CN105332003A - Ultrathin nanosheet array electro-catalytic material with nano-porous structure and oxygen vacancies - Google Patents
Ultrathin nanosheet array electro-catalytic material with nano-porous structure and oxygen vacancies Download PDFInfo
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Abstract
The invention relates to an ultrathin nanosheet array electro-catalytic material with a nano-porous structure and oxygen vacancies. The material is a cobaltosic oxide primary nanosheet array which grows vertically on a conductive substrate and is doped with a metal; an ultrathin nanosheet with oxygen vacancies and nanopores is obtained on each primary nanosheet; the conductive substrate is a titanium sheet or a foamed nickel sheet, and the doped metal is zinc, nickel or manganese; and the thickness of each cobaltosic oxide ultrathin nanosheet doped with the metal is 1.22 nm, nanosheets are in a three-dimensional porous structure, and the nano-pore diameter is 3-6 nm. The ultrathin nanosheet array electro-catalytic material with the nano-porous structure and oxygen vacancies has the following advantages: the material can effectively reduce the overpotential and the spike potential of an oxygen evolution reaction, increase the conversion rate of a single cobalt atom and work continuously and stably in an alkali environment; the steps of a preparation method of the material are simple, the operation is convenient, the cost is low, and the material is environmental-friendly; and new ideas and strategies are provided for the function-oriented design and the performance optimization of an oxygen evolution catalyst of a water electrolysis system.
Description
Technical field
The invention belongs to electrochemical energy transformation technology field, be specifically related to a kind of ultrathin nanometer chip arrays electrocatalysis material with nano-porous structure and Lacking oxygen.
Background technology
Electrolyzed alkaline water hydrogen manufacturing is the effective solution route of one of reply energy shortage and environmental pollution, in this area, design and obtain the target that high performance evolving hydrogen reaction (HER) and oxygen evolution reaction (OER) electro catalytic electrode material are researchists always, but, be limited to Water oxidize and produce oxygen four electron transfer process slowly, make oxygen evolution reaction become the rate constants of restriction hydrogen generation efficiency.Although noble metal catalyst surfactivity is high, because its cost is high, reserves are few, can not practical requirement.Therefore, what development in recent years formed with transition metal analyses the study hotspot that oxygen eelctro-catalyst becomes people.But these catalyzer also exist the problems such as activity is low, poor stability, thus limit their application.Based on this, from structure and component regulation and control, the base metal OER catalyzer of design and synthesis efficient stable is the core concept of present patent application.
Summary of the invention
The object of the invention is for above-mentioned existing problems, a kind of ultrathin nanometer chip arrays electrocatalysis material with nano-porous structure and Lacking oxygen is provided, this material effectively can reduce the overpotential of oxygen evolution reaction and play spike potential, improve the transformation efficiency on single cobalt atom, and work at strong alkali environment continous-stable; Preparation method's step of this material is simple, easy to operate, with low cost, very friendly to environment, for the functional direction design of electric water of decomposition system oxygen-separating catalyst provides new thinking and strategy with performance optimization.
Technical scheme of the present invention:
A kind of ultrathin nanometer chip arrays electrocatalysis material with nano-porous structure and Lacking oxygen, for in conductive substrates perpendicular to the elementary nano-chip arrays of the tricobalt tetroxide of the doping metals of this substrate grown, described in each, elementary nanometer sheet obtains the ultrathin nanometer sheet with Lacking oxygen and nanoporous, described conductive substrates is titanium sheet or foam nickel sheet, described doping metals is zinc, nickel or manganese, and the mol ratio of doping metals and cobalt is 0.2-0.5:1; The tricobalt tetroxide ultrathin nanometer sheet thickness of doping metals is 1.22nm, and nanometer sheet has three-dimensional porous structure, and nano aperture is 3-6nm.
Described in there is the preparation method of the ultrathin nanometer chip arrays electrocatalysis material of nano-porous structure and Lacking oxygen, comprise the following steps:
1) compound concentration is that the hydrochloric acid soln of 1 mol/L is as first aqueous solution, conductive substrates is put into the first aqueous solution ultrasonic cleaning 5 minutes, again conductive substrates to be put in acetone soln ultrasonic 5 minutes, finally put into deionized water for ultrasonic 5 minutes, take out conductive substrates, put into baking oven dry;
2) Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES is prepared, zinc nitrate, urea and Neutral ammonium fluoride mixing solutions are as second aqueous solution, in second aqueous solution, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES concentration is 0.001 mol/L, zinc nitrate concentration is 0.0005 mol/L, urea concentration is 0.01 mol/L, Neutral ammonium fluoride concentration is 0.0125 mol/L, magnetic agitation was transferred in reactor after 10 minutes, again by step 1) conductive substrates after process tiltingly puts into reactor, seal this reactor, be placed in air dry oven and be warming up to 100 DEG C and carry out first time hydro-thermal reaction at autogenous pressures, 10 hours reaction times, obtained zinc cobalt subcarbonate nanometer sheet, take out conductive substrates, with deionized water rinsing surface, then baking oven is put into dry,
3) by step 2) conductive substrates after process puts into sodium borohydride-sodium hydroxide mixing solutions and soaks 2-4 hour, in sodium borohydride-sodium hydroxide mixing solutions, the concentration of sodium borohydride and sodium hydroxide is 1 mol/L, then conductive substrates is taken out, with dry in vacuum drying oven after deionized water wash;
4) by step 3) conductive substrates after process puts into tube furnace argon atmosphere and calcines, calcining temperature is 250-400 DEG C, calcination time is 2-4 hour, zinc cobalt subcarbonate ultrathin nanometer sheet is made to change the tricobalt tetroxide ultrathin nanometer sheet mixing zinc into, the obtained ultrathin nanometer chip arrays electrocatalysis material with nano-porous structure and Lacking oxygen.
The tricobalt tetroxide ultrathin nanometer sheet of multiple containing transition metal element is with the surface growth of the form of array perpendicular to this conductive substrates.Nano-chip arrays, by introducing a large amount of Lacking oxygen containing the alkaline solution treatment of reductive agent and forming nano-porous structure, makes nanometer sheet thickness less simultaneously, is conducive to catalyzer to H
2o/OH
-absorption.Interlaced between nanometer sheet, form network structure, improve the contact of active catalyst sites and electrolyte solution, make chemisorption O by the Lacking oxygen of containing transition metal element zinc and introducing simultaneously
2more easily separate out.
The tricobalt tetroxide ultrathin nanometer sheet of containing transition metal element has the three-dimensional porous structure of similar nano-porous gold, the specific surface area of material of the present invention can be considerably increased, provide not only a large amount of avtive spots, the transfer that also can be electronics provides high-speed channel, improves the electroconductibility of catalyzer.The present inventor finds, material of the present invention is suitable as the eelctro-catalyst of oxygen evolution reaction very much, but does not also get rid of material of the present invention and find to there is other purposes in the future.
The invention has the beneficial effects as follows: this electrocatalysis material is eelctro-catalyst fabulous in oxygen evolution reaction, playing spike potential is 1.371 ± 0.003V (relative to reversible hydrogen electrode), when current density is 10mA/cm
2time, overpotential is 0.182 ± 0.005V (relative to reversible hydrogen electrode), and on single cobalt atom, transformation efficiency reaches 1.19 ± 0.07s
-1, and excellent stability, being far superior to business-like iridium C catalyst (Ir/C), is best in the electrocatalysis oxygen-separating catalyst reported at present; Electrocatalysis material has abundant Lacking oxygen, is conducive to improving reactant (OH
-) absorption, the doping of metal and the existence of Lacking oxygen improve electroconductibility effectively, the oxygen simultaneously also making catalyst surface produce is easy to chemical desorption occurs, super thin aerosphere face constructed by nano-array, be conducive to the oxygen bubble generation desorption of catalyst surface physical adsorption, the existence of nano-porous structure considerably increases the specific surface area of electrode active material, provides more avtive spot, and these factors are worked in coordination with and enhanced the electrocatalysis ability of this material in oxygen evolution reaction; Its preparation method forms by simple hydro-thermal reaction with containing the aqueous slkali soaking method of reductive agent, and step is simple, easy to operate, with low cost, and preparation process does not adopt any organic solvent and tensio-active agent, very friendly to environment; The product structure obtained is homogeneous, ordered arrangement, what is more important this be a monoblock type material, metal-doped tricobalt tetroxide as active substance in this material is directly connected with the conductive substrates as collector, preparation process does not need to use conductive polymers or binding agent, not only simplifies technical process but also have good electroconductibility; By regulating and controlling the conditions such as the concentration of alkaline solution and reductive agent, the three-dimensional porous ultrathin nanometer chip architecture with different thickness and different Lacking oxygen content can be synthesized, realize the controlled synthesis of the different-shape of material.
Accompanying drawing explanation
Fig. 1 is the structural representation with the ultrathin nanometer chip arrays electrocatalysis material of nano-porous structure of the present invention.
Fig. 2 is with the scanning electron microscope (SEM) photograph (SEM) containing material before the alkaline solution treatment of borane reducing agent sodium hydride.
Fig. 3 is with the stereoscan photograph figure (SEM) containing material after the alkaline solution treatment of borane reducing agent sodium hydride.
Fig. 4 is with the high resolution scanning Electronic Speculum figure containing material after the alkaline solution treatment of borane reducing agent sodium hydride.
Fig. 5 is with the atomic power test curve containing material after the alkaline solution treatment of borane reducing agent sodium hydride.
Fig. 6 is with the X-ray diffractogram (XRD) containing material after the alkaline solution treatment of borane reducing agent sodium hydride.
Fig. 7 is with the nitrogen adsorption desorption curve containing material and Ir/C before and after the alkaline solution treatment of borane reducing agent sodium hydride shown in Fig. 2 and Fig. 3.
Fig. 8 is by the graph of pore diameter distribution containing material and Ir/C before and after the alkaline solution treatment of borane reducing agent sodium hydride shown in Fig. 2 and Fig. 3.
Fig. 9 is with the x-ray photoelectron energy spectrogram (XPS) containing the cobalt element of material before and after the alkaline solution treatment of borane reducing agent sodium hydride shown in Fig. 2 and Fig. 3.
Figure 10 is with the x-ray photoelectron energy spectrogram (XPS) containing the oxygen element of material before and after the alkaline solution treatment of borane reducing agent sodium hydride shown in Fig. 2 and Fig. 3.
Figure 11 is with the fluorescence spectrum figure (PL) containing material before and after the alkaline solution treatment of borane reducing agent sodium hydride shown in Fig. 2 and Fig. 3.
Figure 12 tries hard to containing the adhesion of material and Ir/C catalyzer before and after the alkaline solution treatment of borane reducing agent sodium hydride shown in Fig. 3.
Figure 13 is with the impedance contrast figure containing material before and after the alkaline solution treatment of borane reducing agent sodium hydride shown in Fig. 2 and Fig. 3.
Figure 14 is that reference electrode is reversible hydrogen electrode with polarization curve (LSV) comparison diagram containing the oxygen evolution reaction of material and Ir/C before and after the alkaline solution treatment of borane reducing agent sodium hydride shown in Fig. 2 and Fig. 3.
Figure 15 is polarization curve (LSV) comparison diagram not using sodium borohydride and sodium hydroxide solution process material, embodiment 4 and embodiment 5 material oxygen evolution reaction shown in Fig. 2, and reference electrode is reversible hydrogen electrode.
Figure 16 is with Tafel curve slope (Tafel) comparison diagram containing material and Ir/C before and after the alkaline solution treatment of borane reducing agent sodium hydride shown in Fig. 2 and Fig. 3.
Figure 17 uses material and the inversion frequency of Ir/C under different overpotential (TOF) comparison diagram before and after the alkaline solution treatment containing borane reducing agent sodium hydride shown in Fig. 2 and Fig. 3.
Figure 18 is with the stability comparison diagram containing material and Ir/C before and after the alkaline solution treatment of borane reducing agent sodium hydride shown in Fig. 2 and Fig. 3.
Embodiment
The present invention is further illustrated by following examples.Embodiment is only illustrative, and not restrictive.
Embodiment 1:
A kind of ultrathin nanometer chip arrays electrocatalysis material with nano-porous structure and Lacking oxygen, for in conductive substrates perpendicular to the elementary nano-chip arrays of the tricobalt tetroxide of the doping metals of this substrate grown, described in each, elementary nanometer sheet obtains the ultrathin nanometer sheet with Lacking oxygen and nanoporous, described conductive substrates is titanium sheet, described doping metals is zinc, and the mol ratio of doping metals and cobalt is 0.5:1; The tricobalt tetroxide ultrathin nanometer sheet thickness of doping metals is 1.22nm, and nanometer sheet has three-dimensional porous structure, and nano aperture is 3.6nm
The described preparation method with the ultrathin nanometer chip arrays electrocatalysis material of nano-porous structure and Lacking oxygen, comprises the following steps:
1) compound concentration is hydrochloric acid first aqueous solution of 1 mol/L, conductive substrates is put into hydrochloric acid soln ultrasonic cleaning 5 minutes, then conductive substrates to be put in acetone soln ultrasonic 5 minutes, finally put into deionized water for ultrasonic 5 minutes, take out conductive substrates, put into baking oven dry;
2) Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES is prepared, zinc nitrate, urea and Neutral ammonium fluoride mixing solutions are as second aqueous solution, in second aqueous solution, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES concentration is 0.001 mol/L, zinc nitrate concentration is 0.0005 mol/L, urea concentration is 0.01 mol/L, Neutral ammonium fluoride concentration is 0.0125 mol/L, magnetic agitation is transferred to after 10 minutes in the first reactor, by step 1) conductive substrates after process tiltingly puts into the first reactor, seal this reactor, be placed in air dry oven and be warming up to 100 DEG C and carry out first time hydro-thermal reaction at autogenous pressures, 10 hours reaction times, with this substrate grown nickel cobalt subcarbonate nano-chip arrays vertical on this titanium sheet substrate surface, take out conductive substrates, with deionized water rinsing surface, then baking oven is put into dry,
3) by step 2) conductive substrates after process puts into sodium borohydride-sodium hydroxide mixing solutions and soaks 2 hours, make zinc cobalt subcarbonate nanometer sheet thinner, and a large amount of Lacking oxygen is introduced by sodium borohydride reduction in nanometer sheet, in sodium borohydride-sodium hydroxide mixing solutions, the concentration of sodium borohydride and sodium hydroxide is 1 mol/L, then conductive substrates is taken out, with dry in vacuum drying oven after deionized water wash;
4) by step 4) conductive substrates after process puts into tube furnace argon atmosphere and calcines, calcining temperature is 250 DEG C, calcination time is 3 hours, zinc cobalt subcarbonate ultrathin nanometer sheet is made to change the tricobalt tetroxide ultrathin nanometer sheet mixing zinc into, the obtained ultrathin nanometer chip arrays electrocatalysis material with nano-porous structure and Lacking oxygen.
Fig. 1 is the structural representation with the ultrathin nanometer chip arrays electrocatalysis material of nano-porous structure of the present invention.
Fig. 2 is with the scanning electron microscope (SEM) photograph (SEM) containing material before the alkaline solution treatment of borane reducing agent sodium hydride, can be clear that the tricobalt tetroxide ultrathin nanometer chip arrays of zinc doping is perpendicular to substrate surface homoepitaxial, interlaced between nanometer sheet, form network structure; Wherein substrate is titanium sheet.
Fig. 3 is that wherein clearly show, the material after process maintains original nano-chip arrays structure with the stereoscan photograph figure (SEM) containing material after the alkaline solution treatment of borane reducing agent sodium hydride, and owing to becoming thinner, some bends nanometer sheet.
Fig. 4 is with the high resolution scanning Electronic Speculum figure containing material after the alkaline solution treatment of borane reducing agent sodium hydride, and can be clear that nanometer sheet surface has the three-D nano-porous structure of similar nano-porous gold, primary aperture is 1.9nm.
Fig. 5 is with containing material atom Force meansurement curve after the alkaline solution treatment of borane reducing agent sodium hydride, can find out that the thickness of nanometer sheet is 1.22nm.
Fig. 6 is that contrasting the ultrathin nanometer sheet composition that can pick out on material of the present invention with standard spectrogram is tricobalt tetroxide crystal with the X-ray diffractogram (XRD) containing material after the alkaline solution treatment of borane reducing agent sodium hydride.
Fig. 7 is with the nitrogen adsorption desorption curve containing material and Ir/C before and after the alkaline solution treatment of borane reducing agent sodium hydride shown in Fig. 2 and Fig. 3, show in figure: through increasing containing the sample specific surface area after the alkaline solution treatment of borane reducing agent sodium hydride, reach 125m2/g, untreated samples is then 104m2/g.
Fig. 8 is by the graph of pore diameter distribution containing material and Ir/C before and after the alkaline solution treatment of borane reducing agent sodium hydride shown in Fig. 2 and Fig. 3, show in figure: the sample aperture mainly 3.6nm after containing the alkaline solution treatment of borane reducing agent sodium hydride, untreated samples is then 3.2nm.
Fig. 9 is with the x-ray photoelectron energy spectrogram (XPS) containing the cobalt element of material before and after the alkaline solution treatment of borane reducing agent sodium hydride shown in Fig. 2 and Fig. 3, show in figure: in the sample after containing the alkaline solution treatment of borane reducing agent sodium hydride, the XPS peak of cobalt element there occurs skew to low in conjunction with energy direction, and the divalence cobalt on surface increases.
Figure 10 is with the x-ray photoelectron energy spectrogram (XPS) containing the oxygen element of material before and after the alkaline solution treatment of borane reducing agent sodium hydride shown in Fig. 2 and Fig. 3, show in figure: in the sample after containing the alkaline solution treatment of borane reducing agent sodium hydride, the oxygen defect peak of cobalt element strengthens, and shows that the Lacking oxygen that sample contains increases.
Figure 11 is the fluorescence spectrum figure (PL) using material before and after the alkaline solution treatment containing borane reducing agent sodium hydride shown in Fig. 2 and Fig. 3, shows in figure: in the sample after containing the alkaline solution treatment of borane reducing agent sodium hydride, oxygen vacancy concentration increases.
Figure 12 tries hard to containing the adhesion of material and Ir/C catalyzer before and after the alkaline solution treatment of borane reducing agent sodium hydride shown in Fig. 3, shows: nano-array electrode, compared to plane electrode (Ir/C), has less surface tension in figure.
Figure 13 is the impedance contrast figure using material before and after the alkaline solution treatment containing borane reducing agent sodium hydride shown in Fig. 2 and Fig. 3, shows in figure: through reducing containing the sample electric conductivity increase after the alkaline solution treatment of borane reducing agent sodium hydride, reaction resistance.
Figure 14 is with polarization curve (LSV) comparison diagram containing the oxygen evolution reaction of material and Ir/C before and after the alkaline solution treatment of borane reducing agent sodium hydride shown in Fig. 2 and Fig. 3, reference electrode is reversible hydrogen electrode, show in figure: through having increase containing the sample oxygen evolution activity after the alkaline solution treatment of borane reducing agent sodium hydride, and exceed business-like Ir/C catalyzer.
Figure 16 is Tafel curve slope (Tafel) comparison diagram using material and Ir/C before and after the alkaline solution treatment containing borane reducing agent sodium hydride shown in Fig. 2 and Fig. 3, shows in figure: through having electrode reaction kinetic rate faster containing the sample after the alkaline solution treatment of borane reducing agent sodium hydride.
Figure 17 uses material and the inversion frequency of Ir/C under different overpotential (TOF) comparison diagram before and after the alkaline solution treatment containing borane reducing agent sodium hydride shown in Fig. 2 and Fig. 3, show in figure: the oxygen transformation efficiency of analysing in the sample after containing the alkaline solution treatment of borane reducing agent sodium hydride on single cobalt atom significantly improves.
Figure 18 is the stability comparison diagram using material and Ir/C before and after the alkaline solution treatment containing borane reducing agent sodium hydride shown in Fig. 2 and Fig. 3, shows in figure: through having stability more better than commercialization Ir/C catalyzer containing the sample after the alkaline solution treatment of borane reducing agent sodium hydride.
Embodiment 2:
A kind of ultrathin nanometer chip arrays electrocatalysis material with nano-porous structure and Lacking oxygen, for in conductive substrates perpendicular to the elementary nano-chip arrays of the tricobalt tetroxide of the doping metals of this substrate grown, described in each, elementary nanometer sheet obtains the ultrathin nanometer sheet with Lacking oxygen and nanoporous, described conductive substrates is titanium sheet, described doping metals is nickel, and the mol ratio of doping metals and cobalt is 1:1; The tricobalt tetroxide ultrathin nanometer sheet thickness of doping metals is 10nm, and nanometer sheet has three-dimensional porous structure, and nano aperture is 3.9nm.
The preparation method of this electrocatalysis material is substantially the same manner as Example 1, and difference is: the zinc nitrate in step 2 and 3 is changed to nickelous nitrate.
Embodiment 3:
A kind of ultrathin nanometer chip arrays electrocatalysis material with nano-porous structure and Lacking oxygen, for in conductive substrates perpendicular to the elementary nano-chip arrays of the tricobalt tetroxide of the doping metals of this substrate grown, described in each, elementary nanometer sheet obtains the ultrathin nanometer sheet with Lacking oxygen and nanoporous, described conductive substrates is foam nickel sheet, described doping metals is zinc, and the mol ratio of doping metals and cobalt is 0.5:1; The tricobalt tetroxide ultrathin nanometer sheet thickness of doping metals is 1.5nm, and nanometer sheet has three-dimensional porous structure, and nano aperture is 5nm.
The preparation method of this electrocatalysis material is identical with embodiment 1.The material that the material obtained and embodiment 1 obtain in appearance and performance roughly the same.
Comparative example 4:
A kind of ultrathin nanometer chip arrays electrocatalysis material with nano-porous structure, for in conductive substrates perpendicular to the elementary nano-chip arrays of the tricobalt tetroxide of the doping metals of this substrate grown, described in each, elementary nanometer sheet obtains the ultrathin nanometer sheet with nanoporous, described conductive substrates is titanium sheet, described doping metals is zinc, and the mol ratio of doping metals and cobalt is 0.5:1; The tricobalt tetroxide ultrathin nanometer sheet thickness of doping metals is 1.5nm, and nanometer sheet has three-dimensional porous structure, and nano aperture is 5nm.
See the method in embodiment 1, the soaking solution in embodiment 1 step 3 is changed into independent sodium hydroxide solution or, all the other conditions are constant.Obtain material oxygen evolution reaction polarization curve show see in accompanying drawing 15, figure: nano-chip arrays, can be obviously thinning after sodium hydroxide corrosion, adds the specific surface area of material, thus oxygen evolution reaction activity is improved.
Comparative example 5:
A kind of nano-chip arrays electrocatalysis material with Lacking oxygen, for in conductive substrates perpendicular to the elementary nano-chip arrays of the tricobalt tetroxide of the doping metals of this substrate grown, described in each, elementary nanometer sheet obtains the ultrathin nanometer sheet with Lacking oxygen and nanoporous, described conductive substrates is titanium sheet, described doping metals is zinc, and the mol ratio of doping metals and cobalt is 0.5:1; The tricobalt tetroxide ultrathin nanometer sheet thickness of doping metals is 10nm, and nanometer sheet has three-dimensional porous structure, and nano aperture is 7nm.
See the method in embodiment 1, change the soaking solution in embodiment 1 step 3 into independent sodium borohydride solution, all the other conditions are constant.Obtain the oxygen evolution reaction polarization curve of material see accompanying drawing 15, show in figure: nano-chip arrays is after sodium borohydride reduction, create Lacking oxygen defect, improve the electroconductibility of material and the amount of absorption reaction thing (OH-), thus oxygen evolution reaction activity is improved.
Being described in of above embodiment of the present invention is only exemplary in essence, and its change is not counted as deviating from the spirit and scope of the present invention.
Claims (2)
1. one kind has the ultrathin nanometer chip arrays electrocatalysis material of nano-porous structure and Lacking oxygen, it is characterized in that: in conductive substrates perpendicular to the elementary nano-chip arrays of the tricobalt tetroxide of the doping metals of this substrate grown, described in each, elementary nanometer sheet obtains the ultrathin nanometer sheet with Lacking oxygen and nanoporous, described conductive substrates is titanium sheet or foam nickel sheet, described doping metals is zinc, nickel or manganese, and the mol ratio of doping metals and cobalt is 0.2-0.5:1; The tricobalt tetroxide ultrathin nanometer sheet thickness of doping metals is 1.22nm, and nanometer sheet has three-dimensional porous structure, and nano aperture is 3-6nm.
2. there is a preparation method for the ultrathin nanometer chip arrays electrocatalysis material of nano-porous structure and Lacking oxygen as claimed in claim 1, it is characterized in that comprising the following steps:
1) compound concentration is that the hydrochloric acid soln of 1 mol/L is as first aqueous solution, conductive substrates is put into the first aqueous solution ultrasonic cleaning 5 minutes, again conductive substrates to be put in acetone soln ultrasonic 5 minutes, finally put into deionized water for ultrasonic 5 minutes, take out conductive substrates, put into baking oven dry;
2) Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES is prepared, zinc nitrate, urea and Neutral ammonium fluoride mixing solutions are as second aqueous solution, in second aqueous solution, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES concentration is 0.001 mol/L, zinc nitrate concentration is 0.0005 mol/L, urea concentration is 0.01 mol/L, Neutral ammonium fluoride concentration is 0.0125 mol/L, magnetic agitation was transferred in reactor after 10 minutes, again by step 1) conductive substrates after process tiltingly puts into reactor, seal this reactor, be placed in air dry oven and be warming up to 100 DEG C and carry out first time hydro-thermal reaction at autogenous pressures, 10 hours reaction times, obtained zinc cobalt subcarbonate nanometer sheet, take out conductive substrates, with deionized water rinsing surface, then baking oven is put into dry,
3) by step 2) conductive substrates after process puts into sodium borohydride-sodium hydroxide mixing solutions and soaks 2-4 hour, in sodium borohydride-sodium hydroxide mixing solutions, the concentration of sodium borohydride and sodium hydroxide is 1 mol/L, then conductive substrates is taken out, with dry in vacuum drying oven after deionized water wash;
4) by step 3) conductive substrates after process puts into tube furnace argon atmosphere and calcines, calcining temperature is 250-400 DEG C, calcination time is 2-4 hour, zinc cobalt subcarbonate ultrathin nanometer sheet is made to change the tricobalt tetroxide ultrathin nanometer sheet mixing zinc into, the obtained ultrathin nanometer chip arrays electrocatalysis material with nano-porous structure and Lacking oxygen.
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