CN116510719A - Core-shell material ZnO/SnO 2 Preparation method and application of (C) - Google Patents

Core-shell material ZnO/SnO 2 Preparation method and application of (C) Download PDF

Info

Publication number
CN116510719A
CN116510719A CN202310402876.8A CN202310402876A CN116510719A CN 116510719 A CN116510719 A CN 116510719A CN 202310402876 A CN202310402876 A CN 202310402876A CN 116510719 A CN116510719 A CN 116510719A
Authority
CN
China
Prior art keywords
zno
sno
reaction
preparation
core
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.)
Granted
Application number
CN202310402876.8A
Other languages
Chinese (zh)
Other versions
CN116510719B (en
Inventor
高岩
何景楠
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian University of Technology
Original Assignee
Dalian University of Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dalian University of Technology filed Critical Dalian University of Technology
Priority to CN202310402876.8A priority Critical patent/CN116510719B/en
Publication of CN116510719A publication Critical patent/CN116510719A/en
Application granted granted Critical
Publication of CN116510719B publication Critical patent/CN116510719B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/33—Electric or magnetic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • 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
    • 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
    • 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
    • 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
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • C25B3/26—Reduction of carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrochemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Biomedical Technology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Core-shell material ZnO/SnO 2 The preparation method and the application thereof belong to the field of inorganic synthesis. The method comprises the following steps: configuration containsThe zinc salt solution is reacted through a reaction kettle or directly reacted with alkali liquor, and spherical ZnO is obtained through centrifugation, washing, drying and calcination. Adding spherical ZnO, tin salt, PVP and sodium citrate into water, reacting in a reaction kettle, centrifuging, washing and drying to obtain ZnO/SnO 2 . The preparation method is simple, efficient and energy-saving; the obtained catalyst has rich catalytic sites and controllable morphology.

Description

Core-shell material ZnO/SnO 2 Preparation method and application of (C)
Technical Field
The invention relates to a core-shell material ZnO/SnO 2 The preparation method and the application thereof belong to the field of inorganic synthesis.
Technical Field
With the rapid development of economic society, a large amount of stone energy is used (coal, oil, natural gas) and a large amount of forest trees are cut down, causing a series of social and environmental problems. On one hand, the demand of fossil energy is increasing, but the reserves are limited and the exploitation difficulty is increasing, so that the energy crisis is caused; on the other hand, carbon dioxide (CO 2 ) And toxic gases are excessively discharged, so that environmental problems such as greenhouse effect, glacier melting, sea level rising and the like are caused, and great threat is brought to life and social development of people. 2021, global CO 2 The emission amount is 363 hundred million tons, and CO in the atmosphere 2 The content of CO is 417ppm 2 The problem needs to be solved.
CO by ECR 2 Conversion to chemicals and fuels is recycle CO 2 Because it has low energy consumption, strong controllability and environmental protection, thereby alleviating the energy crisis and environmental problems. ECR can give complex and diverse products, such as CO, HCOOH, CH, due to multiprotocol coupling, electron transfer and poor catalytic selectivity during the reaction 4 、CH 3 OH、C 2 H 5 OH、C 2 H 6 、CH 3 COOH, etc. Among them, HCOOH is a promising industrial ECR product, which is an important liquid chemical raw material in industrial production processes. In addition, HCOOH is an important hydrogen storage material for fuel cells. Worldwide implementation of carbon dioxide utilization roadmap predictions by 2030, the global market for carbon dioxide reduction of HCOOH can reach 47.5 ten thousand tons/year if suitable electrocatalyst materials are designed and prepared. Thus, HCOOH is an economically valuable product compared to other ECR products.
Tin-based catalysts have been considered as promising electrocatalysts for the production of HCOOH/HCOO-due to their environmental friendliness, low cost, high reserves and selective adsorption of the OCHO intermediate. However, most unmodified tin-based catalysts present low selectivities (FE<90%) and catalytic Activity (j)<20mA/cm 2 ) And high overpotential. The large overpotential is used to overcome the formation of CO 2 ·- Is hindered by the initial electron transfer energy of CO 2 ·- The stability on Sn surface is poor, resulting in low catalytic activity and energy efficiency of Sn-based catalysts. In addition, metallic tin is easily oxidized to tin oxide or stannous oxide in air, so that it is not easy to prepare and store a tin electrode.
Disclosure of Invention
The invention aims to provide a core-shell material ZnO/SnO 2 Is prepared by the preparation method of (1). The core-shell material ZnO/SnO provided by the invention 2 The preparation method is simple, efficient and energy-saving; the obtained catalyst has rich catalytic sites and controllable morphology.
In order to achieve the purpose, the invention adopts the following technical scheme: core-shell material ZnO/SnO 2 The preparation method of (2) comprises two steps: firstly preparing ZnO and then preparing ZnO/SnO 2 。
ZnO/SnO as core-shell material 2 The preparation method of (2) comprises the following steps:
(1) Adding zinc salt, sodium citrate and urea into deionized water, mixing, and then dispersing by using ultrasonic to obtain uniformly dispersed reaction liquid; zinc salt in the reaction liquid: sodium citrate: the mass ratio of the urea is 1 (0.1-0.3) to 0.3-0.4;
(2) Pouring the reaction liquid into a reaction kettle, wherein the reaction temperature is 110-130 ℃ and the reaction time is 10-12h; taking out the product mixed solution after the reaction is finished, centrifugally washing, drying in vacuum, calcining at 400-500 ℃ for 3-5 hours, and grinding for standby to obtain ZnO;
(3) Adding ZnO, tin salt, PVP and sodium citrate into deionized water, and performing ultrasonic dispersion to obtain uniformly dispersed mixed solution; znO in the mixed solution: tin salt: PVP: the mass ratio of the sodium citrate is (8-12): (3-5): (3-5): (2-4);
(4) Placing the mixed solution into a reaction kettle, wherein the reaction temperature is 150-170 ℃ and the reaction time is 2-3h; after the reaction is finished, washing and drying to obtain ZnO/SnO 2 。
In the method, the size of the reaction kettle in the step (2) is 100mL, and the reaction condition is 110-130 ℃ for 10-12h; the centrifugal washing condition is deionized water for 3 times, and the drying condition is 40-50 ℃ for 8-12h. Further preferably, the reaction conditions are 120℃for 12 hours and the drying conditions are 50℃for 10 hours.
The calcining condition in the step (2) is 400-500 ℃, 3-5h, and the heating rate is 4-5 ℃/min; further preferably, the calcination conditions are 400℃for 3 hours and the temperature rising rate is 5℃per minute.
In the step (3), the ZnO mass is 40-55mg, the tin salt is selected from stannous chloride dihydrate, the PVP mass is 15-25mg, the sodium citrate mass is 10-20mg, and the deionized water volume is 8-15mL. The mass of tin salt is 20mg, the mass of ZnO is 50mg, the mass of PVP is 20mg, the mass of sodium citrate is 15mg, and the volume of deionized water is 10mL. The hydrothermal reaction is to make Sn 2+ Adsorbing on spherical ZnO surface, uniformly dispersing under PVP and sodium citrate to form SnO 2 A nano thin layer. The thin layer is used as a main active site of the catalytic ECR, and the thickness directly influences the selectivity and the activity of the catalyst. The core-shell structure of the material can lead ZnO and SnO to be 2 And a synergistic effect is generated, so that the catalyst performance is further improved.
The reaction kettle in the step (4) is 20mL in size, and the reaction condition is 150-170 ℃ for 2-3h; the centrifugal washing condition is deionized water for 3 times, and the drying condition is 40-50 ℃ for 8-12h. Further preferably, the reaction conditions are 160℃for 2 hours and the drying conditions are 50℃for 10 hours.
ZnO/SnO as second core-shell material 2 The preparation method of (2) comprises the following steps:
(1) Zinc salt is dissolved in deionized water to obtain zinc salt solution, and the concentration of the zinc salt solution is 0.01-0.02g/mL;
(2) Gradually adding NaOH aqueous solution into zinc salt solution, wherein the concentration of the NaOH aqueous solution is 0.1-0.3M, and the molar ratio of zinc salt to NaOH is 1:1.1-1.3;
washing and vacuum drying after the reaction is finished, calcining for 3-5 hours at 400-500 ℃, and grinding for standby to obtain ZnO;
(3) Adding ZnO, tin salt, PVP and sodium citrate into deionized water, and performing ultrasonic dispersion to obtain uniformly dispersed mixed solution; znO in the mixed solution: tin salt: PVP: the mass ratio of the sodium citrate is (8-12): (3-5): (3-5): (2-4);
(4) The mixed solution is put into a reaction kettle for reverse reactionThe reaction temperature is 150-170 ℃ and the reaction time is 2-3h; after the reaction is finished, washing and drying to obtain ZnO/SnO 2 。
Further, in the step (2) of the method, a magnetic stirrer is used for stirring at a speed of 300-1000rpm/min; using a constant pressure dropping funnel, wherein the dropping speed is 4-10 s/drop, and the molar concentration of NaOH is 0.1-0.5M; further preferably, the stirring speed is 500rpm/min, the NaOH dropping rate is 5 s/drop, and the concentration is 0.2M.
The calcining condition in the step (2) is 400-500 ℃, 3-5h, and the heating rate is 4-5 ℃/min; further preferably, the calcination conditions are 400℃for 3 hours and the temperature rising rate is 5℃per minute.
The reaction kettle in the step (4) is 20mL in size, and the reaction condition is 150-170 ℃ for 2-3h; the centrifugal washing condition is deionized water for 3 times, and the drying condition is 40-50 ℃ for 8-12h. Further preferably, the reaction conditions are 160℃for 2 hours and the drying conditions are 50℃for 10 hours.
In the two preparation methods, the zinc salt is zinc nitrate hexahydrate or zinc chloride hexahydrate. The washing condition is deionized water washing for 3 times, and the drying condition is 40-50 ℃ drying for 8-12h. The tin salt is stannous chloride dihydrate. When NaOH aqueous solution is gradually added into zinc salt solution, the stirring speed is 300-1000rpm/min. The dropping rate was 4-10 s/drop using a constant pressure dropping funnel.
The beneficial effects of the invention are as follows: let Sn 2+ Adsorbing on spherical ZnO surface, uniformly dispersing under PVP and sodium citrate to form SnO 2 A nano thin layer. The thin layer is used as a main active site of the catalytic ECR, and the thickness directly influences the selectivity and the activity of the catalyst. The core-shell structure of the material can lead ZnO and SnO to be 2 And a synergistic effect is generated, so that the catalyst performance is further improved. The core-shell material has homotype or heterotype heterojunction, the internal electric field of the heterointerface is enhanced, more free electrons can appear, the basic electronic characteristics of the material are changed, the charge transfer can be promoted, the activation energy barrier is reduced, and the catalytic activity is improved.
Zinc oxide (ZnO) combines well with tin dioxide because zinc oxide has good doping adaptability and high selectivity to ECR; one partySurface, snO 2 Not only provides good morphological structure and catalytic site, but also enhances CO 2 Is used for the adsorption capacity of the catalyst. On the other hand, because the internal electric field of the two-phase interface is enhanced, more free electrons can appear, the basic electronic characteristics of the material are changed, the charge transfer can be promoted, and the activation energy barrier and the overpotential are reduced, so that the catalytic activity is improved.
(1) The preparation method provided by the invention is simple, and the catalyst with the core-shell structure can be obtained by a two-step hydrothermal method. The preparation method provided by the invention is simple in amplification, and the specification or the number of the reaction kettles is increased.
(2) The size and the shape of the parent spherical ZnO are controllable, and a foundation is provided for further modification; the tin oxide derivative has definite oxygen vacancies and active centers, so that O atoms are better bonded with Sn, an intermediate is stabilized, and the selectivity of the catalyst material to formic acid is improved; znO/SnO prepared by the method 2 The optimal formic acid selectivity reached 93.8% and the yield was 0.16mmol h at-1.05V -1 *cm -2 。ZnO/SnO 2 FE of (2) is higher than 80% in the potential range of-0.9V to-1.2V. ZnO/SnO 2 Has wide potential range for generating HCOOH and is beneficial to future industrial production.
Overall, znO/SnO 2 The active part of the surface is nano-scale, and a larger specific surface area can be obtained, so that the catalyst has higher catalytic activity and more catalytic sites.
Drawings
In fig. 1 a), b) are SEM pictures of ZnO; c) Is ZnO/SnO 2 SEM pictures of (a).
FIG. 2 is a BET adsorption drawing of ZnO in example 1.
FIG. 3 a) ZnO/SnO 2 、SnO 2 And XRD pattern of ZnO; b) ZnO/SnO 2 XPS spectrogram of (b); c) ZnO/SnO 2 O-fit plot of (c).
XRD of ZnO and standard cards thereof in fig. 4 a); b) SnO (SnO) 2 Is a standard card of XRD of (a).
Fig. 5 is a graph of electrochemical data: a) Is ZnO/SnO 2 (CO 2 )、ZnO/SnO 2 (Ar)、SnO 2 +ZnO(CO 2 )、ZnO(CO 2 )、SnO 2 (CO 2 ) LSV of (c); b) Is ZnO/SnO 2 Is a FE of (c).
FIG. 6 a) ZnO/SnO 2 -No. 2 SnO 2 And XRD pattern of ZnO-2; b) SnO (SnO) 2 Is a standard card of XRD of (a); c) XRD of ZnO-number and standard card thereof.
FIG. 7 a) is an SEM photograph of ZnO-2; c) Is ZnO/SnO 2 SEM picture No. 2.
FIG. 8 a) ZnO/SnO 2 -XPS survey spectrum number 2; b) ZnO/SnO 2 -O-fit map No. 2; c) ZnO/SnO 2 -LSV number 2; d) Is ZnO/SnO 2 FE of-2.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1
Core-shell material ZnO/SnO 2 The preparation method of (2) comprises the following steps:
(1) 90mL of deionized water, zn (NO 3), was added to a 100mL beaker 2 (1g) Sodium citrate (0.2 g) and urea (0.35 g) and then sonicated for 10min to disperse them uniformly. 70mL of the reaction solution was placed in a reaction vessel containing 100mL of the reaction solution at 120℃for 12 hours. After the reaction was completed, the white solid was washed with ultrapure water 3 times and dried in vacuo at 50℃for 6 hours. Then the solid is put into a muffle furnace, the heating rate is 5 ℃/min, and the solid is calcined for 3 hours at 400 ℃. Finally, grinding and collecting the product.
(2) ZnO (50 mg), snCl were added to a glass bottle containing 11mL of deionized water 2 (20 mg), PVP (20 mg) and sodium citrate (15 mg). The mixture was then sonicated for 10min to disperse it uniformly. The reaction solution was poured into a reactor having a 20mL polytetrafluoroethylene liner. The reactor was placed in a blast furnace set at 160 ℃ for 2h. After the reaction was completed, the solid was washed with ultrapure water 3 times and dried in vacuo at 50℃for 6 hours. Finally, the product ZnO-1 is collected.
Examples 2 to 6:
the difference from example 1 is that in step (1) the reaction temperature is 110 ℃ (example 2), 115 ℃ (example 3), 125 ℃ (example 4), 130 ℃ (example 5) and in step (2) the reaction temperature is 170 ℃ (example 6).
Example 7:
90mL deionized water, zn (NO), was added to a 100mL beaker 3 ) 2 6H 2 O (1 g,3.37 mmol); 150mg NaOH (3.75 mmol) was dissolved in 185mL deionized water to prepare a 0.02M aqueous NaOH solution; naOH aqueous solution was added dropwise through a constant pressure dropping funnel at a stirring rate of 500rpm/min and a dropping rate of 5 s/drop. After the reaction was completed, the white solid was washed with ultrapure water 3 times and dried in vacuo at 50℃for 6 hours. Then the solid is put into a muffle furnace, the heating rate is 5 ℃/min, and the solid is calcined for 3 hours at 400 ℃. Finally, grinding and collecting the ZnO-2 product.
Step (2) is the same as step (2) of example 1.
Examples 8 to 10:
the difference from example 1 is that in examples 8 to 10, step (2), snCl 2 The mass is respectively 10mg, 15mg and 25mg.
Examples 11 to 13:
the difference from example 1 is that the ZnO masses in step (2) are 45mg, 55mg, 60mg, respectively.
Example 14
The material obtained in example 1 is subjected to physical characterization SEM, XRD, XPS and the like, and the appearance, structure, outer layer electronic property, element composition and the like of the material are analyzed, so that the material has a deep effect on analysis of a reaction mechanism.
The surface morphology of the catalyst was observed and analyzed by SEM. The surface morphology of the ZnO catalyst is clearly shown in figures 1 and 2. As shown in fig. 1a and 1b, we therefore classified ZnO catalysts as microspheres consisting of nanoplatelets formed by stacking nanospheres. In FIG. 2, this shape has an optimal specific surface area (34.2694 m 2 /g), providing a large number of active sites and allowing for further modification. For ZnO/SnO 2 Is evident from the shape of (FIG. 1 c) SnO 2 The thin layer is tightly combined on the surface of the ZnO nano-sheet. The contact part of the two substances is heterojunction ZnO/SnO 2 Not only provides a large number of reaction sites, but also promotes the reaction by increasing the local CO2 concentration. Thin SnO 2 The layer being the main contact between the catalyst and the electrolyteThe reduction product is therefore mainly HCOOH.
Study of ZnO/SnO by XRD 2 、SnO 2 And the chemical structure of ZnO (fig. 3 a). As shown in FIG. 3a, the catalyst ZnO/SnO 2 Is of SnO appearance 2 And the characteristic peak of the ZnO catalyst, the peak position is not changed basically. Therefore, we insist on SnO 2 And ZnO, which form a new compound (ZnO/SnO) containing heterojunction 2 )。SnO 2 And ZnO catalysts and standard cards (ZnO: 36-1451, snO) 2 : 41-1445) are compared. SnO (SnO) 2 Or all diffraction peaks of ZnO can be specified in the card (fig. 4a and 4 b), while solving the crystal plane assignment problem. Attention is drawn to ZnO/SnO 2 Some of the peaks are shifted to some extent, especially those originally belonging to SnO 2 Is a peak of (2). This may increase the selectivity of the material.
ZnO/SnO 2 The surface chemistry of the catalyst was analyzed by XPS. High resolution and strong Zn, sn, O peaks can be seen from the spectra (fig. 3 b). High resolution Zn 2p and Sn 3d spectra clearly demonstrate Zn 2+ (1021.75 eV,1044.98 eV) and Sn 4+ Single oxidation state of species (486.34 ev,494.75 ev). The O1s spectrum (fig. 3c, after fitting) can then be split into three peaks: the peak at 529.89eV can be assigned to O (Sn-O-Sn or Zn-O-Sn) in the lattice; the peak at 531.43eV is attributed to O bound by hydroxide and metal; the peak at 533.28eV can be attributed to O adsorbed from the outside. This indicates that the material has a heterojunction, which is consistent with the results of the above analysis.
To test the electrocatalytic activity of the catalyst deeper, it was characterized by electrochemical performance tests LSV, FE, etc., with the following results:
the catalytic activity of the catalyst is generally evaluated by the onset potential and selectivity (FE). ZnO/SnO 2 、SnO 2 +ZnO、SnO 2 And ZnO (FIG. 5 a) in Ar or CO 2 Saturated 0.1M KHCO 3 The potential ranges from-0.3V to-1.4V (vs. RHE, supra). As shown in FIG. 5a, in CO 2 ZnO/SnO in atmosphere 2 Is higher than at the same timeCurrent density in Ar atmosphere at potential. Comparison of CO 2 4 curves under atmosphere, znO/SnO 2 The current density of (c) is almost always higher than the other 3 curves at the same potential.
To more directly and accurately measure ZnO/SnO 2 All products were collected and analyzed after 1H electrolysis in H-cells of different potentials (-0.8V to-1.2V). As shown in FIG. 5b, znO/SnO 2 The optimum formic acid selectivity of (2) was 93.8% and the yield at-1.05V was 0.16mmol h -1 *cm -2 . This performance has been superior to most tin-based electrocatalysts (fig. 6 b). Interestingly, znO/SnO 2 FE of (2) is higher than 80% in the potential range of-0.9V to-1.2V. ZnO/SnO 2 Has wide potential range for generating HCOOH and is beneficial to future industrial production.
Example 15
The material obtained in example 7 is subjected to physical characterization SEM, XRD, XPS and the like, and the appearance, structure, outer layer electronic property, element composition and the like of the material are analyzed, so that the material has a deep effect on analysis of a reaction mechanism.
Analysis of ZnO/SnO by XRD 2 Crystalline nature of No. 2. In FIGS. 6a-c, znO/SnO 2 -No. 2, znO-2 and SnO 2 The characteristic peaks of (2) are clearly shown. Analysis of ZnO-2 and ZnO/SnO by SEM 2 -No. 2 surface topography. As shown in fig. 7a and 7b, the morphology of ZnO-2 is nanospheres; and ZnO/SnO 2 And the number 2 is in a block shape agglomerated by the nano-spheres. Then, znO/SnO was analyzed by XPS 2 Surface electronic properties of No. 2, strong Zn 2d, sn 3, O1s characteristic peaks appear in fig. 8 a; in fig. 8b, O1s can be divided into 3 peaks: the peak at 533.2eV may be attributed to oxygen adsorbed from the outside; a peak at 531.77eV, which can be attributed to oxygen vacancies; finally, the peak at 530.67eV is lattice oxygen (Zn-O or Sn-O). We therefore consider ZnO-2 and SnO 2 Perfect combination, forming a material with a core-shell heterostructure.
To obtain the electrocatalytic performance of the material, we performed electrochemical tests of LSV, FE, etc. As shown in FIGS. 8c, 8d, 5a, znO/SnO is according to the LSV curve 2 -Current Density ratio of number 2High, indicating good ECR activity; the FE of formic acid is higher than 70% when the electrolyte is electrolyzed under different potentials. Thus, we consider ZnO/SnO 2 -No. 2 has good electrochemical properties.

Claims (8)

1. Core-shell material ZnO/SnO 2 The preparation method of (2) is characterized by comprising the following steps:
(1) Adding zinc salt, sodium citrate and urea into deionized water, mixing, and then dispersing by using ultrasonic to obtain uniformly dispersed reaction liquid; zinc salt in the reaction liquid: sodium citrate: the mass ratio of the urea is 1 (0.1-0.3) to 0.3-0.4;
(2) Pouring the reaction liquid into a reaction kettle, wherein the reaction temperature is 110-130 ℃ and the reaction time is 10-12h; taking out the product mixed solution after the reaction is finished, centrifugally washing, drying in vacuum, calcining at 400-500 ℃ for 3-5 hours, and grinding for standby to obtain ZnO;
(3) Adding ZnO, tin salt, PVP and sodium citrate into deionized water, and performing ultrasonic dispersion to obtain uniformly dispersed mixed solution; znO in the mixed solution: tin salt: PVP: the mass ratio of the sodium citrate is (8-12): (3-5): (3-5): (2-4);
(4) Placing the mixed solution into a reaction kettle, wherein the reaction temperature is 150-170 ℃ and the reaction time is 2-3h; after the reaction is finished, washing and drying to obtain ZnO/SnO 2 。
2. Core-shell material ZnO/SnO 2 The preparation method of (2) is characterized by comprising the following steps:
(1) Zinc salt is dissolved in deionized water to obtain zinc salt solution, and the concentration of the zinc salt solution is 0.01-0.02g/mL;
(2) Gradually adding NaOH aqueous solution into zinc salt solution, wherein the concentration of the NaOH aqueous solution is 0.1-0.5M, and the molar ratio of zinc salt to NaOH is 1:1.1-1.3; washing and vacuum drying after the reaction is finished, calcining for 3-5 hours at 400-500 ℃, and grinding for standby to obtain ZnO;
(3) Adding ZnO, tin salt, PVP and sodium citrate into deionized water, and performing ultrasonic dispersion to obtain uniformly dispersed mixed solution; znO in the mixed solution: tin salt: PVP: the mass ratio of the sodium citrate is (8-12): (3-5): (3-5): (2-4);
(4) Placing the mixed solution into a reaction kettle, wherein the reaction temperature is 150-170 ℃ and the reaction time is 2-3h; after the reaction is finished, washing and drying to obtain ZnO/SnO 2 。
3. A core-shell material ZnO/SnO according to claim 1 or 2 2 The preparation method of (2) is characterized in that: the zinc salt is zinc nitrate hexahydrate or zinc chloride hexahydrate.
4. A core-shell material ZnO/SnO according to claim 1 or 2 2 The preparation method of (2) is characterized in that: the washing condition is deionized water washing for 3 times, and the drying condition is 40-50 ℃ drying for 8-12h.
5. A core-shell material ZnO/SnO according to claim 1 or 2 2 The preparation method of (2) is characterized in that: the tin salt is stannous chloride dihydrate.
6. A core-shell material ZnO/SnO according to claim 2 2 The preparation method of (2) is characterized in that: when NaOH aqueous solution is gradually added into zinc salt solution, the stirring speed is 300-1000rpm/min.
7. A core-shell material ZnO/SnO according to claim 6 2 The preparation method of (2) is characterized in that: the dropping rate was 4-10 s/drop using a constant pressure dropping funnel.
8. ZnO/SnO prepared by the preparation method according to claim 1 or 2 2 The method is characterized in that: core-shell material ZnO/SnO 2 The method is applied to the electrolytic production of HCOOH.
CN202310402876.8A 2023-04-16 2023-04-16 Core-shell material ZnO/SnO2Preparation method and application of (C) Active CN116510719B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310402876.8A CN116510719B (en) 2023-04-16 2023-04-16 Core-shell material ZnO/SnO2Preparation method and application of (C)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310402876.8A CN116510719B (en) 2023-04-16 2023-04-16 Core-shell material ZnO/SnO2Preparation method and application of (C)

Publications (2)

Publication Number Publication Date
CN116510719A true CN116510719A (en) 2023-08-01
CN116510719B CN116510719B (en) 2024-09-27

Family

ID=87400364

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310402876.8A Active CN116510719B (en) 2023-04-16 2023-04-16 Core-shell material ZnO/SnO2Preparation method and application of (C)

Country Status (1)

Country Link
CN (1) CN116510719B (en)

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101342486A (en) * 2008-08-29 2009-01-14 中国科学院上海硅酸盐研究所 Metallic oxide nano-material
CN103776870A (en) * 2014-02-27 2014-05-07 河南理工大学 ZnO/SnO2 nano composite gas-sensitive material with flower-shaped grading structure and preparation method of material
CN108866561A (en) * 2018-06-27 2018-11-23 大连理工大学 A kind of preparation method and applications of electro-catalysis carbon dioxide reduction electrode
CN110161087A (en) * 2019-05-20 2019-08-23 南京工业大学 Preparation and application of hydrogen sensing material
CN110227453A (en) * 2019-04-17 2019-09-13 江苏省农业科学院 A kind of preparation method of Ag/ZnO/GO composite visible light catalyst
CN110606504A (en) * 2019-10-17 2019-12-24 武汉工程大学 Hierarchical nuclear shell SnO2Microsphere and preparation method and application thereof
CN111900346A (en) * 2020-07-13 2020-11-06 滁州学院 Carbon-coated tin dioxide/zinc sulfide hollow cubic nano composite material, preparation method thereof, lithium ion battery cathode and battery
CN111921525A (en) * 2020-07-20 2020-11-13 西安工程大学 Preparation method of palladium-doped tin dioxide spherical nano material
CN112892518A (en) * 2021-01-26 2021-06-04 重庆茨文科技有限公司 Nd-doped ZnO nanoflower-porous hollow SnO2The photocatalytic material and the preparation method thereof
CN115584531A (en) * 2022-10-10 2023-01-10 大连理工大学 Preparation method of silver modified tin sulfide catalyst and application of silver modified tin sulfide catalyst in carbon dioxide electroreduction

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101342486A (en) * 2008-08-29 2009-01-14 中国科学院上海硅酸盐研究所 Metallic oxide nano-material
CN103776870A (en) * 2014-02-27 2014-05-07 河南理工大学 ZnO/SnO2 nano composite gas-sensitive material with flower-shaped grading structure and preparation method of material
CN108866561A (en) * 2018-06-27 2018-11-23 大连理工大学 A kind of preparation method and applications of electro-catalysis carbon dioxide reduction electrode
CN110227453A (en) * 2019-04-17 2019-09-13 江苏省农业科学院 A kind of preparation method of Ag/ZnO/GO composite visible light catalyst
CN110161087A (en) * 2019-05-20 2019-08-23 南京工业大学 Preparation and application of hydrogen sensing material
CN110606504A (en) * 2019-10-17 2019-12-24 武汉工程大学 Hierarchical nuclear shell SnO2Microsphere and preparation method and application thereof
CN111900346A (en) * 2020-07-13 2020-11-06 滁州学院 Carbon-coated tin dioxide/zinc sulfide hollow cubic nano composite material, preparation method thereof, lithium ion battery cathode and battery
CN111921525A (en) * 2020-07-20 2020-11-13 西安工程大学 Preparation method of palladium-doped tin dioxide spherical nano material
CN112892518A (en) * 2021-01-26 2021-06-04 重庆茨文科技有限公司 Nd-doped ZnO nanoflower-porous hollow SnO2The photocatalytic material and the preparation method thereof
CN115584531A (en) * 2022-10-10 2023-01-10 大连理工大学 Preparation method of silver modified tin sulfide catalyst and application of silver modified tin sulfide catalyst in carbon dioxide electroreduction

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
DANIEL TAN等: "SnO2/ZnO Composite Hollow Nanofiber Electrocatalyst for Efficient CO2 Reduction to Formate", 《ACS SUSTAINABLE CHEMISTRY & ENGINEERING》, 29 June 2020 (2020-06-29), pages 10639 *
JING-NAN HE等: "Highly selective reduction of CO2 to HCOOH by a ZnO/SnO2 electrocatalyst with heterogeneous interfaces", 《 NEW J. CHEM》, 12 June 2023 (2023-06-12), pages 1 - 5 *
付袁媛: "二维锡基材料的构筑及其电催化还原二氧化碳性能的研究", 《中国优秀硕士学位论文数据库 工程科技Ⅰ辑》, 15 February 2023 (2023-02-15), pages 7 - 21 *
刘建奇: "氧化锌氧化锡复合催化剂电催化二氧化碳还原的研究", 《中国学位论文全文数据库》, 2 November 2022 (2022-11-02), pages 11 - 12 *
陈辉: "多层嵌套式二氧化锡及银掺杂氧化锌气敏性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, 15 February 2019 (2019-02-15), pages 15 - 18 *

Also Published As

Publication number Publication date
CN116510719B (en) 2024-09-27

Similar Documents

Publication Publication Date Title
Bhatt et al. Advancement of platinum (Pt)-free (non-Pt precious metals) and/or metal-free (non-precious-metals) electrocatalysts in energy applications: A review and perspectives
Mohammed-Ibrahim et al. Recent advances on hydrogen production through seawater electrolysis
Wang et al. A review of non-noble metal-based electrocatalysts for CO2 electroreduction
Zhang et al. Zn electrode with a layer of nanoparticles for selective electroreduction of CO 2 to formate in aqueous solutions
Biswas et al. Interfacial engineering of CuCo2S4/g-C3N4 hybrid nanorods for efficient oxygen evolution reaction
Chen et al. Regulation of intrinsic physicochemical properties of metal oxide nanomaterials for energy conversion and environmental detection applications
Dutta et al. Facile synthesis of unique hexagonal nanoplates of Zn/Co hydroxy sulfate for efficient electrocatalytic oxygen evolution reaction
Zhu et al. Layered Fe-substituted LiNiO2 electrocatalysts for high-efficiency oxygen evolution reaction
CN110813350B (en) Carbon-based composite electrocatalyst and preparation method and application thereof
CN105618060A (en) Bi-functional oxygen catalyst for graphene/nickel iron type hydrotalcite as well as preparation method and application thereof
CN108339559A (en) A kind of nano combined electrocatalysis material of nickel oxide and its preparation method and application
Kumar et al. A superior and stable electrocatalytic oxygen evolution reaction by one-dimensional FeCoP colloidal nanostructures
CN109967068A (en) A kind of netted doping type perovskite catalyst and its preparation method and application
Zhang et al. Molecular precursor route to CuCo2S4 nanosheets: a high-performance pre-catalyst for oxygen evolution and its application in Zn–air batteries
CN109437374B (en) Cobalt-doped copper sulfide nanosheet material rich in defects and sulfur vacancies, and preparation method and application thereof
CN114525540A (en) Nano material with noble metal particles dispersed on surface of non-noble metal substrate, and preparation method and application thereof
CN110416562A (en) A kind of netted doping type perovskite catalyst and its preparation method and application
Yu et al. Regulation engineering of the surface and structure of perovskite-based electrocatalysts for the oxygen evolution reaction
Helal et al. One-pot formation of an rGO-based ZnAl2O4 nanocomposite for electrochemical studies toward oxygen evolution reactions
CN110354862B (en) Method for in-situ modification of three-dimensional nickel-iron hydrotalcite electrocatalytic oxygen evolution electrode by aid of cerium ions on surface of foamed nickel substrate
Kumar et al. Facile one-step solid-state synthesis of CuO nanoparticles finely decorated over carbon sheets for improved OER activity
Gao et al. Noble metal catalysts for metal-air batteries: From nano-level to atom-level
CN110433810A (en) Preparation method of copper oxide doped nickel-iron hydrotalcite nanosheet/graphene bifunctional water decomposition catalyst
CN116510719B (en) Core-shell material ZnO/SnO2Preparation method and application of (C)
CN108842165B (en) Solvothermal preparation of sulfur doped NiFe (CN)5NO electrolysis water oxygen evolution catalyst and application thereof

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
GR01 Patent grant
GR01 Patent grant