CN111530486A - Novel nitrogen-doped carbon-loaded copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material and preparation method thereof - Google Patents
Novel nitrogen-doped carbon-loaded copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 122
- 239000002131 composite material Substances 0.000 title claims abstract description 109
- 239000000463 material Substances 0.000 title claims abstract description 91
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 77
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 72
- 239000010941 cobalt Substances 0.000 title claims abstract description 72
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000004744 fabric Substances 0.000 claims abstract description 85
- 239000002243 precursor Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims description 81
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 74
- 239000000243 solution Substances 0.000 claims description 71
- 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 58
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 58
- 239000011259 mixed solution Substances 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 23
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 22
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 21
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 239000003446 ligand Substances 0.000 claims description 13
- 238000002791 soaking Methods 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 238000000197 pyrolysis Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000003929 acidic solution Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000013153 zeolitic imidazolate framework Substances 0.000 abstract 2
- 239000008367 deionised water Substances 0.000 description 65
- 229910021641 deionized water Inorganic materials 0.000 description 65
- 238000001816 cooling Methods 0.000 description 57
- 238000005303 weighing Methods 0.000 description 46
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 36
- 239000012298 atmosphere Substances 0.000 description 22
- 239000000919 ceramic Substances 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 19
- 229910052786 argon Inorganic materials 0.000 description 18
- 238000003917 TEM image Methods 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 15
- 239000007789 gas Substances 0.000 description 15
- 230000005540 biological transmission Effects 0.000 description 9
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- 230000000694 effects Effects 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 239000012621 metal-organic framework Substances 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000010411 electrocatalyst Substances 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 150000002739 metals Chemical group 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
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- 238000001179 sorption measurement Methods 0.000 description 2
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 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—
-
- B01J35/60—
-
- 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
-
- 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
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
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- 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
-
- 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
- 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
Abstract
The invention discloses a novel nitrogen-doped carbon-loaded copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material and a preparation method thereof. The method comprises the following steps: the method comprises the steps of taking commercial carbon cloth as a self-supporting template guiding agent, growing a copper-doped ZIFs precursor on the surface of a commercial carbon cloth template in a directional mode, pyrolyzing the commercial carbon cloth template containing the precursor at a high temperature in an argon atmosphere, oxidizing at a relatively low temperature, and phosphorizing to obtain the nitrogen-doped carbon-loaded copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material with a porous structure. The nitrogen-doped carbon-loaded copper-doped cobalt phosphide hollow nanoparticle composite array material reserves the basic skeleton of ZIFs, the structure of the composite array material contains rich and regular mesopores and micropores, and the loaded copper-doped cobalt phosphide nanoparticles have an open double-layer hollow structure. The method of the invention is simple and safe, and the obtained product has high purity, complete structure and good mechanical strength, and is suitable for being used as a catalyst for electrocatalytic reactions (hydrogen evolution reaction and oxygen evolution reaction).
Description
Technical Field
The invention relates to the field of preparation of MOFs derived materials, in particular to a novel nitrogen-doped carbon-loaded copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material and a preparation method thereof.
Background
ZIFs are MOFs materials of molecular sieve topological structures formed by self-assembly of 2-methylimidazole containing nitrogen groups and transition metal ions, the nitrogen content in a framework organic matter of the MOFs materials reaches 3-4 wt%, in addition, the ZIFs are used as precursors, the high-nitrogen-doped porous carbon materials can be prepared, due to good designability in the aspect of structures of the porous carbon materials, appropriate second metal elements can be introduced in the crystallization process of the porous carbon materials, the second metal elements, main body metals and ligands form a framework of the ZIFs, part of metal node positions are occupied, simple physical or chemical adsorption is not needed, and uniform dispersion of doped metals is facilitated to be introduced. The metal doped material can be further obtained through post-treatment, so that new defect sites are created, and active sites and the like are added (L.Yang, X.Zeng, W.Wang, D.Cao,. adv.Funct.Mater.2018,28,1704537; T.Liu, P.Li, N.Yao, T.G.Kong, G.Z.Cheng, S.L.Chen, W.Luo, Adv.Mater.2019, 1806672). However, although the varieties of ZIFs derived materials are numerous and exhibit excellent performance in many practical applications, most of the currently reported nanoparticles loaded with ZIFs derived materials have a closed solid structure, which is not favorable for forming a large amount of open structures, so that the number of exposed active sites is small, and internal atoms are wasted. This closed structure provides a relatively small reactive interface for HER and OER, which is detrimental to the timely diffusion of the generated gases and ions (a.aijaz, j.masa, C).
Xia, P.Weide, A.J.R.Botz, R.A.Fischer, W.Schuhmann, M.Muhler, Angew.chem.int.Ed.2016,55, 4087-. In addition, most of the currently reported ZIFs-derived materials have single active sites and single functions (Y.Pan, K.Sun, S.Liu, X.Cao, K.Wu, W.C.Cheng, Z.Chen, Y.Wang, Y.Li, Y.Q.liu, D.S.Wang, Q.Peng, C.Chen, Y.D.Li, J.Am.chem.Soc. 2018,140, 2610-2618). Therefore, the novel hierarchical structure ZIFs-derived nitrogen-doped carbon-loaded hollow nanoparticle composite material suitable for electrocatalysis is prepared, so that the composite material has the characteristics superior to other MOFs-derived composite materials with single pore structures in the aspects of diffusion, mass transfer and the like, and the preparation method is a great problem faced by material workers. This is also a higher demand for social development demands in the field of MOFs-derived composites.
At present, many cobalt-based electrocatalysts reported at present have irregular pore channels or too small pore diameters, serious agglomeration of active components, less exposure of active sites, no access of electrolyte and poor mass transfer effect, so that the actual usable specific surface area is lower than the actual specific surface area of a material, and the conductivity of the catalyst is poor. In view of the problems and limitations presented by cobalt-based electrocatalysts, currently high performance cobalt-based electrocatalysts are mainly studied around two aspects: 1) optimizing the choice of carrier to create more active sites, increase the utilization of active centers and increase the conductivity of the catalyst itself (a. sivanantham, p. ganesan, l. estevez, b.p. mcgrail, r.k. motkuri, s.shanmugam, adv. energy mater.2018,8,1870065.); 2) multiple active sites with synergistic effect are formed by proper heteroatom doping, mainly including non-metal elements such as N, P, S and the like or proper metal element doping, so that the electronic configuration of the catalytic material and the electronic environment around the active sites and other aspects are adjusted and optimized, and the catalytic activity and stability of the material can be improved through reasonable material design (J.H.Song, C.Z.Zhu, B.Z.Xu, S.F.Fu, M.H.Engelhard, R.F.Ye, D.Du, S.P.Beckman, Y.H.Lin, adv.Energy Mater.2017,7,1601555; y.p.zhu, h.c.chen, c.s.hsu, t.s.lin, c.chang, s.c. Chang, l.d.tsai, h.m.chen, ACS Energy lett.2019,4,987-99.). However, all the reported methods cannot prepare a composite array material with a hierarchical pore structure and doping properties, and it is difficult to obtain a loaded nanoparticle with a double-layer hollow structure. Obviously, in order to further improve the application potential of the existing ZIFs-derived composite materials in many applications, the above bottleneck problems must be overcome, and a new route for preparing a novel multilevel structure nitrogen-doped carbon-loaded copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material is provided.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a novel nitrogen-doped carbon-loaded copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material and a preparation method thereof.
The invention aims to overcome the defects of the existing ZIFs derivative material electrocatalyst, and provides a novel multilevel structure nitrogen-doped carbon-loaded copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material derived from a copper-doped ZIFs array by directionally growing a commercial carbon cloth serving as a template and a method thereof.
The purpose of the invention is realized by at least one of the following technical solutions.
The invention provides a preparation method of a novel nitrogen-doped carbon-loaded copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material, which comprises the following steps:
(1) adding a metal precursor into water, and uniformly mixing to obtain a metal precursor solution;
(2) adding the ligand into water, and uniformly mixing to obtain a ligand solution;
(3) uniformly mixing the metal precursor solution and the ligand solution to obtain a mixed solution;
(4) soaking the commercial carbon cloth in an acid solution, taking out, washing and drying to obtain the pretreated commercial carbon cloth;
(5) soaking the pretreated commercial carbon cloth in the step (4) in the mixed solution in the step (3) (standing at normal temperature, then crystallizing ZIFs and directionally growing on a self-supporting template commercial carbon cloth to prepare a leaf-shaped copper-doped ZIFs array material which is arranged on the commercial carbon cloth in order), taking out, washing, drying, heating in an argon atmosphere for high-temperature pyrolysis treatment to obtain a composite array material (the leaf-shaped ZIFs array-derived nitrogen-doped porous carbon loaded copper-doped metal cobalt nanoparticles composite array material which is arranged on the commercial carbon cloth in order);
(6) heating the composite array material obtained in the step (5) to carry out oxidation treatment (air atmosphere) to obtain an oxidized composite array material (the composite array material contains nitrogen-doped porous carbon loaded copper-doped cobaltosic oxide nanoparticles derived from leaf-shaped ZIFs arrays arranged on commercial carbon cloth); mixing the oxidized composite array material with sodium hypophosphite to obtain a mixture; and heating the mixture in an argon atmosphere to carry out phosphating treatment, thus obtaining the novel nitrogen-doped carbon-loaded copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material (leaf-shaped ZIFs array-derived nitrogen-doped carbon-loaded copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material containing regular commercial carbon cloth).
Further, the metal precursor in the step (1) is one of cobalt nitrate hexahydrate and copper nitrate trihydrate; the mass ratio of the metal precursor to the water is 1: (30-120).
Preferably, in the metal precursor in the step (1), the molar ratio of copper to cobalt is (0.05-0.2): 1.
preferably, the water in step (1) and step (2) is deionized water.
Further, the ligand in the step (2) is 2-methylimidazole; the mass ratio of the ligand to the water is 1: (15-60).
Preferably, the mass ratio of the ligand in the step (2) to the metal precursor in the step (1) is (4.5-9): 1.
Further, the acid solution in the step (4) is a mixture of concentrated sulfuric acid and concentrated nitric acid; the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 1: 3.
Preferably, in the step (5), the pre-treated commercial carbon cloth is soaked in the mixed solution for 2 to 8 hours.
Further, the temperature of the high-temperature pyrolysis treatment in the step (5) is 600-900 ℃, and the time of the high-temperature pyrolysis treatment is 1-5 h.
Further, the temperature of the oxidation treatment in the step (6) is 250 ℃, and the time of the oxidation treatment is 0.5-2.5 h.
Preferably, the atmosphere of the oxidation treatment in the step (6) is an air atmosphere.
Further, the mass ratio of the composite array material subjected to oxidation treatment in the step (6) to the sodium hypophosphite is (20-80): 1; the temperature of the phosphating treatment is 300 ℃, and the time of the phosphating treatment is 0.5-3 h.
The invention provides a novel nitrogen-doped carbon-loaded copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material prepared by the preparation method.
The nitrogen-doped carbon-loaded copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material with the multilevel structure prepared by the preparation method keeps the basic skeleton of a copper-doped ZIFs array precursor with high quality and orderly arrangement, and the loaded nanoparticles have a double-layer hollow structure.
The preparation method provided by the invention takes commercial carbon cloth as a self-supporting template guiding agent, and the nitrogen-doped carbon-loaded copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material with a porous structure can be obtained by directionally growing a precursor of copper-doped Zeolitic Imide Frameworks (ZIFs) on the surface of the commercial carbon cloth template, then pyrolyzing the commercial carbon cloth template containing the precursor at high temperature in an argon atmosphere, then oxidizing at relatively low temperature, and finally further phosphorizing.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the novel nitrogen-doped carbon-loaded copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material provided by the invention has a high specific surface area and a rich porous structure, and has a porous structure with a micropore-mesoporous carbon shell as a core, compared with the traditional carbon-based material, the rich mesopores can improve the reactant transmission efficiency, and the micropores are favorable for reaction ion adsorption and accumulation;
(2) the novel nitrogen-doped carbon-loaded copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material provided by the invention has the structural advantages and the synergistic effect: the copper-doped hollow cobalt phosphide nano-particles are beneficial to forming a large number of open structures, so that more active sites are exposed, and the waste of internal atoms is avoided. This open structure provides a large reactive interface for HER and OER and facilitates the diffusion of the generated gases and ions in time. In addition, due to the synergistic effect, the copper-doped cobalt phosphide active site has better electrocatalytic performance than that of a single metal species active site;
(3) the preparation method provided by the invention has the advantages of simple preparation process, safety, controllability, less time consumption and energy consumption, and most importantly, the prepared multistage-structure nitrogen-doped carbon-loaded copper-doped cobalt phosphide double-layer hollow nanoparticles have excellent catalytic performance on electrocatalytic reaction, and the catalytic activity of the prepared multistage-structure nitrogen-doped carbon-loaded copper-doped cobalt phosphide double-layer hollow nanoparticles is far higher than that of a ZIF-67 derived composite material prepared by a traditional method when the multistage-structure nitrogen-doped carbon-loaded copper-doped cobalt phosphide double-layer hollow nanoparticles.
Drawings
FIG. 1 is a scanning electron microscope photograph, a transmission electron microscope photograph and a partial transmission electron microscope photograph of a nitrogen-doped carbon-loaded copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material prepared in example 5 of the present invention;
fig. 2 is a scanning electron microscope photograph, an XRD diffraction pattern, a transmission electron microscope photograph and a partial transmission electron microscope photograph of the nitrogen-doped carbon-loaded copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material prepared in example 8 of the present invention;
fig. 3 is a scanning electron microscope photograph, a transmission electron microscope photograph and a partial transmission electron microscope photograph of the nitrogen-doped carbon-loaded copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material prepared in example 10 of the present invention;
fig. 4 is a scanning electron microscope photograph, a transmission electron microscope photograph and a partial transmission electron microscope photograph of the nitrogen-doped carbon-loaded copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material prepared in example 12 of the present invention;
FIG. 5 is a scanning electron micrograph, a transmission electron micrograph and a partial transmission electron micrograph of the nitrogen-doped carbon-loaded copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material prepared in example 14 of the present invention;
FIG. 6 is a scanning electron microscope photograph of a nitrogen-doped carbon-supported copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material prepared in example 16 of the present invention; transmission electron micrographs and partial transmission electron micrographs.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Example 1
0.291g of cobalt nitrate hexahydrate and 0.0358g of copper nitrate trihydrate are fully dissolved in 40mL of deionized water to prepare a solution A, 1.312g of 2-methylimidazole is fully dissolved in 40mL of deionized water to prepare a solution B, then the two solutions are added into a flat-bottom beaker with the capacity of 100mL, the pretreated commercial carbon cloth is immersed into the beaker containing the mixed solution, the beaker is kept stand at normal temperature for 4 hours and taken out, then the beaker is respectively washed with deionized water and absolute ethyl alcohol for 3 times, and the beaker is dried in vacuum for later use. And then, heating the system to 800 ℃ at a heating rate of 2 ℃/min under the protection of argon, keeping the temperature for 3h, naturally cooling to 250 ℃, introducing an air atmosphere, keeping the temperature for 1h, cooling to room temperature, taking out and weighing the mass of the system, subtracting the initial mass of the carbon cloth, wherein the difference value is the mass of the loaded composite material, then weighing a certain amount of sodium hypophosphite (the mass ratio of the sodium hypophosphite to the loaded composite material is 50:1), placing the sodium hypophosphite in a ceramic crucible at a section of a gas inlet, placing the obtained material at the other end, heating to 300 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 2h, and naturally cooling to room temperature to obtain the nitrogen-doped mesoporous carbon loaded copper-doped cobalt phosphide nanoparticle compound derived from the commercial carbon cloth self-supported ZIF-67 array.
Example 2
1.164g of cobalt nitrate hexahydrate and 0.1462g of copper nitrate trihydrate are fully dissolved in 40mL of deionized water to prepare a solution A, 1.312g of 2-methylimidazole is fully dissolved in 40mL of deionized water to prepare a solution B, then the two solutions are added into a flat-bottom beaker with the capacity of 100mL, the pretreated commercial carbon cloth is immersed into the beaker containing the mixed solution, the beaker is kept stand at normal temperature for 4 hours and taken out, then the beaker is respectively washed with deionized water and absolute ethyl alcohol for 3 times, and the beaker is dried in vacuum for later use. And then, heating the system to 800 ℃ at a heating rate of 2 ℃/min under the protection of argon, keeping the temperature for 3h, naturally cooling to 250 ℃, introducing an air atmosphere, keeping the temperature for 1h, cooling to room temperature, taking out and weighing the mass of the system, subtracting the initial mass of the carbon cloth, wherein the difference value is the mass of the loaded composite material, then weighing a certain amount of sodium hypophosphite (the mass ratio of the sodium hypophosphite to the loaded composite material is 50:1), placing the sodium hypophosphite in a ceramic crucible at a section of a gas inlet, placing the obtained material at the other end, heating to 300 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 2h, and naturally cooling to room temperature to obtain the nitrogen-doped mesoporous carbon loaded copper-doped cobalt phosphide nanoparticle compound derived from the commercial carbon cloth self-supported ZIF-67 array.
Example 3
0.582g of cobalt nitrate hexahydrate and 0.0716g of copper nitrate trihydrate are fully dissolved in 40mL of deionized water to prepare a solution A, 0.656g of 2-methylimidazole is fully dissolved in 40mL of deionized water to prepare a solution B, then the two solutions are added into a flat-bottom beaker with the capacity of 100mL, the pretreated commercial carbon cloth is immersed into the beaker containing the mixed solution, the beaker is kept stand at normal temperature for 4 hours and taken out, then the beaker is respectively washed with deionized water and absolute ethyl alcohol for 3 times, and the beaker is dried in vacuum for later use. And then, heating the system to 800 ℃ at a heating rate of 2 ℃/min under the protection of argon, keeping the temperature for 3h, naturally cooling to 250 ℃, introducing an air atmosphere, keeping the temperature for 1h, cooling to room temperature, taking out and weighing the mass of the system, subtracting the initial mass of the carbon cloth, wherein the difference value is the mass of the loaded composite material, then weighing a certain amount of sodium hypophosphite (the mass ratio of the sodium hypophosphite to the loaded composite material is 50:1), placing the sodium hypophosphite in a ceramic crucible at a section of a gas inlet, placing the obtained material at the other end, heating to 300 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 2h, and naturally cooling to room temperature to obtain the nitrogen-doped mesoporous carbon loaded copper-doped cobalt phosphide nanoparticle compound derived from the commercial carbon cloth self-supported ZIF-67 array.
Example 4
0.582g of cobalt nitrate hexahydrate and 0.0716g of copper nitrate trihydrate are fully dissolved in 40mL of deionized water to prepare a solution A, 2.624g of 2-methylimidazole are fully dissolved in 40mL of deionized water to prepare a solution B, then the two solutions are added into a flat-bottom beaker with the capacity of 100mL, the pretreated commercial carbon cloth is immersed into the beaker containing the mixed solution, the beaker is kept stand at normal temperature for 4 hours and taken out, then the beaker is respectively washed with deionized water and absolute ethyl alcohol for 3 times, and the beaker is dried in vacuum for later use. And then, heating the system to 800 ℃ at a heating rate of 2 ℃/min under the protection of argon, keeping the temperature for 3h, naturally cooling to 250 ℃, introducing an air atmosphere, keeping the temperature for 1h, cooling to room temperature, taking out and weighing the mass of the system, subtracting the initial mass of the carbon cloth, wherein the difference value is the mass of the loaded composite material, then weighing a certain amount of sodium hypophosphite (the mass ratio of the sodium hypophosphite to the loaded composite material is 50:1), placing the sodium hypophosphite in a ceramic crucible at a section of a gas inlet, placing the obtained material at the other end, heating to 300 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 2h, and naturally cooling to room temperature to obtain the nitrogen-doped mesoporous carbon loaded copper-doped cobalt phosphide nanoparticle compound derived from the commercial carbon cloth self-supported ZIF-67 array.
Example 5
0.582g of cobalt nitrate hexahydrate and 0.0358g of copper nitrate trihydrate are fully dissolved in 40mL of deionized water to prepare a solution A, 1.312g of 2-methylimidazole is fully dissolved in 40mL of deionized water to prepare a solution B, then the two solutions are added into a flat-bottom beaker with the capacity of 100mL, the pretreated commercial carbon cloth is immersed into the beaker containing the mixed solution, the beaker is kept stand at normal temperature for 4 hours and taken out, then the beaker is respectively washed with deionized water and absolute ethyl alcohol for 3 times, and the beaker is dried in vacuum for later use. And then, heating the system to 800 ℃ at a heating rate of 2 ℃/min under the protection of argon, keeping the temperature for 3h, naturally cooling to 250 ℃, introducing an air atmosphere, keeping the temperature for 1h, cooling to room temperature, taking out and weighing the mass of the system, subtracting the initial mass of the carbon cloth, wherein the difference value is the mass of the loaded composite material, then weighing a certain amount of sodium hypophosphite (the mass ratio of the sodium hypophosphite to the loaded composite material is 50:1), placing the sodium hypophosphite in a ceramic crucible at a section of a gas inlet, placing the obtained material at the other end, heating to 300 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 2h, and naturally cooling to room temperature to obtain the nitrogen-doped mesoporous carbon loaded copper-doped cobalt phosphide nanoparticle compound derived from the commercial carbon cloth self-supported ZIF-67 array. FIG. 1 is a diagram illustrating the effect of the nitrogen-doped carbon-loaded copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material prepared in this example; wherein from the scanning electron micrograph (part a of fig. 1), it can be seen that the ZIFs-derived matrix composites are closely arranged and regularly shaped; from the transmission electron micrograph (part b of fig. 1) and the partial transmission electron micrograph (part c of fig. 1), it can be seen that the composite-supported nanoparticle exhibits a double-layered hollow structure.
Example 6
0.582g of cobalt nitrate hexahydrate and 0.1432g of copper nitrate trihydrate are fully dissolved in 40mL of deionized water to prepare a solution A, 1.312g of 2-methylimidazole is fully dissolved in 40mL of deionized water to prepare a solution B, then the two solutions are added into a flat-bottom beaker with the capacity of 100mL, the pretreated commercial carbon cloth is immersed into the beaker containing the mixed solution, the beaker is kept stand at normal temperature for 4 hours and taken out, then the beaker is respectively washed with deionized water and absolute ethyl alcohol for 3 times, and the beaker is dried in vacuum for later use. And then, heating the system to 800 ℃ at a heating rate of 2 ℃/min under the protection of argon, keeping the temperature for 3h, naturally cooling to 250 ℃, introducing an air atmosphere, keeping the temperature for 1h, cooling to room temperature, taking out and weighing the mass of the system, subtracting the initial mass of the carbon cloth, wherein the difference value is the mass of the loaded composite material, then weighing a certain amount of sodium hypophosphite (the mass ratio of the sodium hypophosphite to the loaded composite material is 50:1), placing the sodium hypophosphite in a ceramic crucible at a section of a gas inlet, placing the obtained material at the other end, heating to 300 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 2h, and naturally cooling to room temperature to obtain the nitrogen-doped mesoporous carbon loaded copper-doped cobalt phosphide nanoparticle compound derived from the commercial carbon cloth self-supported ZIF-67 array.
Example 7
0.582g of cobalt nitrate hexahydrate and 0.0716g of copper nitrate trihydrate are fully dissolved in 40mL of deionized water to prepare a solution A, 1.312g of 2-methylimidazole is fully dissolved in 40mL of deionized water to prepare a solution B, then the two solutions are added into a flat-bottom beaker with the capacity of 100mL, the pretreated commercial carbon cloth is immersed into the beaker containing the mixed solution, the beaker is kept stand at normal temperature for 2 hours and taken out, then the beaker is respectively washed with deionized water and absolute ethyl alcohol for 3 times, and the beaker is dried in vacuum for later use. And then, heating the system to 600 ℃ at a heating rate of 2 ℃/min under the protection of argon, keeping the temperature for 3h, naturally cooling to 250 ℃, introducing an air atmosphere, keeping the temperature for 1h, cooling to room temperature, taking out and weighing the mass of the system, subtracting the initial mass of the carbon cloth, wherein the difference value is the mass of the loaded composite material, then weighing a certain amount of sodium hypophosphite (the mass ratio of the sodium hypophosphite to the loaded composite material is 50:1), placing the sodium hypophosphite in a ceramic crucible at a section of a gas inlet, placing the obtained material at the other end, heating to 300 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 2h, and naturally cooling to room temperature to obtain the nitrogen-doped mesoporous carbon loaded copper-doped cobalt phosphide nanoparticle compound derived from the commercial carbon cloth self-supported ZIF-67 array.
Example 8
0.582g of cobalt nitrate hexahydrate and 0.0716g of copper nitrate trihydrate are fully dissolved in 40mL of deionized water to prepare a solution A, 1.312g of 2-methylimidazole is fully dissolved in 40mL of deionized water to prepare a solution B, then the two solutions are added into a flat-bottom beaker with the capacity of 100mL, the pretreated commercial carbon cloth is immersed into the beaker containing the mixed solution, the beaker is kept stand at normal temperature for 4 hours and taken out, then the beaker is respectively washed with deionized water and absolute ethyl alcohol for 3 times, and the beaker is dried in vacuum for later use. Subsequently, the system is heated at the heating rate of 2 ℃/min under the protection of argonAnd keeping the temperature at 800 ℃ for 3h, naturally cooling to 250 ℃, introducing air atmosphere, keeping the temperature for 1h, cooling to room temperature, taking out and weighing the mass of the carbon cloth, subtracting the initial mass of the carbon cloth, wherein the difference value is the mass of the loaded composite material, then weighing a certain amount of sodium hypophosphite (the mass ratio of the sodium hypophosphite to the loaded composite material is 50:1), placing the sodium hypophosphite at one section of the air inlet in a ceramic crucible, placing the obtained material at the other end of the ceramic crucible, heating to 300 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 2h, and naturally cooling to room temperature to obtain the nitrogen-doped mesoporous carbon loaded copper-doped cobalt phosphide nanoparticle composite derived from the commercial carbon cloth self-supported ZIF-67 array. FIG. 2 is a diagram illustrating the effect of the nitrogen-doped carbon-loaded copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material prepared in this example; wherein from the scanning electron micrograph (part a of fig. 2), it can be seen that the ZIFs-derived matrix composites are closely arranged and regularly shaped; from the XRD pattern (part b of fig. 2), it can be seen that the metal species is mainly present in the form of cobalt phosphide, and from the transmission electron micrograph (part c of fig. 2) and the partial transmission electron micrograph (part d of fig. 2), it can be seen that the composite-supported nanoparticle exhibits a double-layered hollow structure; table 1 shows that the current density of the hydrogen evolution reaction and the oxygen evolution reaction in the 1M KOH solution of this example is 10mA/cm2Over-potential of (c).
TABLE 1
Table 1 shows that in example 8, the current density reached 10mA cm during the electrochemical hydrogen and oxygen evolution reaction test-2The overpotential required, as can be seen from table 1, the samples doped with transition metal copper have good performance on electrochemical hydrogen and oxygen evolution reactions in alkaline electrolyte, and the current density reaches 10mA cm-2The overpotential required is only 182mV and 103mV, respectively. Nitrogen-doped carbon-supported copper-doped cobalt phosphide double-layer hollow core prepared in other examplesThe electrocatalytic performance of the nanoparticle composite array material is substantially similar to that of the present example.
Example 9
0.582g of cobalt nitrate hexahydrate and 0.0716g of copper nitrate trihydrate are fully dissolved in 40mL of deionized water to prepare a solution A, 1.312g of 2-methylimidazole is fully dissolved in 40mL of deionized water to prepare a solution B, then the two solutions are added into a flat-bottom beaker with the capacity of 100mL, the pretreated commercial carbon cloth is immersed into the beaker containing the mixed solution, the beaker is kept stand at normal temperature for 8 hours and taken out, then the beaker is respectively washed with deionized water and absolute ethyl alcohol for 3 times, and the beaker is dried in vacuum for later use. And then, heating the system to 800 ℃ at a heating rate of 2 ℃/min under the protection of argon, keeping the temperature for 3h, naturally cooling to 250 ℃, introducing an air atmosphere, keeping the temperature for 1h, cooling to room temperature, taking out and weighing the mass of the system, subtracting the initial mass of the carbon cloth, wherein the difference value is the mass of the loaded composite material, then weighing a certain amount of sodium hypophosphite (the mass ratio of the sodium hypophosphite to the loaded composite material is 50:1), placing the sodium hypophosphite in a ceramic crucible at a section of a gas inlet, placing the obtained material at the other end, heating to 300 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 2h, and naturally cooling to room temperature to obtain the nitrogen-doped mesoporous carbon loaded copper-doped cobalt phosphide nanoparticle compound derived from the commercial carbon cloth self-supported ZIF-67 array.
Example 10
0.582g of cobalt nitrate hexahydrate and 0.0716g of copper nitrate trihydrate are fully dissolved in 40mL of deionized water to prepare a solution A, 1.312g of 2-methylimidazole is fully dissolved in 40mL of deionized water to prepare a solution B, then the two solutions are added into a flat-bottom beaker with the capacity of 100mL, the pretreated commercial carbon cloth is immersed into the beaker containing the mixed solution, the beaker is kept stand at normal temperature for 4 hours and taken out, then the beaker is respectively washed with deionized water and absolute ethyl alcohol for 3 times, and the beaker is dried in vacuum for later use. And then, heating the system to 600 ℃ at a heating rate of 2 ℃/min under the protection of argon, keeping the temperature for 3h, naturally cooling to 250 ℃, introducing an air atmosphere, keeping the temperature for 1h, cooling to room temperature, taking out and weighing the mass of the system, subtracting the initial mass of the carbon cloth, wherein the difference value is the mass of the loaded composite material, then weighing a certain amount of sodium hypophosphite (the mass ratio of the sodium hypophosphite to the loaded composite material is 50:1), placing the sodium hypophosphite in a ceramic crucible at a section of a gas inlet, placing the obtained material at the other end, heating to 300 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 2h, and naturally cooling to room temperature to obtain the nitrogen-doped mesoporous carbon loaded copper-doped cobalt phosphide nanoparticle compound derived from the commercial carbon cloth self-supported ZIF-67 array. FIG. 3 is a diagram illustrating the effect of the nitrogen-doped carbon-loaded copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material prepared in the present example; wherein from the scanning electron micrograph (part a of fig. 3), it can be seen that the ZIFs-derived matrix composites are closely arranged and regularly shaped; from the transmission electron micrograph (part b of fig. 3) and the partial transmission electron micrograph (part c of fig. 3), it can be seen that the composite-supported nanoparticle exhibits a double-layered hollow structure.
Example 11
0.582g of cobalt nitrate hexahydrate and 0.0716g of copper nitrate trihydrate are fully dissolved in 40mL of deionized water to prepare a solution A, 1.312g of 2-methylimidazole is fully dissolved in 40mL of deionized water to prepare a solution B, then the two solutions are added into a flat-bottom beaker with the capacity of 100mL, the pretreated commercial carbon cloth is immersed into the beaker containing the mixed solution, the beaker is kept stand at normal temperature for 4 hours and taken out, then the beaker is respectively washed with deionized water and absolute ethyl alcohol for 3 times, and the beaker is dried in vacuum for later use. And then, heating the system to 900 ℃ at a heating rate of 2 ℃/min under the protection of argon, keeping the temperature for 3h, naturally cooling to 250 ℃, introducing an air atmosphere, keeping the temperature for 1h, cooling to room temperature, taking out and weighing the mass of the system, subtracting the initial mass of the carbon cloth, wherein the difference value is the mass of the loaded composite material, then weighing a certain amount of sodium hypophosphite (the mass ratio of the sodium hypophosphite to the loaded composite material is 50:1), placing the sodium hypophosphite in a ceramic crucible at a section of an air inlet, placing the obtained material at the other end, heating to 300 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 2h, and naturally cooling to room temperature to obtain the nitrogen-doped mesoporous carbon loaded copper-doped cobalt phosphide nanoparticle compound derived from the commercial carbon cloth self-supported ZIF-67 array.
Example 12
0.582g of cobalt nitrate hexahydrate and 0.0716g of copper nitrate trihydrate are fully dissolved in 40mL of deionized water to prepare a solution A, 1.312g of 2-methylimidazole is fully dissolved in 40mL of deionized water to prepare a solution B, then the two solutions are added into a flat-bottom beaker with the capacity of 100mL, the pretreated commercial carbon cloth is immersed into the beaker containing the mixed solution, the beaker is kept stand at normal temperature for 4 hours and taken out, then the beaker is respectively washed with deionized water and absolute ethyl alcohol for 3 times, and the beaker is dried in vacuum for later use. And then, heating the system to 800 ℃ at a heating rate of 2 ℃/min under the protection of argon, keeping the temperature for 1h, naturally cooling to 250 ℃, introducing an air atmosphere, keeping the temperature for 1h, cooling to room temperature, taking out and weighing the mass of the system, subtracting the initial mass of the carbon cloth, wherein the difference value is the mass of the loaded composite material, then weighing a certain amount of sodium hypophosphite (the mass ratio of the sodium hypophosphite to the loaded composite material is 50:1), placing the sodium hypophosphite in a ceramic crucible at a section of a gas inlet, placing the obtained material at the other end, heating to 300 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 2h, and naturally cooling to room temperature to obtain the nitrogen-doped mesoporous carbon loaded copper-doped cobalt phosphide nanoparticle compound derived from the commercial carbon cloth self-supported ZIF-67 array. FIG. 4 is a diagram illustrating the effect of the nitrogen-doped carbon-loaded copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material prepared in the present example; wherein from the scanning electron micrograph (part a of fig. 4), it can be seen that the ZIFs-derived matrix composites are closely arranged and regularly shaped; from the transmission electron micrograph (part b of fig. 4) and the partial transmission electron micrograph (part c of fig. 4), it can be seen that the composite-supported nanoparticle exhibits a double-layered hollow structure.
Example 13
Soaking a 4x4cm commercial carbon cloth in concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 1:3 for 24h, removing, cleaning with deionized water, drying in vacuum, weighing the mass for later use: 0.582g of cobalt nitrate hexahydrate and 0.0716g of copper nitrate trihydrate are fully dissolved in 40mL of deionized water to prepare a solution A, 1.312g of 2-methylimidazole is fully dissolved in 40mL of deionized water to prepare a solution B, then the two solutions are added into a flat-bottom beaker with the capacity of 100mL, the pretreated commercial carbon cloth is immersed into the beaker containing the mixed solution, the beaker is kept stand at normal temperature for 4 hours and taken out, then the beaker is respectively washed with deionized water and absolute ethyl alcohol for 3 times, and the beaker is dried in vacuum for later use. And then, heating the system to 800 ℃ at a heating rate of 2 ℃/min under the protection of argon, keeping the temperature for 5 hours, naturally cooling to 250 ℃, introducing an air atmosphere, keeping the temperature for 1 hour, cooling to room temperature, taking out and weighing the mass of the system, subtracting the initial mass of the carbon cloth, wherein the difference value is the mass of the loaded composite material, then weighing a certain amount of sodium hypophosphite (the mass ratio of the sodium hypophosphite to the loaded composite material is 50:1), placing the sodium hypophosphite in a ceramic crucible at a section of a gas inlet, placing the obtained material at the other end, heating to 300 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 2 hours, and naturally cooling to room temperature to obtain the nitrogen-doped mesoporous carbon loaded copper-doped cobalt phosphide nanoparticle compound derived from the commercial carbon cloth self-supported ZIF-67 array.
Example 14
Soaking a 4x4cm commercial carbon cloth in concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 1:3 for 24h, removing, cleaning with deionized water, drying in vacuum, weighing the mass for later use: 0.582g of cobalt nitrate hexahydrate and 0.0716g of copper nitrate trihydrate are fully dissolved in 40mL of deionized water to prepare a solution A, 1.312g of 2-methylimidazole is fully dissolved in 40mL of deionized water to prepare a solution B, then the two solutions are added into a flat-bottom beaker with the capacity of 100mL, the pretreated commercial carbon cloth is immersed into the beaker containing the mixed solution, the beaker is kept stand at normal temperature for 4 hours and taken out, then the beaker is respectively washed with deionized water and absolute ethyl alcohol for 3 times, and the beaker is dried in vacuum for later use. And then, heating the system to 800 ℃ at a heating rate of 2 ℃/min under the protection of argon, keeping the temperature for 3h, naturally cooling to 250 ℃, introducing an air atmosphere, keeping the temperature for 0.5h, cooling to room temperature, taking out and weighing the mass of the system, subtracting the initial mass of the carbon cloth, wherein the difference value is the mass of the loaded composite material, then weighing a certain amount of sodium hypophosphite (the mass ratio of the sodium hypophosphite to the loaded composite material is 50:1), placing the weighed material in a ceramic crucible at a section of an air inlet, placing the material at the other end, heating to 300 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 2h, and naturally cooling to room temperature to obtain the nitrogen-doped mesoporous carbon loaded copper-doped cobalt phosphide nanoparticle composite derived from the commercial carbon cloth self-supported ZIF-67 array. FIG. 5 is a diagram illustrating the effect of the nitrogen-doped carbon-loaded copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material prepared in this example; wherein from the scanning electron micrograph (part a of fig. 5), it can be seen that the ZIFs-derived matrix composites are closely arranged and regularly shaped; from the transmission electron micrograph (part b of fig. 5) and the partial transmission electron micrograph (part c of fig. 5), it can be seen that the composite-supported nanoparticle exhibits a double-layered hollow structure.
Example 15
Soaking a 4x4cm commercial carbon cloth in concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 1:3 for 24h, removing, cleaning with deionized water, drying in vacuum, weighing the mass for later use: 0.582g of cobalt nitrate hexahydrate and 0.0716g of copper nitrate trihydrate are fully dissolved in 40mL of deionized water to prepare a solution A, 1.312g of 2-methylimidazole is fully dissolved in 40mL of deionized water to prepare a solution B, then the two solutions are added into a flat-bottom beaker with the capacity of 100mL, the pretreated commercial carbon cloth is immersed into the beaker containing the mixed solution, the beaker is kept stand at normal temperature for 4 hours and taken out, then the beaker is respectively washed with deionized water and absolute ethyl alcohol for 3 times, and the beaker is dried in vacuum for later use. And then, heating the system to 800 ℃ at a heating rate of 2 ℃/min under the protection of argon, keeping the temperature for 3h, naturally cooling to 250 ℃, introducing an air atmosphere, keeping the temperature for 2.5h, taking out and weighing the mass of the system after cooling to room temperature, subtracting the initial mass of the carbon cloth, wherein the difference value is the mass of the loaded composite material, then weighing a certain amount of sodium hypophosphite (the mass ratio of the sodium hypophosphite to the loaded composite material is 50:1), placing the weighed material in a ceramic crucible at a section of an air inlet, placing the material at the other end, heating to 300 ℃ at the heating rate of 2 ℃/min, keeping the temperature for 2h, and naturally cooling to room temperature to obtain the nitrogen-doped mesoporous carbon loaded copper-doped cobalt phosphide nanoparticle composite derived from the commercial carbon cloth self-supported ZIF-67 array.
Example 16
Soaking a 4x4cm commercial carbon cloth in concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 1:3 for 24h, removing, cleaning with deionized water, drying in vacuum, weighing the mass for later use: 0.582g of cobalt nitrate hexahydrate and 0.0716g of copper nitrate trihydrate are fully dissolved in 40mL of deionized water to prepare a solution A, 1.312g of 2-methylimidazole is fully dissolved in 40mL of deionized water to prepare a solution B, then the two solutions are added into a flat-bottom beaker with the capacity of 100mL, the pretreated commercial carbon cloth is immersed into the beaker containing the mixed solution, the beaker is kept stand at normal temperature for 4 hours and taken out, then the beaker is respectively washed with deionized water and absolute ethyl alcohol for 3 times, and the beaker is dried in vacuum for later use. And then, heating the system to 800 ℃ at a heating rate of 2 ℃/min under the protection of argon, keeping the temperature for 3h, naturally cooling to 250 ℃, introducing an air atmosphere, keeping the temperature for 1h, cooling to room temperature, taking out and weighing the mass of the system, subtracting the initial mass of the carbon cloth, wherein the difference value is the mass of the loaded composite material, then weighing a certain amount of sodium hypophosphite (the mass ratio of the sodium hypophosphite to the loaded composite material is 20:1), placing the weighed material in a ceramic crucible at a section of an air inlet, placing the material at the other end, heating to 300 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 2h, and naturally cooling to room temperature to obtain the nitrogen-doped mesoporous carbon loaded copper-doped cobalt phosphide nanoparticle compound derived from the commercial carbon cloth self-supported ZIF-67 array. FIG. 6 is a diagram illustrating the effect of the nitrogen-doped carbon-loaded copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material prepared in this example; wherein from the scanning electron micrograph (part a of fig. 6), it can be seen that the ZIFs-derived matrix composites are closely arranged and regularly shaped; from the transmission electron micrograph (part b of fig. 6) and the partial transmission electron micrograph (part c of fig. 6), it can be seen that the composite-supported nanoparticle exhibits a double-layered hollow structure.
Example 17
Soaking a 4x4cm commercial carbon cloth in concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 1:3 for 24h, removing, cleaning with deionized water, drying in vacuum, weighing the mass for later use: 0.582g of cobalt nitrate hexahydrate and 0.0716g of copper nitrate trihydrate are fully dissolved in 40mL of deionized water to prepare a solution A, 1.312g of 2-methylimidazole is fully dissolved in 40mL of deionized water to prepare a solution B, then the two solutions are added into a flat-bottom beaker with the capacity of 100mL, the pretreated commercial carbon cloth is immersed into the beaker containing the mixed solution, the beaker is kept stand at normal temperature for 4 hours and taken out, then the beaker is respectively washed with deionized water and absolute ethyl alcohol for 3 times, and the beaker is dried in vacuum for later use. And then, heating the system to 800 ℃ at a heating rate of 2 ℃/min under the protection of argon, keeping the temperature for 5 hours, naturally cooling to 250 ℃, introducing an air atmosphere, keeping the temperature for 1 hour, cooling to room temperature, taking out and weighing the mass of the system, subtracting the initial mass of the carbon cloth, wherein the difference value is the mass of the loaded composite material, then weighing a certain amount of sodium hypophosphite (the mass ratio of the sodium hypophosphite to the loaded composite material is 80:1), placing the sodium hypophosphite in a ceramic crucible at a section of a gas inlet, placing the obtained material at the other end, heating to 300 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 2 hours, and naturally cooling to room temperature to obtain the nitrogen-doped mesoporous carbon loaded copper-doped cobalt phosphide nanoparticle compound derived from the commercial carbon cloth self-supported ZIF-67 array.
Example 18
Soaking a 4x4cm commercial carbon cloth in concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 1:3 for 24h, removing, cleaning with deionized water, drying in vacuum, weighing the mass for later use: 0.582g of cobalt nitrate hexahydrate and 0.0716g of copper nitrate trihydrate are fully dissolved in 40mL of deionized water to prepare a solution A, 1.312g of 2-methylimidazole is fully dissolved in 40mL of deionized water to prepare a solution B, then the two solutions are added into a flat-bottom beaker with the capacity of 100mL, the pretreated commercial carbon cloth is immersed into the beaker containing the mixed solution, the beaker is kept stand at normal temperature for 4 hours and taken out, then the beaker is respectively washed with deionized water and absolute ethyl alcohol for 3 times, and the beaker is dried in vacuum for later use. And then, heating the system to 800 ℃ at a heating rate of 2 ℃/min under the protection of argon, keeping the temperature for 5 hours, naturally cooling to 250 ℃, introducing an air atmosphere, keeping the temperature for 1 hour, cooling to room temperature, taking out and weighing the mass of the system, subtracting the initial mass of the carbon cloth, wherein the difference value is the mass of the loaded composite material, then weighing a certain amount of sodium hypophosphite (the mass ratio of the sodium hypophosphite to the loaded composite material is 50:1), placing the sodium hypophosphite in a ceramic crucible at a section of an air inlet, placing the obtained material at the other end, heating to 300 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 0.5 hour, and naturally cooling to room temperature to obtain the nitrogen-doped mesoporous carbon loaded copper-doped cobalt phosphide nanoparticle composite derived from the commercial carbon cloth self-supported ZIF-67 array.
Example 19
Soaking a 4x4cm commercial carbon cloth in concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 1:3 for 24h, removing, cleaning with deionized water, drying in vacuum, weighing the mass for later use: 0.582g of cobalt nitrate hexahydrate and 0.0716g of copper nitrate trihydrate are fully dissolved in 40mL of deionized water to prepare a solution A, 1.312g of 2-methylimidazole is fully dissolved in 40mL of deionized water to prepare a solution B, then the two solutions are added into a flat-bottom beaker with the capacity of 100mL, the pretreated commercial carbon cloth is immersed into the beaker containing the mixed solution, the beaker is kept stand at normal temperature for 4 hours and taken out, then the beaker is respectively washed with deionized water and absolute ethyl alcohol for 3 times, and the beaker is dried in vacuum for later use. And then, heating the system to 800 ℃ at a heating rate of 2 ℃/min under the protection of argon, keeping the temperature for 5 hours, naturally cooling to 250 ℃, introducing an air atmosphere, keeping the temperature for 1 hour, cooling to room temperature, taking out and weighing the mass of the system, subtracting the initial mass of the carbon cloth, wherein the difference value is the mass of the loaded composite material, then weighing a certain amount of sodium hypophosphite (the mass ratio of the sodium hypophosphite to the loaded composite material is 50:1), placing the sodium hypophosphite in a ceramic crucible at a section of a gas inlet, placing the obtained material at the other end, heating to 300 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 3 hours, and naturally cooling to room temperature to obtain the nitrogen-doped mesoporous carbon loaded copper-doped cobalt phosphide nanoparticle compound derived from the commercial carbon cloth self-supported ZIF-67 array.
Hydrogen evolution and oxygen evolution reactions in alkaline electrolytes: weighing 1x1cm3The catalyst, graphite rod as the counter electrode, saturated Ag/AgCl as the reference electrode, the reaction in oxygen saturated 0.1M KOH solution. Hydrogen evolution test: the sweep rate was 5m V/s, and the potential interval was-1.0 to 0.05V (vs. Ag/AgCl). Oxygen evolution reaction test: the sweep rate was 5m V/s, and the potential interval was 1.0 to 0.8V (vs. Ag/AgCl).
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.
Claims (10)
1. A preparation method of a novel nitrogen-doped carbon-loaded copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material is characterized by comprising the following steps:
(1) adding a metal precursor into water, and uniformly mixing to obtain a metal precursor solution;
(2) adding the ligand into water, and uniformly mixing to obtain a ligand solution;
(3) uniformly mixing the metal precursor solution and the ligand solution to obtain a mixed solution;
(4) soaking the commercial carbon cloth in an acid solution, taking out, washing and drying to obtain the pretreated commercial carbon cloth;
(5) soaking the pretreated commercial carbon cloth in the step (4) in the mixed solution in the step (3), taking out, washing, drying, and then heating in an argon atmosphere to perform high-temperature pyrolysis treatment to obtain a composite array material;
(6) heating the composite array material obtained in the step (5) for oxidation treatment to obtain an oxidized composite array material; mixing the oxidized composite array material with sodium hypophosphite to obtain a mixture; and heating the mixture in an argon atmosphere to carry out phosphating treatment to obtain the novel nitrogen-doped carbon-loaded copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material.
2. The preparation method of the novel nitrogen-doped carbon-supported copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material according to claim 1, wherein the metal precursor in the step (1) is one of cobalt nitrate hexahydrate and copper nitrate trihydrate; the mass ratio of the metal precursor to water is 1: (30-120).
3. The preparation method of the novel nitrogen-doped carbon-supported copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material according to claim 1, wherein the mass ratio of the ligand in the step (2) to the metal precursor in the step (1) is (4.5-9): 1.
4. The preparation method of the novel nitrogen-doped carbon-supported copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material according to claim 1, wherein the ligand in the step (2) is 2-methylimidazole; the mass ratio of the ligand to the water is 1: (15-60).
5. The preparation method of the novel nitrogen-doped carbon-supported copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material according to claim 1, wherein the acidic solution in the step (4) is a mixture of concentrated sulfuric acid and concentrated nitric acid; the volume ratio of the concentrated sulfuric acid to the concentrated nitric acid is 1: 3.
6. The preparation method of the novel nitrogen-doped carbon-supported copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material as claimed in claim 1, wherein in the step (5), the time for soaking the pretreated commercial carbon cloth in the mixed solution is 2-8 hours.
7. The method for preparing the novel nitrogen-doped carbon-supported copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material as claimed in claim 1, wherein the temperature of the high-temperature pyrolysis treatment in the step (5) is 600-900 ℃, and the time of the high-temperature pyrolysis treatment is 1-5 h.
8. The preparation method of the novel nitrogen-doped carbon-supported copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material according to claim 1, wherein the temperature of the oxidation treatment in the step (6) is 250 ℃, and the time of the oxidation treatment is 0.5-2.5 h.
9. The preparation method of the novel nitrogen-doped carbon-supported copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material according to claim 1, wherein the mass ratio of the composite array material subjected to oxidation treatment in the step (6) to sodium hypophosphite is (20-50): 1; the temperature of the phosphating treatment is 300 ℃, and the time of the phosphating treatment is 0.5-3 h.
10. A novel nitrogen-doped carbon-loaded copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material prepared by the preparation method of any one of claims 1-9.
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