CN117568843A - Selenium-defect-enriched tin diselenide nanosheet electrocatalyst and preparation method and application thereof - Google Patents
Selenium-defect-enriched tin diselenide nanosheet electrocatalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN117568843A CN117568843A CN202311455651.5A CN202311455651A CN117568843A CN 117568843 A CN117568843 A CN 117568843A CN 202311455651 A CN202311455651 A CN 202311455651A CN 117568843 A CN117568843 A CN 117568843A
- Authority
- CN
- China
- Prior art keywords
- selenium
- tin
- tin diselenide
- nanosheet electrocatalyst
- enriched
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- KBPGBEFNGHFRQN-UHFFFAOYSA-N bis(selanylidene)tin Chemical compound [Se]=[Sn]=[Se] KBPGBEFNGHFRQN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000002135 nanosheet Substances 0.000 title claims abstract description 45
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 49
- 235000019253 formic acid Nutrition 0.000 claims abstract description 42
- 239000011669 selenium Substances 0.000 claims abstract description 42
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 38
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims abstract description 38
- 230000007547 defect Effects 0.000 claims abstract description 28
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 9
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 14
- 230000002950 deficient Effects 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 abstract description 24
- 239000003792 electrolyte Substances 0.000 abstract description 14
- 230000002378 acidificating effect Effects 0.000 abstract description 9
- 230000007935 neutral effect Effects 0.000 abstract description 6
- 230000036961 partial effect Effects 0.000 abstract description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 34
- 239000001569 carbon dioxide Substances 0.000 description 17
- 229910002092 carbon dioxide Inorganic materials 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- 238000004435 EPR spectroscopy Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229940036348 bismuth carbonate Drugs 0.000 description 4
- GMZOPRQQINFLPQ-UHFFFAOYSA-H dibismuth;tricarbonate Chemical compound [Bi+3].[Bi+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GMZOPRQQINFLPQ-UHFFFAOYSA-H 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Chemical group O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001621 bismuth Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- XIMIGUBYDJDCKI-UHFFFAOYSA-N diselenium Chemical compound [Se]=[Se] XIMIGUBYDJDCKI-UHFFFAOYSA-N 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000011366 tin-based material Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
-
- 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
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a tin diselenide nanosheet electrocatalyst rich in selenium defects, which comprises the following steps: and dissolving selenium dioxide and metallic tin salt, adding hydrazine hydrate solution, stirring and mixing, and performing hydrothermal reaction to obtain the selenium-enriched tin diselenide nanosheet electrocatalyst. The invention also discloses the tin diselenide nanosheet electrocatalyst rich in selenium defects obtained by the preparation method and application of the tin diselenide nanosheet electrocatalyst serving as a working electrode in formic acid electrosynthesis. The catalyst provided by the invention realizes high selectivity of HCOOH electrosynthesis in alkaline, neutral and acidic electrolytes respectively, and the HCOOH partial current density reaches the industrial level under the corresponding pH condition, so that the catalyst fully shows excellent HCOOH electrosynthesis performance in the full pH range.
Description
Technical Field
The invention relates to the technical field of electrocatalysts, in particular to a tin diselenide nanosheet electrocatalyst rich in selenium defects, and a preparation method and application thereof.
Background
Carbon dioxide (CO) using renewable energy sources 2 ) Among various reduction products, formic acid (HCOOH) is considered as one of the most technically economical products, and has been widely used in practical applications. Several major p-region metal main group catalysts have been reported to date, including Sn, in, bi, and the like, and a series of corresponding metal oxides (such as tin oxide and indium oxide) for the electroreduction of CO 2 Synthesizing HCOOH. Wherein, because of low cost of metal tin-based material, the adsorption energy of OOCH intermediate in the process of electrosynthesis of HCOOH is moderate, so that the catalyst is widely applied to the electroreduction of CO 2 Synthesizing HCOOH. However, the metallic tin-based catalysts reported to date do @ achieve high selectivity commercial current densities>200mA cm -2 ) The aspects of HCOOH electrosynthesis still face significant challenges.
Currently, HCOOH electrosynthesis is mostly carried out in alkaline or neutral electrolytes, and thus, the formation of carbonate byproducts is unavoidable, leading to CO 2 The utilization efficiency is lowered. The use of an acidic electrolyte is one of the effective methods for solving these problems. However, due to the electroreduction of CO 2 Competitive hydrogen evolution side reactions and unavoidable proton concentration changes in the process, achieving sustained effective CO in acidic electrolytes 2 Transformation still faces a significant challenge. Therefore, in industrial applications, it is highly necessary to develop ideal catalysts that work well over the full pH range. The Chinese patent document with publication number CN115584522A discloses a preparation method of a three-dimensional porous electrode and an acidic electrocatalytic CO thereof 2 The application of preparing formic acid by reduction is that a catalyst, a polymer and an organic solvent are uniformly mixed to prepare composite slurry, the slurry is uniformly coated on carbon cloth by a scraper to obtain an unformed blank, and finally a three-dimensional porous electrode is obtained by drying treatment, so that HCOOH is prepared by electric reduction under the acidic condition that the pH is less than 3.77.
The formation of OOCH intermediates is typically the rate-determining reaction step due to slow reaction kinetics during proton formation and transport. Thus, accelerating proton generation and transfer is an effective method of increasing OOCH/HCOOH generation rate. The introduction of defective structures is considered to be one of the most direct and effective methods for regulating metal electrons and surface structures, and has been studied extensively in recent years. The Chinese patent document of publication No. CN116103680A discloses an oxygen vacancy-enriched bismuth carbonate electrocatalyst and a preparation method thereof, bismuth salt is dissolved in glycol and aqueous solution, a proper amount of auxiliary conductive salt is added, and then the bismuth salt is refrigerated to obtain electrolyte, and electrochemical deposition is carried out on a working electrode by using a constant current method to obtain oxygen vacancy-enriched bismuth carbonate nanosheets, wherein the introduction of oxygen vacancies improves the conductivity of bismuth carbonate, and improves the water splitting ability of bismuth carbonate and the intrinsic activity of HCOOH synthesis.
Although CO is reduced electrically for different electrolyte environments 2 Research on the synthesis of HCOOH has been greatly advanced, but industrial current density achieved over the full pH range>200mA cm -2 ) The HCOOH electrosynthesis of (c) still faces the problem of low selectivity.
Disclosure of Invention
The invention aims to provide a preparation method of a tin diselenide nanosheet electrocatalyst rich in selenium defects, and the prepared catalyst is rich in selenium defects and shows excellent catalysis performance of HCOOH electrosynthesis.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for preparing a tin diselenide nanosheet electrocatalyst rich in selenium defects, the method comprising the steps of: and dissolving selenium dioxide and metallic tin salt, adding hydrazine hydrate solution, stirring and mixing, and performing hydrothermal reaction to obtain the selenium-enriched tin diselenide nanosheet electrocatalyst.
The preparation principle of the tin diselenide nanosheet electrocatalyst rich in selenium defects provided by the invention is as follows: adding a reducing reagent hydrazine hydrate into the mixed solution of uniformly dispersed selenium dioxide and metallic tin salt, and adding Sn in the solution into hydrazine hydrate molecules with strong reducibility 2+ And Se (Se) 4+ Reduced to atoms with high reflectionThe Sn atoms and Se atoms that should be active combine to form a tin diselenide molecule, accompanied by the formation of selenium defects. The selenium defect is introduced to transfer more electrons from Se sites to Sn sites, so that dissociation of water molecules is effectively accelerated, proton transfer rate is improved, and CO is accelerated 2 High efficiency conversion at tin active site.
The metallic tin salt is a soluble salt, preferably the metallic tin salt is stannous chloride dihydrate.
The molar ratio of the selenium dioxide to the metallic tin salt is 1.5-2.5:1. According to the invention, the tin diselenide nano-sheets with different purity and rich selenium defects are prepared by changing the dosage of selenium dioxide. When the molar concentration of selenium dioxide is too low, the purity of the resulting tin diselenide is reduced, and the presence of heterogeneous tin is observed for the electroreduction of CO 2 The performance of synthesizing HCOOH is not obviously improved; when the molar concentration of selenium dioxide is too high, a selenous phase can appear, so that the electrosynthesis performance of HCOOH is obviously reduced.
Further, dissolving selenium dioxide and metallic tin salt in water to obtain a mixed solution, wherein the mass concentration of the selenium dioxide is 7.4-22.2 g L -1 The mass concentration of the tin salt is 15.0. 15.0g L -1 . Preferably, the mass concentration of the selenium dioxide is 14.8g L -1 。
Wherein, the selenium dioxide and the metallic tin salt are dissolved in a certain amount of aqueous solution, the reaction temperature is room temperature, and the stirring time is 10-20 min. Preferably, the stirring time is 20min.
Further, the mass concentration of the hydrazine hydrate is 54.8g L in the mixed solution after the hydrazine hydrate is added -1 。
And after the mixed solution of the selenium dioxide and the metallic tin salt is added into the hydrazine hydrate solution, the reaction temperature is normal temperature, and the stirring time is 3-8 min. Too long stirring time can affect the morphology of tin diselenide to be uneven and the formation of selenium defects, thereby affecting the performance of the electrocatalyst. Preferably, the stirring time is 3 minutes.
The hydrothermal reaction temperature is 160-200 ℃. The selenium defects with different contents are prepared by changing the hydrothermal reaction temperatureTin diselenide nanosheets of (a). When the hydrothermal reaction temperature is too low, tin diselenide nano-sheets rich in selenium defects are not easy to form; when the hydrothermal reaction temperature is too high, the nano-sheet of the tin diselenide is easy to generate crystal phase transition at high temperature, so that CO is electrically reduced 2 The performance of preparing HCOOH is reduced.
Preferably, the molar ratio of the selenium dioxide to the metallic tin salt is 1.5-2:1, and the hydrothermal reaction temperature is 180-200 ℃. By limiting the molar ratio and the reaction temperature, the purity and the content of selenium defects in the prepared tin diselenide nano-sheet are more beneficial to improving the electric reduction CO 2 Selectivity for the preparation of HCOOH.
The invention also provides the tin diselenide nanosheet electrocatalyst rich in selenium defects, which is obtained by the preparation method.
The abundant selenium defects in the catalyst exist in the tin diselenide nanosheets, and the atomic ratio of selenium to tin in the tin diselenide nanosheets electrocatalyst is 1.8-2.0:1.
The invention also provides an application of the selenium-enriched tin diselenide nanosheet electrocatalyst serving as a working electrode in formic acid electrosynthesis.
Furthermore, the tin diselenide nanosheet electrocatalyst rich in selenium defects is used as a working electrode in formic acid electrosynthesis under the condition of industrial-grade current density in a full pH range.
The tin diselenide nanosheet electrocatalyst rich in selenium defects provided by the invention has the following advantages under the industrial current density>200mA cm -2 ) High selectivity performance is achieved. Wherein the highest HCOOH selectivities in alkaline, neutral and acidic electrolytes are 94.1%, 81.7% and 78.1%, respectively, and the peak partial current densities of HCOOH are 800, 568 and 495mA cm, respectively -2 The electrocatalytic performance is far superior to that of commercial tin diselenide catalysts.
The tin diselenide nanosheet electrocatalyst rich in selenium defects provided by the invention can effectively improve the adsorption and dissociation capacities of the tin diselenide nanosheet electrocatalyst on water molecules, and accelerate the proton transfer and intermediate formation rate, so that the electrocatalyst activity of the tin diselenide nanosheet electrocatalyst is further improved, and the tin diselenide nanosheet electrocatalyst is very significant in preparing HCOOH under industrial conditions.
Compared with the prior art, the invention has the following beneficial effects:
(1) The tin diselenide nanosheet electrocatalyst rich in selenium defects provided by the invention realizes high-selectivity CO 2 Catalytic conversion to HCOOH, and has a broad operable pH window (2.0-14.0). Realizes the electrosynthesis of HCOOH with industrial current density under different pH environments, and provides possibility for further industrial large-scale application.
(2) According to the selenium-defect-enriched tin diselenide nanosheet electrocatalyst provided by the invention, through the introduction of selenium defects, the electronic structure of tin diselenide is effectively regulated, so that the electron density around tin sites is more abundant, water molecules are effectively accelerated to dissociate more protons, further the formation of an intermediate COOH is accelerated, and finally the synthesis process of HCOOH is accelerated.
Drawings
FIG. 1 is a SEM image of the catalyst prepared in example 1;
FIG. 2 is an X-ray diffraction XRD pattern of the catalyst prepared in example 1;
FIG. 3 is an electron paramagnetic resonance EPR plot of the catalysts prepared in example 1 and examples 2-3;
FIG. 4 shows the electrical reduction of CO in the application example of the catalyst prepared in example 1 2 Faradaic efficiency of HCOOH preparation.
FIG. 5 shows the electroreduction of CO in the application of the catalysts prepared in example 1 and examples 2 to 3 2 Faradaic efficiency of HCOOH preparation.
FIG. 6 shows the electroreduction of CO at pH=14.0 in the examples of application for the catalysts prepared in example 1 and examples 4 to 5 2 Faradaic efficiency of HCOOH preparation.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. Modifications and equivalents will occur to those skilled in the art upon understanding the present teachings without departing from the spirit and scope of the present teachings. The raw materials used in the following embodiments are all commercially available.
Example 1
(1) 443.8mg of selenium dioxide solid particles and 451.3mg of stannous chloride dihydrate solid particles are weighed and dissolved in 30mL of deionized water solution, and stirred at normal temperature for 20min for later use;
(2) Adding 2mL of the solution prepared in the step (1) into 85wt.% hydrazine hydrate solution, and stirring for 5min; transferring the obtained mixed solution into a 50mL hydrothermal kettle, and carrying out hydrothermal reaction for 24 hours at 180 ℃;
(3) And (3) centrifugally separating the initial product obtained in the step (2), respectively washing with water and ethanol for more than 3 times, and finally drying in a vacuum oven at 60 ℃ for 12 hours to obtain the tin diselenide nano-sheet catalyst rich in selenium defects.
The microscopic morphology of the prepared catalyst is observed through a scanning electron microscope SEM, and the SEM result is shown in figure 1, so that the morphological structure of the tin diselenide catalyst rich in selenium defects is a hexagonal lamellar structure, and the thickness of the lamellar layer is about 50nm. The X-ray diffraction XRD pattern of the selenium-defect-enriched tin diselenide prepared in this example is shown in fig. 2, the characteristic peak of the crystal phase of the tin diselenide can be seen, the electron paramagnetic resonance EPR pattern is shown in fig. 3, and the existence of the selenium defect can be clearly seen, which indicates the successful preparation of the selenium-defect-enriched tin diselenide nanosheet electrocatalyst.
Example 2
The catalyst of example 2 was obtained by changing the hydrothermal reaction temperature in step (2) to 160℃according to the preparation process of example 1.
Example 3
The catalyst of example 3 was obtained by changing the hydrothermal reaction temperature in step (2) to 200℃according to the preparation process of example 1.
Example 4
According to the preparation process of example 1, the mass of the selenium dioxide solid particles in the step (1) is changed to 332.8mg to obtain the catalyst of example 4.
Example 5
According to the preparation process of example 1, the mass of the selenium dioxide solid particles in the step (1) is changed to 554.7mg to obtain the catalyst of example 5.
Application example HCOOH electrosynthesis at Industrial grade Current Density in full pH Range
First, 10mg of the catalyst prepared above was dispersed in 1000. Mu.L of a 9:1 ethanol/Nafion volume ratio dispersion, and then 100. Mu.L of the dispersion was sprayed to 0.5 x 0.5cm 2 After natural drying, it is placed as a working electrode in a three-electrode flow cell measuring device consisting of two compartments separated by an anion exchange membrane. Wherein, 1.0M KOH solution is used as alkaline electrolyte, and 1.0M KHCO is used 3 Solution as neutral electrolyte, 0.5. 0.5M K 2 SO 4 And H 2 SO 4 The mixed solution serves as an acidic electrolyte. The counter electrode of the alkaline electrolyte and the neutral electrolyte is foam nickel, the counter electrode of the acidic electrolyte is a platinum sheet, and the reference electrode is a silver/silver chloride electrode.
Cyclic Voltammetry (CV) activation: the electrochemical workstation of Shanghai Chenhua CHI 760E is used, a CV program is adopted, the test interval is between 0 and minus 1.4V vs. RHE, and the sweeping speed is 50mV s -1 The electrode reaches a stable state after 40 circles of cyclic scanning.
Linear Sweep Voltammetry (LSV) test: after CV activation, switching the program to LSV program, wherein the test interval is 0 to-1.4V vs. RHE, and the sweeping speed is 5mV s -1 。
Faraday Efficiency (FE) test: the switching procedure is a constant current voltage-time test, during which the gas chromatography is used to determine the gas product concentration and calculate FE of the product. On-line quantification by gas chromatography (GC, fuli 9790 II) using 1 And (3) analyzing the FE of the liquid product by using an H nuclear magnetic resonance analyzer, and measuring by using an internal standard method, namely using dimethyl sulfoxide as a standard.
As shown in FIG. 4, the selenium-enriched tin diselenide nanosheet electrocatalyst prepared in example 1 exhibited excellent HCOOH electrosynthesis performance over the full pH range, achieving 94.1%, 81.7% and 78.1% selectivities of HCOOH in alkaline, neutral and acidic electrolytes, respectively, corresponding HCOOH partial current densities of 800, 568 and 495mA cm -2 Reaching the industrial level.
Comparing the HCOOH Faraday efficiencies of the electrocatalysts prepared in example 1 and examples 2-3 under different pH environments at-0.8V vs. RHE, the results are shown in FIG. 5, wherein the HCOOH electrosynthesis performance of the tin diselenide nanosheet electrocatalysts rich in selenium defects prepared in example 1 is far better than that of examples 2 and 3 over the full pH range.
Comparing the electrosynthesis performance of HCOOH with the electrocatalysts prepared in examples 1 and 4-5 at ph=14.0, the result is that, as shown in fig. 6, the electrosynthesis selectivity of the tin diselenide nanosheet electrocatalyst enriched in selenium defects prepared in example 1 is far higher than that of examples 4 and 5.
Claims (8)
1. The preparation method of the tin diselenide nanosheet electrocatalyst rich in selenium defects is characterized by comprising the following steps of: and dissolving selenium dioxide and metallic tin salt, adding hydrazine hydrate solution, stirring and mixing, and performing hydrothermal reaction to obtain the selenium-enriched tin diselenide nanosheet electrocatalyst.
2. The method for preparing the selenium-defect-enriched tin diselenide nanosheet electrocatalyst according to claim 1, wherein the molar ratio of selenium dioxide to metallic tin salt is 1.5-2.5:1.
3. The method for preparing the selenium-defect-enriched tin diselenide nanosheet electrocatalyst according to claim 1, wherein the hydrothermal reaction temperature is 160-200 ℃.
4. The method for preparing the selenium-defect-enriched tin diselenide nanosheet electrocatalyst according to claim 1, wherein the molar ratio of selenium dioxide to metallic tin salt is 1.5-2:1, and the hydrothermal reaction temperature is 180-200 ℃.
5. A tin nanosheet electrocatalyst enriched in selenium defects obtainable by the process according to any one of claims 1 to 4.
6. The selenium-defect-enriched tin diselenide nanosheet electrocatalyst according to claim 5, wherein the atomic ratio of selenium to tin in the tin diselenide nanosheet electrocatalyst is from 1.8 to 2.0:1.
7. Use of the selenium-enriched defective tin diselenide nanosheet electrocatalyst according to claim 5 or 6 as a working electrode in the electrosynthesis of formic acid.
8. The use of the selenium-rich and defective tin diselenide nanosheet electrocatalyst according to claim 7, wherein the selenium-rich and defective tin diselenide nanosheet electrocatalyst is used as a working electrode for formic acid electrosynthesis at industrial grade current densities in the full pH range.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311455651.5A CN117568843A (en) | 2023-11-03 | 2023-11-03 | Selenium-defect-enriched tin diselenide nanosheet electrocatalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311455651.5A CN117568843A (en) | 2023-11-03 | 2023-11-03 | Selenium-defect-enriched tin diselenide nanosheet electrocatalyst and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117568843A true CN117568843A (en) | 2024-02-20 |
Family
ID=89861507
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311455651.5A Pending CN117568843A (en) | 2023-11-03 | 2023-11-03 | Selenium-defect-enriched tin diselenide nanosheet electrocatalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117568843A (en) |
-
2023
- 2023-11-03 CN CN202311455651.5A patent/CN117568843A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111672514A (en) | Bifunctional electrocatalytic material and preparation method and application thereof | |
| CN113828300B (en) | Preparation method of metal doped bismuth layered oxide and electrocatalytic reduction of CO 2 Application in (a) | |
| CN112481653B (en) | Defect-rich molybdenum-doped cobalt selenide/nano carbon electrocatalyst and preparation method and application thereof | |
| CN113235104B (en) | ZIF-67-based lanthanum-doped cobalt oxide catalyst and preparation method and application thereof | |
| CN113249739B (en) | Metal phosphide-loaded monatomic catalyst, preparation method thereof and application of metal phosphide-loaded monatomic catalyst as hydrogen evolution reaction electrocatalyst | |
| CN110560094B (en) | Preparation method of 3D porous cobalt-tin-molybdenum trimetal catalyst | |
| CN113789545B (en) | Electrolytic water catalyst and preparation method and application thereof | |
| CN112921351B (en) | Preparation method and application of self-supporting catalytic electrode | |
| CN117089881A (en) | Preparation method of Pt nanoparticle modified bimetallic LDH catalyst and industrial current density electrolyzed water application thereof | |
| CN112458483B (en) | Preparation method of NiFe LDH @ Super-P composite electro-catalytic material | |
| CN115404513A (en) | Carbon-coated heterostructure electrocatalyst and preparation and application thereof | |
| CN114774983A (en) | Ultra-small Ru nanocluster loaded on MoO3-xDouble-function composite material of nanobelt and preparation method and application thereof | |
| CN117568843A (en) | Selenium-defect-enriched tin diselenide nanosheet electrocatalyst and preparation method and application thereof | |
| CN113774425A (en) | Preparation method and application of Ru-modified FeCo @ NF electrocatalyst | |
| CN113293407A (en) | Iron-rich nanobelt oxygen evolution electrocatalyst and preparation method thereof | |
| CN117904673B (en) | Electrocatalyst and preparation and application thereof | |
| CN114045514B (en) | Preparation method of V@CoxP catalyst | |
| CN115094475B (en) | Electrode material with high-performance oxygen evolution catalytic activity and preparation method thereof | |
| CN115652357B (en) | Sulfur-doped yttrium ruthenate, preparation method thereof and oxygen evolution reaction electrode | |
| CN114892212B (en) | Preparation method of sulfur-doped nickel-based metal organic frame electrode material with bionic active domain, product and application thereof | |
| CN114717599B (en) | Ruthenium-supported nickel metal three-dimensional carbon sphere electrocatalyst and preparation method and application thereof | |
| CN111774071B (en) | Ternary metal sulfide nanosheet material, preparation method thereof and application of ternary metal sulfide nanosheet material in water electrolysis | |
| CN114214636B (en) | Method for preparing cobalt-based nanosheet self-supporting electrode by selenium-containing ligand and application of cobalt-based nanosheet self-supporting electrode | |
| CN118326441A (en) | Preparation method and application of Y-composite Cu-MOF carbon dioxide reduction electrocatalyst | |
| CN118461061A (en) | Ru-Sn-Ce ternary composite material, preparation method thereof and application of Ru-Sn-Ce ternary composite material as electrocatalyst for oxygen evolution reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |