is 700-900 ℃, and the calcining time is 2-3 h.
2. The method for preparing a biocompatible hydrogen evolution electrocatalyst for the electrocatalytic conversion of carbon dioxide by a microorganism according to claim 1, comprising the steps of:
(1) Respectively dissolving terephthalic acid and nickel acetate in N, N-dimethylformamide to obtain a terephthalic acid solution and a nickel acetate solution, dripping the nickel acetate solution into the terephthalic acid solution, heating, stirring, reacting, collecting a solid product, washing and drying to obtain the Ni-PTA metal organic framework;
(2) Calcining the Ni-PTA metal organic frame obtained in the step (1) at a high temperature in an inert gas atmosphere, cooling to obtain black powder, and pickling to obtain the biocompatible hydrogen evolution electrocatalyst for the electrocatalytic conversion of carbon dioxide by microorganisms;
in the step (1), the concentration of the terephthalic acid solution is 0.1-0.3 mol L -1; the concentration of the nickel acetate solution is 0.1-0.3 mol L -1; the volume ratio of the terephthalic acid solution to the nickel acetate solution is 1:1-2; heating and stirring to react at 80-120 deg.c and 2-8 h;
in the step (2), the inert gas atmosphere is nitrogen atmosphere, the calcining temperature is 700-900 ℃, and the calcining time is 2-3 h.
3. The method for preparing a biocompatible hydrogen evolution electrocatalyst for the electrocatalytic conversion of carbon dioxide by a microorganism according to claim 2, wherein in step (2), the rate of temperature rise of the high temperature calcination is 5 to 10 ℃ min -1.
4. The method for preparing a biocompatible hydrogen evolution electrocatalyst for the electrocatalytic conversion of carbon dioxide by a microorganism according to claim 2, wherein in step (2), sulfuric acid is used for pickling 12 to 24 h.
5. Use of a biocompatible hydrogen evolution electrocatalyst for the electrocatalytic conversion of carbon dioxide by a microorganism according to claim 1.
6. The use of a biocompatible hydrogen evolution electrocatalyst for the electrocatalytic conversion of carbon dioxide by a microorganism according to claim 5, wherein the biocompatible hydrogen evolution electrocatalyst for the electrocatalytic conversion of carbon dioxide by a microorganism is supported on a cathode, promoting the immobilization of CO 2 by aerobic or anaerobic microorganisms and its conversion into high value added products, using a microbial electrosynthesis system.
7. A method for the electrocatalytic conversion of carbon dioxide by microorganisms, comprising the steps of: constructing a three-electrode system, taking a carbon electrode loaded with the biocompatible hydrogen evolution electrocatalyst for the electrocatalytic conversion of carbon dioxide by microorganisms as a cathode, taking Ag/AgCl as a reference electrode, taking a platinum electrode as an anode, forming a closed loop by the cathode, the reference electrode, the anode and an electrochemical workstation, taking an aerobic microorganism culture solution as an electrolyte, connecting the electrochemical workstation, inoculating aerobic microorganisms, controlling the OD 600 of the electrolyte at the initial inoculation to be 0.2-0.3, and operating at a cathode voltage of minus 0.9 to minus 1.2V at room temperature to convert CO 2 into a high added value product.
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