CN112076766B - Metal organic framework derived ZnTe/ZnO @ C nanosheet electrocatalytic material and preparation and application thereof - Google Patents
Metal organic framework derived ZnTe/ZnO @ C nanosheet electrocatalytic material and preparation and application thereof Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 39
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0576—Tellurium; Compounds thereof
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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Abstract
The invention relates to a metal organic framework derived ZnTe/ZnO @ C nanosheet electrocatalytic material as well as preparation and application thereof, wherein the preparation method specifically comprises the following steps: (1) weighing Na2TeO3And Zn (NO)3)2Dissolving in mixed solution of ethylene glycol and water, respectively, adding Na2TeO3The solution is dropwise added to Zn (NO) under ultrasonic condition3)2Solution, centrifuging, washing and drying the prepared white product; (2) weighing ZnTeO prepared in the step (1)xRespectively dissolving the precursor and 2-methylimidazole in water, mixing and stirring, reacting at room temperature, centrifuging, washing and drying; (3) and (3) calcining the ZnTe-MOF prepared in the step (2) under the Ar condition to obtain a ZnTe/ZnO @ C nanosheet derived from a metal organic framework. According to the invention, a ZnTe-MOF nanosheet is formed by introducing a Te element at the early stage of Zn-MOF synthesis. Through high-temperature Ar calcination and carbonization, a metal organic framework derived ZnTe/ZnO @ C nanosheet is formed, so that the environment around Zn is effectively adjusted, and the selectivity of a reduction product of the Zn is changed.
Description
Technical Field
The invention belongs to the technical field of electrocatalytic nano materials, and relates to a metal organic framework derived ZnTe/ZnO @ C nanosheet electrocatalytic material as well as preparation and application thereof.
Background
CO in the atmosphere2The concentration has reached a new high level and if fossil fuels are used further, CO will result2Continues to increase in concentration. The climate warming and sea level elevation caused by it has attracted much attention. Conversion of CO from renewable energy sources2And H2O to chemical can reduce CO2The amount of discharge of (c). Formic acid or formate is of high value and can be stored and transported better than the reduced gas products to CO or alkane gases. At present, CO is mainly synthesized under the conditions of high temperature and high pressure, and the electrochemical reduction of carbon dioxide into formate by utilizing renewable power has recently received great attention, and is expected to replace the traditional synthesis method. It is well known that Zn-based electrocatalysts are on CO2The reduction to CO is very selective, but not very selective to formate, or requires very high overpotentials to proceed. The present invention has been made to solve the above problems.
Disclosure of Invention
The invention aims to provide a metal organic framework derived ZnTe/ZnO @ C nanosheet electro-catalytic material, and preparation and application thereof, and the obtained catalyst is used for CO2The electrocatalytic reduction to formate has extremely high selectivity, and the activity, stability and the like of the catalyst are excellent.
The purpose of the invention can be realized by the following technical scheme:
on one hand, the invention provides a preparation method of a metal organic framework derived ZnTe/ZnO @ C nanosheet electrocatalytic material, which comprises the following steps:
(1) first, Na is weighed2TeO3And Zn (CH)3COO)2Respectively dissolving in mixed solution of glycol and water to obtain solution A and solution B, dropwise adding the solution A into the solution B, separating, washing and drying to obtain ZnTe (OH)xA precursor;
(2) then ZnTe (OH)xRespectively dissolving the precursor and 2-methylimidazole in an ethylene glycol/water mixed solution to obtain a solution C and a solution D, mixing and stirring, reacting at room temperature, centrifuging, washing and drying the obtained product to obtain a ZnTe-MOF nanosheet;
(3) and calcining the ZnTe-MOF nanosheet under the protective atmosphere of inert gas to obtain a target product.
Further, in the step (1), Na2TeO3And Zn (CH)3COO)2Is 1: 1.
Further, in the step (1), Na in the solution A2TeO3And the addition ratio of the ethylene glycol to the water is 2 mmol: 5mL of: 15 mL.
Further, in the step (1), Zn (CH) in the solution B3COO)2And the addition ratio of the ethylene glycol to the water is 2 mmol: 5mL of: 15 mL.
Further, in the step (1), the solution A is added dropwise into the solution B under ultrasonic conditions.
Further, in the step (2), ZnTe (OH)xThe mass ratio of the precursor to the 2-methylimidazole is 0.12: 0.65.
Further, in the step (2), ZnTe (OH) in the solution CxThe addition ratio of the precursor to water is 0.12 g: 20 mL.
Further, in the step (2), the addition amount ratio of 2-methylimidazole to water in the solution D is 0.65 g: 20 mL.
Further, in the step (2), the reaction time at room temperature is 12 h.
Further, in the step (3), the calcining temperature is 600 ℃ and the calcining time is 2 hours.
Further, in the preparation process, the drying process of the synthesized precursor and the sample can be carried out in an oven at 60 ℃. In addition, the collected sample is washed and centrifugally separated for multiple times by deionized water and ethanol.
Wherein, first, Na2TeO3And Zn (CH)3COO)2The molar ratio is 1:1 coprecipitation to form ZnTe (OH)xCombining Zn and Te elements; second 2-methylimidazole linkage ZnTe (OH)xForming a ZnTe-MOF metal organic framework structure; and finally, calcining under Ar at the temperature higher than the carbonization temperature of imidazole to carbonize ZnTe-MOF, thereby forming the target catalyst with high conductivity and high activity. Wherein if Na2TeO3And Zn (CH)3COO)2A molar ratio other than 1:1, the raw material reaction is insufficient. Meanwhile, the carbonization temperature is required to be higher than 500 ℃, and if the calcination temperature is too low to reach the carbonization temperature, a target catalyst with high conductivity and high activity cannot be formed.
On the other hand, the invention also provides a metal organic framework derived ZnTe/ZnO @ C nanosheet electrocatalytic material, which is prepared by adopting the preparation method.
On the other hand, the invention also provides a metal organic framework derived ZnTe/ZnO @ C nanosheet electrocatalytic material in CO2Application in electrocatalytic reduction.
According to the invention, a ZnTe-MOF nanosheet is formed by introducing a Te element at the early stage of Zn-MOF synthesis. Through high-temperature Ar calcination and carbonization, a metal organic framework derived ZnTe/ZnO @ C nanosheet is formed, so that the environment around Zn is effectively adjusted, and the selectivity of a reduction product of the Zn is changed.
Compared with the prior art, the invention has the following advantages:
(1) ZnTe is taken as an active catalytic component, and Zn-based catalyst CO can be changed2The selectivity of the electrocatalytic reduction product ensures that the electrocatalytic reduction product has extremely high selectivity on reduction into formate at the voltage of-1.0 to-1.3V, and the maximum Faraday efficiency can reach 83 percent.
(2) The nitrogen-doped carbon material derived from the metal organic framework can improve the stability and the conductivity of the catalyst.
(3) The two-dimensional nanosheet structure enables greater exposure of catalytically active sites.
Drawings
FIG. 1 is a synthetic route of ZnTe/ZnO @ C nanosheets.
FIG. 2 shows ZnTe (OH)xSEM images of the precursors at different magnifications.
FIG. 3 shows ZnTe (OH)xXRD spectrum of (1).
FIG. 4 is an SEM image of ZnTe-MOF at different magnifications.
FIG. 5 is an XRD spectrum of ZnTe-MOF.
FIG. 6 is an SEM image of ZnTe/ZnO @ C at different magnifications.
FIG. 7 is a detection spectrum of ZnTe/ZnO @ C, wherein A is an XRD spectrum of ZnTe/ZnO @ C, B-E are XPS spectra of elements in ZnTe/ZnO @ C material, and F is a Raman spectrum of ZnTe/ZnO @ C and ZnO @ C
FIG. 8 shows CO2And N2Nuclear magnetic resonance hydrogen spectrogram of the electrolyte under atmosphere reduction potential.
FIG. 9 shows CO2Gas chromatogram of atmospheric reduction potential gas product.
FIG. 10 is the CO of ZnTe/ZnO @ C2A performance diagram, wherein A is CO2And N2LSV curve diagram under atmosphere, B is electrolysis curve under different potentials for 2h, wherein the electrolysis curve under the potential of-0.8 to-1.3V is respectively from top to bottom, and C is farad of liquid phase productThe third efficiency, D, is the Faraday efficiency of the gas phase product.
FIG. 11 is an SEM image of Zn-MOF.
FIG. 12 is an XRD spectrum of Zn-MOF.
FIG. 13 is an SEM image of ZnO @ C.
FIG. 14 is an XRD spectrum of ZnO @ C.
FIG. 15 CO of ZnO @ C2Faradaic efficiency of the different products.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In the following examples, Na2TeO3、Zn(CH3COO)22-methylimidazole and ethylene glycol are commercially available from Michael.
The remaining raw material products or processing techniques which are not specifically described are conventional commercial products or conventional processing techniques in the art.
Example 1:
a metal organic framework derived ZnTe/ZnO @ C nanosheet is prepared by the following method:
a synthetic catalyst, the route of which is shown in figure 1:
A. weighing 2mmol of Na2TeO3Dissolving in 5mL of ethylene glycol/15 mL of water to form a solution A;
B. weighing 2mmol of Zn (CH)3COO)2Dissolving in 5mL of glycol/15 mL of water to form a solution B;
C. dropwise adding the solution A into the solution B under the ultrasonic condition, centrifuging the obtained white product, washing with water and ethanol for multiple times, centrifuging, and drying in an oven at 60 ℃ to obtain ZnTe (OH)xA precursor material;
C. 0.12g of ZnTe (OH) was weighedxDissolving the precursor in 20mL of water to form a solution C;
D. weighing 0.65g of 2-methylimidazole, and dissolving in 20mL of water to form a solution D;
E. pouring the solution C into the solution D, stirring at room temperature for 12h to form ZnTe-MOF nanosheets, washing with water and ethanol for multiple times, centrifuging, and placing in a 60 ℃ drying oven for drying;
F. and (3) putting the ZnTe-MOF nanosheet precursor into a tubular furnace, and calcining for 2h at 600 ℃ under the Ar condition to prepare the ZnTe/ZnO @ C nanocomposite.
Characterization test
ZnTe (OH) in example 1 abovexThe precursor, ZnTe-MOF nanosheet and ZnTe/ZnO @ C nanosheet are respectively shot under a scanning electron microscope (Hitachi S-4800, Japan), the microscopic morphology of the material in each step in the synthesis process is recorded, and the detailed description is shown in the figure, wherein figure 2 is an ultrasonic precursor ZnTe (OH)xIt can be seen that the material has very small dimensions. By combining with 2-methylimidazole, it can be seen from fig. 4 that the ZnTe-MOF material formed is a nanoflower composed of nanosheets. Finally, Ar is carbonized at 600 ℃, and the ZnTe-MOF is converted into ZnTe/ZnO @ C nanosheets as shown in figure 6.
Referring to FIGS. 3, 5 and 7A, the synthesized material from each step was passed through an X-ray differentiation (Bruker Foucs D8 Advanced with Cu K.alpha.radiation of
) And testing and comparing with a standard material PDF card to determine the material composition of each step of the material.
As shown in FIGS. 7B-E, the presence of the C, N, Zn and Te elements was confirmed by an X-ray phosphor Spectrometer (Kratos Axis Ultra DLD X-ray phosphor Spectrometer using 60W monochromated Mg K.alpha.radiation as the X-ray source for the excitation) test.
Referring to fig. 7F, the higher degree of graphitization in the carbon layer was confirmed by InVia type micro confocal raman spectroscopy testing.
Electrochemical testing
The process adopts a standard three-electrode system, an Ag/AgCl electrode as a reference electrode and a carbon rod as a counter electrode, and the prepared material is dripped on a 1 multiplied by 1cm2The glassy carbon piece is used as a working electrode. The cells used for the tests being custom madeH-type and separated from each other by a Nafion115 proton exchange membrane. All tests were performed on an electrochemical workstation (CHI660 e).
Both electrolytes were 0.5M NaHCO3The solution volume was 30 mL. In electrochemical testing, all potentials were not resistance compensated and converted to potentials relative to a standard hydrogen electrode (RHE) as a reference, as follows: e (rhe) ═ E (Ag/AgCl) +0.0591pH + 0.2V. All electrochemical CO2The reduction tests are all carried out in CO2Saturated 0.5M NaHCO3In solution (pH 7.5). The reduction potential interval of the constant voltage electrolysis test is-0.8 to-1.3V vs RHE, and the reduction time is 2 h.
In CO2In the reduction test, gas chromatography is used for detecting gas products and measuring the content of the gas products. The main reduction product is provided as H in FIG. 82And CO. Figure 10D calculates and collates the faradaic efficiency of gas phase products at different potentials. Characterization of the liquid product the catholyte was collected by detection. Using 600MHz NMR1H spectrum to determine liquid product composition: DMSO is used as an internal standard substance, and the sample preparation steps are as follows: 0.5mL of the reaction solution and 0.1mL of D were measured2O and 10. mu.L DMSO, mixed well and transferred to a dry nuclear magnetic tube for testing. FIG. 9 comparative CO2And N2NMR spectrum of the electrolyte at atmospheric reduction potential, it can be seen that CO is converted into CO in the presence of the catalyst2Reduced to formate. In FIG. 10, A is ZnTe/ZnO @ C in N2And CO2The LSV curve of the reduction product is tested under the reduction potential, and the two LSV curves have a large difference value, thereby proving that ZnTe/ZnO @ C has extremely high CO2Reducing power. B is a test curve of ZnTe/ZnO @ C electrolyzed for 2h at a potential of between-0.8 and-1.3V respectively, wherein the electrolysis curves are respectively at a potential of between-0.8 and-1.3V from top to bottom. And the corresponding current densities under different potentials of the carbon nanotubes are basically consistent with those of the carbon nanotubes A, and after 2 hours of testing, gas-phase and liquid-phase products are collected and calculated to obtain C. C proves that the ZnTe/ZnO @ C nano composite material has extremely high selectivity on reduction into formate at the voltage of-1.0 to-1.3V, and the highest Faraday efficiency can reach 83 percent.
Comparative example 1:
compared with example 1, most of them are the same except that Na is omitted2TeO3Addition of this component. The method comprises the following specific steps:
A. 0.6g of Zn (CH) is weighed3COO)2Dissolving in 20mL of water to form solution A;
B. weighing 1.3g of 2-methylimidazole, and dissolving in 20mL of water to form a solution B;
C. pouring the solution A into the solution B, stirring at room temperature for 12h to form Zn-MOF, washing with water and ethanol for multiple times, centrifuging, and drying in a 60 ℃ drying oven;
D. and (3) putting the Zn-MOF precursor into a tube furnace, and calcining for 2h at 600 ℃ under the Ar condition to obtain the ZnO @ C nano material.
FIGS. 11 and 13 are SEM images of Zn-MOF and ZnO @ C, respectively, with good retention of the morphology of the material before and after carbonization. Meanwhile, compared with the shape of ZnO @ C, the ZnTe/ZnO @ C has larger active site exposure degree, and is more beneficial to improving the catalytic performance. FIGS. 12 and 14 are XRD spectra of Zn-MOF and ZnO @ C, respectively, confirming that no Te element was added. FIG. 15 CO of ZnO @ C2Faradaic efficiency of the different products. CO comparing ZnTe/ZnO @ C with ZnO @ C2As can be seen from the Faraday efficiencies of the different products, the introduction of Te element improves CO2Faradaic efficiency of reduction to formate.
The ZnTe/ZnO @ C nano material designed by the invention realizes that the Zn-based electrocatalyst is applied to CO by introducing Te element before the synthesis of Zn-MOF2The selectivity of the reduction product is changed to build CO2Electrochemical reduction of catalytic materials provides a new concept.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (9)
1. A preparation method of a metal organic framework derived ZnTe/ZnO @ C nanosheet electrocatalytic material is characterized by comprising the following steps of:
(1) first, Na is weighed2TeO3And Zn (CH)3COO)2Respectively dissolving in mixed solution of glycol and water to obtain solution A and solution B, dropwise adding the solution A into the solution B, separating, washing and drying to obtain ZnTe (OH)xA precursor;
(2) then ZnTe (OH)xRespectively dissolving the precursor and 2-methylimidazole in an ethylene glycol/water mixed solution to obtain a solution C and a solution D, mixing and stirring, reacting at room temperature, centrifuging, washing and drying the obtained product to obtain a ZnTe-MOF nanosheet;
(3) calcining the ZnTe-MOF nanosheet in an inert gas protective atmosphere to obtain a target product;
in the step (3), the calcining temperature is 600 ℃ and the calcining time is 2 hours.
2. The preparation method of the metal organic framework derived ZnTe/ZnO @ C nanosheet electrocatalytic material as claimed in claim 1, wherein in the step (1), Na is added2TeO3And Zn (CH)3COO)2Is 1: 1.
3. The preparation method of the metal organic framework derived ZnTe/ZnO @ C nanosheet electrocatalytic material as claimed in claim 1, wherein in step (1), Na in the A solution2TeO3And the addition ratio of the ethylene glycol to the water is 2 mmol: 5mL of: 15 mL;
zn (CH) in B solution3COO)2And the addition ratio of the ethylene glycol to the water is 2 mmol: 5mL of: 15 mL.
4. The preparation method of the metal-organic framework derived ZnTe/ZnO @ C nanosheet electrocatalytic material as set forth in claim 1, wherein in the step (1), the solution A is added dropwise to the solution B under ultrasonic conditions.
5. The preparation method of the metal organic framework derived ZnTe/ZnO @ C nanosheet electrocatalytic material as claimed in claim 1, wherein in the step (2), ZnTe (OH)xThe mass ratio of the precursor to the 2-methylimidazole is 0.12: 0.65.
6. The preparation method of the metal organic framework derived ZnTe/ZnO @ C nanosheet electrocatalytic material as claimed in claim 1, wherein in the step (2), ZnTe (OH) in the C solutionxThe addition ratio of the precursor to water is 0.12 g: 20 mL;
the addition ratio of 2-methylimidazole to water in the solution D is 0.65 g: 20 mL.
7. The preparation method of the metal organic framework derived ZnTe/ZnO @ C nanosheet electrocatalytic material as claimed in claim 1, wherein in the step (2), the reaction time at room temperature is 12 h.
8. A metal organic framework-derived ZnTe/ZnO @ C nanosheet electrocatalytic material prepared by the preparation method of any one of claims 1-7.
9. The metal-organic framework-derived ZnTe/ZnO @ C nanosheet electrocatalytic material of claim 8 in CO2Application in electrocatalytic reduction.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107447228A (en) * | 2017-08-09 | 2017-12-08 | 中国科学院理化技术研究所 | A kind of method of electro-catalysis reduction carbon dioxide |
| CN108435155A (en) * | 2018-03-23 | 2018-08-24 | 中国科学院理化技术研究所 | One kind being used for electro-catalysis CO2Carbon-supported catalysts of reduction and its preparation method and application |
| CN110075853A (en) * | 2019-04-12 | 2019-08-02 | 济南大学 | Water CoZn-LDHs-ZIF@C sandwich and preparation method, application are decomposed in a kind of electro-catalysis entirely |
| CN111530502A (en) * | 2020-05-08 | 2020-08-14 | 台州学院 | Preparation method of ZnTe-Mo/Mg-MOF photocathode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107447228A (en) * | 2017-08-09 | 2017-12-08 | 中国科学院理化技术研究所 | A kind of method of electro-catalysis reduction carbon dioxide |
| CN108435155A (en) * | 2018-03-23 | 2018-08-24 | 中国科学院理化技术研究所 | One kind being used for electro-catalysis CO2Carbon-supported catalysts of reduction and its preparation method and application |
| CN110075853A (en) * | 2019-04-12 | 2019-08-02 | 济南大学 | Water CoZn-LDHs-ZIF@C sandwich and preparation method, application are decomposed in a kind of electro-catalysis entirely |
| CN111530502A (en) * | 2020-05-08 | 2020-08-14 | 台州学院 | Preparation method of ZnTe-Mo/Mg-MOF photocathode material |
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