CN113368878A - MnCoP catalyst, preparation and application - Google Patents
MnCoP catalyst, preparation and application Download PDFInfo
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- CN113368878A CN113368878A CN202110602872.5A CN202110602872A CN113368878A CN 113368878 A CN113368878 A CN 113368878A CN 202110602872 A CN202110602872 A CN 202110602872A CN 113368878 A CN113368878 A CN 113368878A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 claims abstract description 18
- 238000009713 electroplating Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011159 matrix material Substances 0.000 claims abstract description 12
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000003792 electrolyte Substances 0.000 claims abstract description 11
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 11
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 11
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 10
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 10
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 10
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 10
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 7
- 230000007062 hydrolysis Effects 0.000 claims abstract description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004327 boric acid Substances 0.000 claims abstract description 6
- 238000002791 soaking Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 18
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 16
- 239000004917 carbon fiber Substances 0.000 claims description 16
- 239000004744 fabric Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims 1
- 230000001588 bifunctional effect Effects 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000011572 manganese Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 239000002135 nanosheet Substances 0.000 description 5
- 230000010355 oscillation Effects 0.000 description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 2
- 229910003252 NaBO2 Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011217 control strategy Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/187—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a MnCoP catalyst, preparation and application, and the preparation steps are as follows: (1) preparing an electrolyte: mixing cobalt chloride, manganese sulfate, sodium hypophosphite and boric acid in an aqueous solution to obtain an electrolyte; (2) preparation of MnCoP catalyst: and soaking the cleaned porous matrix material in the electrolyte, connecting the porous matrix material with a power supply cathode for a cathode of an electrolysis device, and electroplating to obtain the MnCoP catalytic material loaded on the porous matrix material. The invention can enable metal to be fully plated on the carrier without a surface catalyst, and can synthesize the bifunctional MnCoP catalyst which has good binding force, large area and high catalytic performance and is used for sodium borohydride hydrolysis and water electrolysis hydrogen production by only two steps.
Description
Technical Field
The invention belongs to the field of hydrogen energy and fuel cells, and particularly relates to a MnCoP catalyst, and preparation and application thereof.
Background
Hydrogen energy is a clean energy source and is increasingly favored by consumers as a zero-carbon energy source. Compared with traditional energy sources such as petroleum, natural gas and coal, the hydrogen energy has the following advantages: (1) the combustion heat value is very high, the heat produced by burning hydrogen with the same mass is about 3 times of gasoline, 3.9 times of alcohol and 4.5 times of coke; (2) the combustion product is water, which is the cleanest energy in the world and is abundant in resource reserves. At present, scientists are exploring new technology capable of producing hydrogen in large quantity and low cost, and although the hydrogen production by water electrolysis is convenient to operate and raw materials are easy to obtain, the cost for producing the same hydrogen is too large. Due to the normal temperature and normal atmospheric pressure, H2Is extremely easy to burn and explode, has unstable performance, is not safe in the process of storage, loading and unloading and has danger. In recent years, many advanced energy storage and conversion technologies, such as sodium borohydride hydrolysis and water electrolysis hydrogen production technologies, have been developed rapidly, and the technologies can effectively realize the conversion between chemical energy and electric energy, and play an important role in efficiently utilizing renewable clean energy, relieving energy crisis and environmental pollution, and the core of these energy conversion devices is the electrochemical process: wherein sodium borohydride is hydrolysable in an aqueous alkaline solution in the presence of a catalyst to produce hydrogen gas and sodium metaborate, the reaction being as follows: NaBH4 + 2H2O →4H2↑+ NaBO2(ii) a The electrolysis of water is divided into two half-reactions, Hydrogen Evolution (HER) and oxygen evolutionThe reaction (OER) is taken out.
In the process of electrocatalysis reaction, the high-efficiency electrocatalyst can effectively reduce the energy consumption required by the reaction process, so the research on the high-efficiency electrocatalyst becomes important for the research on sustainable energy technology,
at present, catalysts for hydrogen production in the prior art mainly comprise Pt, Ru noble metals and alloy particle catalysts thereof, and have the defects of high cost, difficult recovery, difficult reaction control, complex steps and long time, so that the development of a bifunctional catalyst for high-efficiency sodium borohydride hydrolysis and water electrolysis hydrogen production based on non-noble metals becomes very important, cobalt (Co) becomes a non-noble metal which is very much concerned by scientists due to good catalytic performance, and a great deal of research is focused on a cobalt-based compound as a homogeneous molecular catalyst for sodium borohydride hydrolysis or hydrogen evolution at present. Particularly, the cobalt-based phosphide has high electrocatalytic activity and is paid attention to by a plurality of researchers, the manganese (Mn) element is abundant in nature, the 3d orbit is not full, Mn can be doped to realize double regulation and control of an electronic structure and a shape and a size, and the electrocatalytic activity is effectively improved. .
Disclosure of Invention
Aiming at the problems of the catalyst for hydrogen production by electrolytic catalysis in the prior art, the invention provides a bifunctional MnCoP catalyst for sodium borohydride hydrolysis and hydrogen production by electrolytic water, and preparation and application thereof.
The technical purpose is achieved, the technical effect is achieved, and the invention is realized through the following technical scheme:
a preparation method of a MnCoP catalyst comprises the following steps:
preparing an electrolyte: mixing cobalt chloride, manganese sulfate, sodium hypophosphite and boric acid in an aqueous solution to obtain an electrolyte;
preparation of MnCoP catalyst: and soaking the cleaned porous matrix material in the electrolyte, connecting the porous matrix material with a power supply cathode for a cathode of an electrolysis device, and electroplating to obtain the MnCoP catalytic material loaded on the porous matrix material.
As a further improvement of the invention, in the electrolyte
The concentration of the cobalt chloride is 11.9-95.2 g/L;
the concentration of the manganese sulfate is 1.7-10.15 g/L;
the concentration of the sodium hypophosphite is 8.8-43.88 g/L.
As a further improvement of the invention, the concentration of the boric acid is 25-45 g/L.
As a further improvement of the invention, the areal density of the porous matrix material is 200-300g/m2。
As a further improvement of the invention, the porous matrix material is any one of carbon fiber cloth or foamed nickel.
As a further improvement of the invention, the electroplating is carried out by adopting a double-pulse electroplating method, and the technological parameters of the electroplating are that the electroplating time is 0.5-4min, the electroplating temperature is 40-50 ℃, and the current density is 0.3-0.7A/cm2。
The MnCoP catalyst is prepared by the preparation method of the MnCoP catalyst.
Use of a MnCoP catalyst as described above for the hydrolysis of sodium borohydride and for the electrolysis of water to produce hydrogen.
The invention has the beneficial effects that:
(1) in view of the preparation process, the catalyst mainly containing manganese can be fully plated on the carrier without a surface catalyst, and only two steps are needed to synthesize the catalyst, so that the operation is easy and short, the operation steps can be further simplified, and the cost can be saved.
(2) From the structure of the prepared catalyst, Mn is doped to realize double regulation and control of an electronic structure and a shape and a size of a Co active site, a layer of Mn-doped CoP nanosheet is directly deposited on a substrate, the size of a precursor CoP nanosheet is increased, the electrochemical active area is increased, gas diffusion is facilitated, meanwhile, the electronic structure can be regulated and controlled to enable the negative shift of a Co electronic peak to be beneficial to the improvement of catalytic performance, and the electrocatalysis performance is more efficiently improved through the double regulation and control strategy of the specific surface area and the electronic structure.
Drawings
FIG. 1 is a graph showing the influence of the reaction temperature on the catalyst performance in the example of the present invention;
FIG. 2 is an SEM photograph of CoP/CC catalyst prepared after double pulse plating of undoped manganese;
FIG. 3 is an SEM photograph of a MnCoP/CC catalyst prepared after double pulse plating according to an embodiment of the invention;
FIG. 4 is an XRD photograph of a MnCoP/CC catalyst prepared after double pulse plating according to an embodiment of the present invention;
FIG. 5 is a graph of the effect of cobalt chloride concentration on the performance of a MnCoP/CC catalyst;
FIG. 6 is a graph showing the effect of manganese sulfate concentration on the performance of a MnCoP/CC catalyst;
FIG. 7 is a graph of the effect of sodium hypophosphite concentration on performance for making MnCoP/CC catalysts;
FIG. 8 is a graph of HER polarization for comparative CoP/CC catalysts, MnCoP/CC catalysts.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The following detailed description of the principles of the invention is provided in connection with the accompanying drawings.
Examples
(1) The surface density is 250g/m2Soaking the carbon fiber cloth sample in absolute ethyl alcohol, and cleaning for 5min at 25 ℃ by ultrasonic oscillation so as to fully remove stains on the surface of the carbon fiber cloth;
(2) washing the carbon fiber cloth soaked in the ethanol in the step (1) by using deionized water, and then soaking the carbon fiber cloth in 0.01 mol/L diluted hydrochloric acid for ultrasonic oscillation for 2min to remove surface impurities and oxides;
(3) cleaning the carbon fiber cloth soaked by dilute hydrochloric acid by using deionized water ultrasonic oscillation for 10min, drying the carbon fiber cloth in a drying oven at 50 ℃ for 1-2h after oscillation cleaning, weighing and storing for later use;
(4) preparing (0.05 mol/L) 11.9g/L cobalt chloride, (0.008 mol/L) 1.7g/L manganese sulfate, and (0.25 mol/L) 26.3g/L manganous oxideAdding 25.28 g/L boric acid serving as a buffering agent into the sodium phosphate mixed solution, soaking the carbon fiber cloth obtained in the step (3) in the mixed solution for double-pulse electroplating, connecting a power supply anode with a platinum electrode, connecting a power supply cathode with the carbon fiber cloth, and electroplating at 50 ℃ and a current density of 0.3A/cm for 3min2(ii) a And taking out the carbon fiber cloth after electroplating, cleaning the carbon fiber cloth for 2-3 times by using absolute ethyl alcohol, immersing the carbon fiber cloth in deionized water, carrying out ultrasonic oscillation for 5min, and finally drying the carbon fiber cloth in a drying oven at 50 ℃ for 30-45 min. Obtaining the dual-function catalyst for hydrolyzing the MnCoP sodium borohydride loaded on the carbon fiber cloth and producing hydrogen by electrolyzing water.
And (3) performance testing:
(1) effect of temperature on Hydrogen production Performance of catalyst
Placing the MnCoP/CC catalyst prepared in the example 1 in a sodium borohydride solution, and inspecting the change rule of the hydrogen production performance along with the temperature change; the temperature was 30-60 ℃ and the results are shown in FIG. 1. From fig. 1, it can be seen that the hydrogen production rate of the catalyst prepared by the invention is increased along with the increase of the temperature, which shows that the temperature of the hydrogen production solution has great influence on the hydrogen production rate.
(2) Appearance observation SEM
The MnCoP/CC catalyst prepared in the example 1 is subjected to electron microscope scanning, the SEM photo of the MnCoP/CC catalyst is shown in figure 3, the SEM photo of the CoP/CC catalyst before being doped with manganese is shown in figure 2, and the MnCoP is uniformly distributed on the surface of the carbon fiber cloth and is combined compactly according to figures 2 and 3, so that the MnCoP/CC catalyst prepared by the invention is compact in distribution, large in large-particle active area and good in small-particle density. After Mn element is doped into CoP/CC, the structural characteristics of a nanosheet of the CoP/CC are well preserved by MnCoP/CC without any change basically, but the size is changed, the average size (the length is 0.75-0.9 μm, and the thickness is-0.25 μm) of the MnCoP nanosheet is larger and rougher than the size of the CoP nanosheet (the length is 1.3-1.6 μm, and the thickness is-0.35 μm, which is probably because the Co atom of CoP is replaced by Mn to increase the structural size, and the MnCoP/CC diffraction peak is widened compared with the CoP/CC in figure 4, which shows that the doping of Mn element can improve the content of the substance and is related to the increase of the size of the appearance.
(3) Influence of reaction reagent concentration on hydrogen production performance of catalyst
The same experimental raw materials and steps as those in example 1 are adopted, and the concentrations of cobalt chloride, manganese sulfate and sodium hypophosphite are respectively changed by adopting a single-factor control method; the concentration values of the substances are shown in fig. 5, 6 and 7, respectively.
FIG. 5 corresponds to the adjustment of the concentration of cobalt chloride to vary from 0.05 mol/l to 0.4mol/l, and it can be seen from FIG. 5 that the hydrogen production rate of the prepared catalyst MnCoP/CC is the greatest when the concentration of cobalt chloride is 0.3 mol/l.
FIG. 6 corresponds to the adjustment of the concentration variation range of manganese sulfate to be 0.008-0.046mol/l, and it can be seen from FIG. 6 that the prepared MnCoP/CC hydrogen production rate is the maximum when the concentration of manganese sulfate is 0.046 mol/l.
FIG. 7 corresponds to the adjustment of the variation range of the sodium hypophosphite concentration to 0.08-0.42mol/l, and it can be seen from FIG. 7 that the maximum MnCoP/CC hydrogen production rate is obtained when the sodium hypophosphite concentration is 0.33 mol/l.
(4) HER and OER tests were carried out on CoP/CC catalysts and MnCoP/CC catalysts before and after doping with manganese, respectively, using the cobalt chloride concentration of 0.3mol/l and the sodium hypophosphite concentration of 0.33mol/l at the time of the maximum hydrogen production rate in test example 1.
As can be seen from FIG. 8, the original CoP/CC exhibited good hydrogen evolution catalytic performance at 10 mA cm-2The overpotential of the current density of (1) is 124 mV, and after Mn element doping, the MnCoP/CC can reach 10 mA cm only by 69 mV overpotential-2The current density of (a) indicates that the Mn-doped CoP can play a significant promoting role.
When MnCoP/CC reaches 10 mA cm-2And 100 mA cm-2The required overpotentials at current densities were 261 mV and 460 mV, respectively, lower than the CoP/CC, indicating that Mn-doped CoP also has a very good promoting effect in the OER test.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (8)
1. The preparation method of the MnCoP catalyst is characterized by comprising the following steps of:
preparing an electrolyte: mixing cobalt chloride, manganese sulfate, sodium hypophosphite and boric acid in an aqueous solution to obtain an electrolyte;
preparation of MnCoP catalyst: and soaking the cleaned porous matrix material in the electrolyte, connecting the porous matrix material with a power supply cathode for a cathode of an electrolysis device, and electroplating to obtain the MnCoP catalytic material loaded on the porous matrix material.
2. The method of claim 1 for preparing a MnCoP catalyst, wherein the MnCoP catalyst comprises: in the electrolyte
The concentration of the cobalt chloride is 11.9-95.2 g/L;
the concentration of the manganese sulfate is 1.7-10.15 g/L;
the concentration of the sodium hypophosphite is 8.8-43.88 g/L.
3. The method of claim 1 for preparing a MnCoP catalyst, wherein the MnCoP catalyst comprises: the concentration of the boric acid is 25-45 g/L.
4. The method of claim 1 for preparing a MnCoP catalyst, wherein the MnCoP catalyst comprises: the areal density of the porous matrix material is 200-300g/m2。
5. The method for preparing a MnCoP catalyst according to claim 1 or 4, wherein: the porous base material is any one of carbon fiber cloth or foam nickel.
6. The method of claim 1 for preparing a MnCoP catalyst, wherein the MnCoP catalyst comprises: by usingElectroplating by double-pulse electroplating method, wherein the electroplating time is 0.5-4min, the electroplating temperature is 40-50 deg.C, and the current density is 0.3-0.7A/cm2。
7. A MnCoP catalyst, characterized by: a catalyst prepared by the method of any one of claims 1 to 6 for the preparation of a MnCoP catalyst.
8. Use of a MnCoP catalyst according to claim 7 for the hydrolysis of sodium borohydride and for the electrolysis of water for the production of hydrogen.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114751369A (en) * | 2022-05-19 | 2022-07-15 | 重庆大学 | MnCo2O4.5-MgH2Composite hydrogen storage material and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060292067A1 (en) * | 2005-06-28 | 2006-12-28 | Qinglin Zhang | Hydrogen generation catalysts and methods for hydrogen generation |
| CN101347736A (en) * | 2007-07-20 | 2009-01-21 | 中国科学院金属研究所 | Catalyst for hydrogen production by catalyzing and hydrolyzing borohydride and preparation method thereof |
| CN107188122A (en) * | 2016-03-15 | 2017-09-22 | 四川大学 | Transition metal phosphide reacts the application of catalyst for preparing hydrogen as borohydride hydrolytic |
| CN107413360A (en) * | 2017-08-22 | 2017-12-01 | 江苏师范大学 | A kind of carbon cloth load C oMoP preparing hydrogen by sodium borohydride hydrolysis catalyst and preparation method thereof |
| CN108525685A (en) * | 2017-03-01 | 2018-09-14 | 中国科学院理化技术研究所 | Hydrogen storage material hydrolysis hydrogen release system using monodisperse or supported phosphorus-containing metal compound as catalyst |
| CN109652830A (en) * | 2019-01-04 | 2019-04-19 | 中国计量大学 | A kind of cobalt-manganese-phosphorus magnetism electroplate liquid and preparation method thereof |
| CN111790415A (en) * | 2020-06-28 | 2020-10-20 | 江苏师范大学 | B-P co-doped double-transition metal catalyst and preparation method and application thereof |
| CN112121829A (en) * | 2020-09-25 | 2020-12-25 | 合肥工业大学 | Manganese-doped transition metal atom metal phosphide catalyst, preparation method thereof and application thereof in hydrogen production by water electrolysis |
-
2021
- 2021-05-31 CN CN202110602872.5A patent/CN113368878B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060292067A1 (en) * | 2005-06-28 | 2006-12-28 | Qinglin Zhang | Hydrogen generation catalysts and methods for hydrogen generation |
| CN101347736A (en) * | 2007-07-20 | 2009-01-21 | 中国科学院金属研究所 | Catalyst for hydrogen production by catalyzing and hydrolyzing borohydride and preparation method thereof |
| CN107188122A (en) * | 2016-03-15 | 2017-09-22 | 四川大学 | Transition metal phosphide reacts the application of catalyst for preparing hydrogen as borohydride hydrolytic |
| CN108525685A (en) * | 2017-03-01 | 2018-09-14 | 中国科学院理化技术研究所 | Hydrogen storage material hydrolysis hydrogen release system using monodisperse or supported phosphorus-containing metal compound as catalyst |
| CN107413360A (en) * | 2017-08-22 | 2017-12-01 | 江苏师范大学 | A kind of carbon cloth load C oMoP preparing hydrogen by sodium borohydride hydrolysis catalyst and preparation method thereof |
| CN109652830A (en) * | 2019-01-04 | 2019-04-19 | 中国计量大学 | A kind of cobalt-manganese-phosphorus magnetism electroplate liquid and preparation method thereof |
| CN111790415A (en) * | 2020-06-28 | 2020-10-20 | 江苏师范大学 | B-P co-doped double-transition metal catalyst and preparation method and application thereof |
| CN112121829A (en) * | 2020-09-25 | 2020-12-25 | 合肥工业大学 | Manganese-doped transition metal atom metal phosphide catalyst, preparation method thereof and application thereof in hydrogen production by water electrolysis |
Non-Patent Citations (1)
| Title |
|---|
| SIRAN XU, ET AL.: "Contrallable synthesis of peony-like porous Mn-CoP nanorod electrocatalyst for highly efficient hydrogen evolution in acid and alkaline" * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114751369A (en) * | 2022-05-19 | 2022-07-15 | 重庆大学 | MnCo2O4.5-MgH2Composite hydrogen storage material and preparation method thereof |
| CN114751369B (en) * | 2022-05-19 | 2023-07-04 | 重庆大学 | MnCo 2 O 4.5 -MgH 2 Composite hydrogen storage material and preparation method thereof |
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