CN110652992A - Synthesis method and application of hollow oxide/phosphide carbon-coated composite material for electrocatalytic hydrogen production - Google Patents
Synthesis method and application of hollow oxide/phosphide carbon-coated composite material for electrocatalytic hydrogen production Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 239000001257 hydrogen Substances 0.000 title claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 239000002131 composite material Substances 0.000 title claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 9
- 229910052799 carbon Inorganic materials 0.000 title claims description 9
- 238000001308 synthesis method Methods 0.000 title claims description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 43
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 11
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 11
- 239000002077 nanosphere Substances 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 6
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 5
- 239000012300 argon atmosphere Substances 0.000 claims description 5
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 5
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 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 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000010411 electrocatalyst Substances 0.000 claims description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 238000011144 upstream manufacturing Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims 2
- 238000007789 sealing Methods 0.000 claims 1
- 238000010189 synthetic method Methods 0.000 claims 1
- 238000009210 therapy by ultrasound Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 229910052723 transition metal Inorganic materials 0.000 abstract description 8
- 150000003624 transition metals Chemical class 0.000 abstract description 7
- 239000003792 electrolyte Substances 0.000 abstract description 6
- 230000007062 hydrolysis Effects 0.000 abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 239000000377 silicon dioxide Substances 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 3
- 238000010494 dissociation reaction Methods 0.000 abstract description 2
- 230000005593 dissociations Effects 0.000 abstract description 2
- 239000007789 gas Substances 0.000 abstract description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 5
- 229910000420 cerium oxide Inorganic materials 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000527 sonication Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000002052 molecular layer Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229920001690 polydopamine Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000011712 cell development Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 150000003623 transition metal compounds Chemical class 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- B01J35/51—
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- B01J37/28—Phosphorising
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention belongs to the technical field of electrocatalysis, and discloses hollow oxygen for electrocatalysis hydrogen productionThe synthesis process of composite material with carbide/phosphide as main material includes the main steps of synthesizing nanometer silica particle; synthesizing hollow nano cerium dioxide; synthesis of H-CeO2/Ni @ NC; synthesis of target product H-CeO2/Ni @ NC. The invention utilizes the transition metal oxide to regulate and control the transition metal, realizes rapid dissociation of water molecules and hydrogen removal reaction, and realizes high-efficiency catalytic hydrolysis hydrogen production reaction. The hollow cerium dioxide nanospheres are composed of octahedral sub-nano cerium dioxide particles, so that the hollow cerium dioxide nanospheres have the characteristic of being porous, namely electrolyte and gas are transported more rapidly; the hollow structure can expose larger specific surface area, so that the utilization rate of active sites is improved.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis, and particularly relates to synthesis of a ternary heterostructure catalyst material with a carbon nano-layer coated hollow cerium dioxide nano-sphere surface loaded with nickel phosphide nano-particles and application of the ternary heterostructure catalyst material in hydrolysis hydrogen production.
Background
The hydrogen is an energy carrier with high energy density and clean combustion without pollution, and the electrocatalytic hydrolysis is a mode capable of producing hydrogen in a large scale and sustainable manner. However, the main reason for hindering the large-scale application of the electrocatalytic hydrolysis hydrogen production is that the commercial electrocatalysts are expensive, low in catalytic activity and not satisfactory in stability to meet industrial requirements, which severely restricts the development of the water electrolysis hydrogen production technology, so that the development of materials with low cost, low synthesis method threshold, high activity and high stability is urgently needed to solve the above-mentioned problems.
Transition metals and their compounds are important candidates because of their abundant earth reserves and low prices. Among many transition metal compounds, transition metal phosphide has shown its potential application value, and has been extensively studied since the fact that phosphide was discovered in 2005 to have catalytic activity similar to noble metals. Although many years of research have shown that the HER catalytic activity of transition metal phosphides for acidic conditions is greatly improved, the catalytic activity under alkaline conditions is still poor, in contrast to the more mature commercial electrolytic cell development under alkaline conditions and the higher catalytic activity exhibited by the other half reaction (OER) under alkaline conditions. Thus, alkaline conditions were controlledThe catalytic activity of medium transition metal phosphides is very valuable but challenging. Nickel (Ni) phosphide2P) as one of the transition metal phosphorus group compounds, attention of a wide range of researchers has recently been paid, and the catalytic activity under acidic conditions has platinum-like catalytic activity thanks to its excellent electrical conductivity and suitable hydrogen proton adsorption energy. However, due to the slow water molecule splitting capacity (volmerstein), the catalytic activity under alkaline conditions is 2-3 times smaller than that under acidic conditions, so how to accelerate the hydrogen proton supply rate of water molecules under alkaline conditions is very critical. In addition, the structural design of the catalyst is also very important, and the porous hollow structure can shorten the space transmission distance of the electrolyte to enable the electrolyte to be rapidly transmitted to active sites and expose more specific surface area to enable the utilization rate of the active sites to be more efficient.
Based on the above analysis, we designed a universal method to load nickel phosphide nanoparticles on the surface of hollow ceria, wherein the porous hollow ceria not only provides nucleation sites and large specific surface area, but also can effectively capture water molecules and activate them to generate hydrogen protons required for the next reaction. The nickel phosphide nano-particles are uniformly dispersed on the surface of the cerium dioxide nanospheres and form a heterojunction with the cerium dioxide. Due to the strong interaction influence of the heterojunction, the electronic structure of the nickel phosphide is changed, and then the adsorption strength of the nickel phosphide on hydrogen protons is regulated and controlled, so that the nickel phosphide is easier to desorb from the surface of the catalyst to generate hydrogen. The carbon nano-layer coating structure can inhibit the falling off or the partial aggregation growth of the catalyst, and can also accelerate the transmission of electrons to active sites, thereby improving the conductivity of the catalyst.
Therefore, the invention firstly uses silicon dioxide as a hard template to prepare hollow porous cerium dioxide nanospheres (H-CeO) by a hydrothermal method2) Then coating a poly-dopamine chelated nickel ion layer (H-CeO) on the surface of the nanosphere2～Ni2+@ PDA), then high temperature CVD calcining is carried out to obtain a hollow cerium dioxide surface loaded elemental nickel particle externally coated nitrogen-doped carbon layer (H-CeO)2/Ni @ NC), and finally carrying out phosphating treatment to obtain a target product H-CeO2/Ni2P @ NC. Through electrochemical test, H-CeO2/Ni2The HER activity of P @ NC under alkaline condition is greatly improved, and the current density of 10mA cm in 1M KOH electrolyte is calculated based on the geometric area of a glassy carbon electrode-2The HER over-potential is only 123mV, and the Tafel slope is reduced to 60mV dec-1。
Disclosure of Invention
The invention aims to synthesize H-CeO by a universal hydrothermal and CVD method2/Ni2The P @ NC heterostructure realizes efficient hydrolysis hydrogen production reaction under alkaline conditions.
The technical scheme of the invention is realized by the following steps:
(1) synthesizing nano-silica particles: 4mL of tetraethyl silicate (25%) was added rapidly to a mixed solution of 60mL of ethanol and 25mL of deionized water with moderate stirring. The mixed solution was stirred at room temperature for one hour, centrifuged, washed three times with water and ethanol, and finally evaporated to dryness in vacuo at 60 ℃.
(2) Synthesizing hollow nano cerium dioxide: 0.15g of silica powder was dispersed in a solution of ethanol/deionized water (40mL/20mL) and sonicated for half an hour to form a uniform suspension. Then 3.5g of cerium nitrate hexahydrate and 0.5g of urea were added to the above solution in this order and stirred for 30 minutes to finally form a uniform white solution. The solution was transferred to a 100mL high temperature resistant stainless steel autoclave and sealed. And (3) placing the hydrothermal kettle in a hydrothermal box at 160 ℃ for heat preservation for 8 hours, and naturally cooling to room temperature to obtain a product. Washed with water three times and evaporated to dryness at 50 ℃. And finally, putting the obtained white powder into 1MKOH solution, keeping the temperature at 50 ℃ for 12 hours, washing and drying to obtain the hollow cerium dioxide nanosphere.
(3) Synthesis of H-CeO2/Ni @ NC: first, 0.15g of hollow ceria was dispersed in an ethanol/deionized water (30/30mL) solution, sonicated for 0.5 hour, and then 1mL of ammonia (25%) was injected and stirred. After ten minutes, 0.8g of nickel nitrate hexahydrate and 0.25g of dopamine hydrochloride powder were sequentially added, and the mixed solution was stirred at room temperature for 6 hours, then centrifuged and washed three times, and dried at 60 ℃ under vacuum. Then the obtained brown black powder is kept warm for 2 hours at 750 ℃ in argon atmosphere to finally obtainTo precursor H-CeO2(ii)/Ni @ NC powder.
(4) Synthesis of target product H-CeO2/Ni@NC：H-CeO2Respectively placing 0.1g of/Ni @ NC powder and 0.1g of sodium hypophosphite in a square boat, wherein the sodium hypophosphite is placed at the upstream of the tube furnace, then preserving the heat at 300 ℃ for 2H, and naturally cooling to room temperature to obtain a target product H-CeO2a/Ni @ NC black powder.
The H-CeO2/Ni2P @ NC is applied to HER electrocatalyst.
Compared with the prior art, the invention has the advantages that:
(1) the hollow cerium dioxide surface-loaded nickel phosphide nanoparticles synthesized by the silica hard template method can be popularized to other transition metal phosphide such as cobalt phosphide, copper phosphide and the like, and have good universality.
(2) The invention utilizes the transition metal oxide to regulate and control the transition metal, realizes rapid dissociation of water molecules and hydrogen removal reaction, and realizes high-efficiency catalytic hydrolysis hydrogen production reaction.
(3) The hollow cerium dioxide nanospheres are composed of octahedral sub-nano cerium dioxide particles, so that the hollow cerium dioxide nanospheres have the characteristic of being porous, namely, electrolyte and gas transmission is faster; the hollow structure can expose larger specific surface area, so that the utilization rate of the active sites is improved; the carbon coating layer structure can effectively inhibit the segregation growth and the falling deactivation of the active substances on one hand, and can be used as an electron transport carrier to accelerate the electron transport to the active sites on the other hand.
Drawings
FIG. 1 is an SEM photograph of the hollow cerium oxide obtained in example 1 of the present invention. From the figure, spherical morphology and surface prominence are evident, and further amplification can find the configuration composed of sub-nanoparticles with octahedral structure.
FIG. 2 shows H-CeO obtained in example 1 of the present invention2SEM photograph of/Ni @ NC. From the figure, it is apparent that the nano hollow ceria surface supports many nano metallic nickel particles.
FIG. 3 shows H-CeO obtained in example 1 of the present invention2/Ni2TEM image of P @ NC. The carbon-coated hollow structure is evident from the figure.
FIG. 4 shows H-CeO obtained in example 1 of the present invention2/Ni2LSV curve measured in alkaline electrolyte of P @ NC, normalized by electrochemical surface area (ECSA). The excellent intrinsic electrocatalytic activity of the electrocatalyst is evident from the figure.
Detailed Description
Specific examples of the preparation process according to the invention are given below, the only variable in these cases being the amount of nickel nitrate added, the rest remaining unchanged. These examples are only intended to illustrate the preparation process of the present invention in detail and do not limit the scope of protection of the claims of the present application. Nothing in this specification is said to apply to the prior art.
Example 1
Synthesis of H-CeO2/[email protected]
First, 0.15g of hollow cerium oxide powder was dispersed in an ethanol/deionized water (30/30mL) mixed solution, 1mL of ammonia water (25%) was injected after 0.5 hour of sonication and stirring was performed at room temperature for ten minutes, then 0.8g of nickel nitrate hexahydrate and 0.25g of dopamine hydrochloride powder were sequentially added, and after stirring the mixed solution at room temperature for 6 hours, the mixed solution was washed three times by centrifugation and dried at 60 ℃ in vacuum. Then the obtained brown black powder is subjected to heat preservation for 2 hours in argon atmosphere at the temperature of 750 ℃, and finally a precursor H-CeO is obtained2(ii)/Ni @ NC powder. Then carrying out low-temperature phosphating treatment to obtain H-CeO2/Ni2[email protected]。
Example 2
Synthesis of H-CeO2/[email protected]
First, 0.15g of hollow cerium oxide powder was dispersed in an ethanol/deionized water (30/30mL) mixed solution, 1mL of ammonia water (25%) was injected after 0.5 hour of sonication and stirring was performed at room temperature for ten minutes, then 0.4g of nickel nitrate hexahydrate and 0.25g of dopamine hydrochloride powder were sequentially added, and after stirring the mixed solution at room temperature for 6 hours, the mixed solution was washed three times by centrifugation and dried at 60 ℃ in vacuum. Then the obtained brown black powder is subjected to heat preservation for 2 hours in argon atmosphere at the temperature of 750 ℃, and finally a precursor H-CeO is obtained2(ii)/Ni @ NC powder. Then low-temperature phosphating treatment is carried out to obtainH-CeO2/Ni2[email protected]。
Example 3
Synthesis of H-CeO2/[email protected]
First, 0.15g of hollow cerium oxide powder was dispersed in an ethanol/deionized water (30/30mL) mixed solution, 1mL of ammonia water (25%) was injected after 0.5 hour of sonication and stirring was performed at room temperature for ten minutes, then 1.6g of nickel nitrate hexahydrate and 0.25g of dopamine hydrochloride powder were sequentially added, and after stirring the mixed solution at room temperature for 6 hours, the mixed solution was washed three times by centrifugation and dried at 60 ℃ in vacuum. Then the obtained brown black powder is subjected to heat preservation for 2 hours in argon atmosphere at the temperature of 750 ℃, and finally a precursor H-CeO is obtained2(ii)/Ni @ NC powder. Then carrying out low-temperature phosphating treatment to obtain H-CeO2/[email protected]。
Claims (2)
1. A synthetic method of a hollow oxide/phosphide carbon-coated composite material for electrocatalytic hydrogen production is characterized by comprising the following steps:
(1) synthesizing nano-silica particles: 4mL of tetraethyl silicate (25%) was added rapidly to a mixed solution of 60mL of ethanol and 25mL of deionized water with moderate stirring. Stirring the mixed solution for one hour at room temperature, centrifuging, washing with water and ethanol for three times, and finally evaporating to dryness under the vacuum condition at 60 ℃;
(2) synthesizing hollow nano cerium dioxide: 0.15g of silicon dioxide powder was dispersed in a solution of ethanol/deionized water (40mL/20mL) and sonicated for half an hour to form a homogeneous suspension;
then 3.5g of cerous nitrate hexahydrate and 0.5g of urea are sequentially added into the solution and stirred for 30 minutes, and finally uniform white solution is formed;
transferring the solution to a 100mL high-temperature-resistant stainless steel reaction kettle, and sealing;
placing the hydrothermal kettle in a hydrothermal box at 160 ℃ for heat preservation for 8 hours, and naturally cooling to room temperature to obtain a product;
washing with water for three times, and evaporating to dryness at 50 ℃;
finally, putting the obtained white powder into 1MKOH solution, keeping the temperature at 50 ℃ for 12 hours, washing and drying to obtain hollow cerium dioxide nanospheres;
(3) synthesis of H-CeO2/Ni @ NC: firstly, 0.15g of hollow cerium dioxide is dispersed into an ethanol/deionized water (30/30mL) solution, ultrasonic treatment is carried out for 0.5 hour, and then 1mL of ammonia water (25%) is injected and stirred;
after ten minutes, sequentially adding 0.8g of nickel nitrate hexahydrate and 0.25g of dopamine hydrochloride powder, stirring the mixed solution at room temperature for 6 hours, centrifugally washing for three times, and drying at 60 ℃ in vacuum;
then the obtained brown black powder is subjected to heat preservation for 2 hours in argon atmosphere at the temperature of 750 ℃, and finally a precursor H-CeO is obtained2(ii)/Ni @ NC powder.
(4) Synthesis of target product H-CeO2/Ni@NC：H-CeO2Respectively placing 0.1g of/Ni @ NC powder and 0.1g of sodium hypophosphite in a square boat, wherein the sodium hypophosphite is placed at the upstream of the tube furnace, then preserving the heat at 300 ℃ for 2H, and naturally cooling to room temperature to obtain a target product H-CeO2a/Ni @ NC black powder.
2. Use of the synthesis method according to claim 1 to obtain a hollow oxide/phosphide carbon-coated composite material for electrocatalytic hydrogen production, characterized in that the H-CeO2/Ni2P @ NC is applied to HER electrocatalyst.
Priority Applications (1)
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