CN112301375B - Sulfur-modified Cu-based MOF material, preparation method and application thereof in electrocatalysis of CO 2 Application of reduction reaction - Google Patents
Sulfur-modified Cu-based MOF material, preparation method and application thereof in electrocatalysis of CO 2 Application of reduction reaction Download PDFInfo
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Abstract
The invention relates to a sulfur-modified Cu-based MOF material, a preparation method and application thereof in electrocatalysis of CO2 reduction reaction. The material consists of sulfur and Cu-based MOF, wherein the Cu-based MOF material is HKUST-1, and the Cu-based MOF material is of a regular octahedral structure and has the size of 10-100 micrometers. The material is prepared by preparing a Cu-based MOF precursor, preparing a sulfur-containing precursor solution and doping sulfur elements into the Cu-based MOF material by adopting a wet chemical reaction method. Application to electrocatalysis of CO 2 Compared with the existing Cu-based material, the reduction reaction system provided by the invention has the advantages that the electrocatalytic CO is obviously improved only by modifying the Cu-based MOF material with trace sulfur 2 Selectivity of reduction reaction to ethylene. The method is simple and convenient to synthesize, low in cost, short in reaction period and high in repeatability, and has very important application in the field of clean energy.
Description
Technical Field
The invention relates to the field of energy catalysis, in particular to a preparation method of sulfur modified Cu-based MOF and electrocatalysis CO thereof 2 The reduction application also has potential application value in the fields of other energy development and environmental protection.
Background
With the large consumption of fossil fuels, excessive carbon dioxide emissions are caused, thereby causing serious environmental pollution and climate problems. Therefore, there is an urgent need to efficiently convert carbon dioxide to reduce its content in the atmosphere. Electrocatalytic carbon dioxide reduction (CO) 2 RR) can convert CO 2 Conversion to valuable carbon-based fuels and chemical feedstocks, e.g. CO, CH 4 、C 2 H 4 、HCOOH、C 2 H 5 OH、CH 3 COOH and C 3 H 7 OH, etc. to therebyCO considered to be very effective 2 Emission reduction means and utilization strategies are widely concerned by researchers. The electro-catalyst can reduce the overpotential of the reaction and improve the Faraday efficiency of the product, thereby leading the electro-catalysis of CO 2 The reduction technique is more feasible. At present, although the noble metal-based electrocatalyst shows excellent selectivity, the large-scale application of the noble metal-based electrocatalyst is limited due to the shortage of reserves and high price, so that a catalyst for CO is developed 2 RR has high activity, high selectivity and cheap catalyst and has important theoretical significance and practical value.
Disclosure of Invention
The invention aims to overcome the defects and provide an enhanced electrocatalytic CO 2 Reduced sulfur-modified Cu-based MOF materials that utilize trace amounts of sulfur to produce locally unique Cu structures to enhance CO 2 Selective properties of the reduction to ethylene.
The purpose of the invention can be realized by the following technical scheme:
a sulfur-modified Cu-based MOF material is composed of sulfur and Cu-based MOF, wherein the Cu-based MOF material is HKUST-1, and the Cu-based MOF material is of a regular octahedral structure and has the size of 10-100 micrometers.
Furthermore, the sulfur modification adopts a wet chemical method to dope sulfur into the Cu-based MOF material, wherein the molar ratio of sulfur to copper is 1 (1-100).
The invention also provides a preparation method of the sulfur modified Cu-based MOF material, which is characterized by comprising the following steps of:
(1) Preparation of Cu-based MOF material (HKUST-1): copper nitrate trihydrate was dissolved in deionized water, and trimesic acid was additionally dissolved in an ethanol solution. And then stirring and mixing the two solutions, transferring the mixed solution into a polytetrafluoroethylene lining, sealing the lining, putting the sealed lining into a high-pressure reaction kettle, reacting in an oven at the temperature of 100 ℃ for 24 hours, and taking out the reaction kettle. And collecting the obtained product through centrifugation, repeatedly washing for a plurality of times, and drying to obtain the Cu-based MOF material.
(2) Preparing a sulfur-containing precursor solution: dissolving a certain amount of sulfur-containing precursor into the ethanol solution to prepare the sulfur-containing precursor ethanol solutions with different concentrations.
(3) Preparation of sulfur-modified Cu-based MOF material (HKUST-1): and (3) adding the Cu-based MOF material powder prepared in the step (1) into the solution obtained in the step (2), and reacting at room temperature under the stirring condition to obtain the sulfur-modified Cu-based MOF materials with different degrees.
Further, the stirring time in the step (1) is 1 to 3 hours.
Further, the sulfur-containing precursor in step (2) may be one or more of thioacetamide, thiourea and dithiourea.
Further, the room temperature reaction time in the step (3) is 1 to 3 hours.
The invention also provides application of the sulfur-modified Cu-based MOF material in electrocatalysis of CO2 reduction reaction, and the sulfur-modified Cu-based MOF material is applied to CO 2 In the reduction reaction of (3).
The sulfur modified Cu-based MOF material is added into CO 2 In the reduction reaction system of (a), carrying out electrocatalytic reaction, and carrying out electrocatalytic reaction on the sulfur modified Cu-based MOF material in the electrocatalytic CO 2 The current density of the reduction reaction system is 10-30mA/cm 2 And the faradaic efficiency of ethylene is 30-60%. Introducing CO 2 The gas was continuously delivered to the catholyte at an average rate of 5mL/min, through tubing and into a gas chromatograph (rami, GC 2060). The gas products were then analyzed by GC gas chromatography every 15 minutes.
Calculating CO, CH according to the following formula 4 ，C 2 H 4 And H 2 Faradaic efficiency of (a):
V CO 、V CH4 、V C2H4 and V H2 Is CO and H in the exhaust gas of the electrolytic cell 2 Volume concentration (data measured by gas chromatography). I (mA) is the steady state total current, G is CO at room temperature and ambient pressure 2 Flow rate, p = 1.013 × 10 5 Pa,T＝273.15K,F＝96485C mol -1 ,R＝8.3145J mol -1 K -1 .
Compared with the prior art, the invention has the beneficial effects that:
(1) The Cu-based MOF material modified by sulfur is synthesized by a simple wet chemical method, and the method has the advantages of simple synthesis method, simple and convenient experimental operation, mild reaction conditions, safety, no toxicity, low cost, short reaction period and high repeatability.
(2) Application of sulfur-modified Cu-based MOF material to electrocatalysis of CO 2 In the reduction field, the performance test result shows that the catalyst is applied to CO 2 Saturated 0.1M KHCO 3 (pH = 6.8) electrolyte, excellent ethylene selectivity was exhibited. FE over a wide range of operating potentials from-1.20 to-1.40V C2H4 Higher than 50%. In particular, the maximum FE at an operating potential of-1.30V C2H4 The content was 60%.
(3) In the preparation process of the material, all reagents are commercial products, further purification treatment is not needed, and the obtained material is easy to apply.
Drawings
FIG. 1 is an electron photograph of a sulfur-modified Cu-based MOF material prepared in example 1 versus an unmodified Cu-based MOF material;
FIG. 2 is a scanning electron micrograph of a sulfur-modified Cu-based MOF material and an unmodified Cu-based MOF material prepared in example 1;
FIG. 3 is an X-ray diffraction pattern of a sulfur-modified Cu-based MOF material versus an unmodified Cu-based MOF material prepared in example 1;
FIG. 4 is an X-ray photoelectron spectra of a sulfur-modified Cu-based MOF material and an unmodified Cu-based MOF material prepared in example 1;
FIG. 5 is an infrared spectrum of a sulfur-modified Cu-based MOF material versus an unmodified Cu-based MOF material prepared in example 1;
FIG. 6 is an X-ray absorption fine structure near-edge spectrum of the sulfur-modified Cu-based MOF material prepared in example 1 versus an unmodified Cu-based MOF material;
FIG. 7 is an R-space spectrum of the X-ray absorption fine structure spectrum of the sulfur-modified Cu-based MOF material prepared in example 1;
FIG. 8 is an in situ R-space spectrum of the X-ray absorption fine structure spectrum of the sulfur-modified Cu-based MOF material prepared in example 1;
FIG. 9 shows the sulfur-modified Cu-based MOF material and the unmodified Cu-based MOF material prepared in example 1 at 0.1M KHCO on a glassy carbon electrode as working electrodes 3 A linear scan curve in the electrolyte;
FIG. 10 shows the sulfur-modified Cu-based MOF material and the unmodified Cu-based MOF material prepared in example 1 loaded on a glassy carbon electrode as a working electrode at 0.1M KHCO 3 Faradaic efficiency plot of ethylene in electrolyte.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
Enhanced electrocatalytic CO 2 A preparation method of sulfur modified Cu-based MOF by reduction reaction is characterized by comprising the following steps:
(1) Preparation of Cu-based MOF material (HKUST-1): in a glass beaker, 5.5g of copper nitrate trihydrate was dissolved in 40mL of deionized water. Then, 2.45g of 1,3, 5-benzenetricarboxylic acid was dissolved in 40mL of an ethanol solution. Subsequently, the above two solutions were mixed with stirring and stirred for 1 hour. And transferring the mixed solution into a polytetrafluoroethylene lining after uniformly stirring, sealing, putting into a high-pressure reaction kettle, reacting in an oven at the temperature of 100 ℃ for 24 hours, and taking out. After that, the resultant product was collected by centrifugation and washed repeatedly several times with DMF and ethanol. Finally, drying in a vacuum oven at 60 ℃ for 12 hours yielded a Cu-based MOF material as a blue powder.
(2) Preparing a sulfur-containing precursor solution: 10mg of thioacetamide is dissolved in 15mL of ethanol solution to prepare sulfur-containing precursor ethanol solution.
(3) Preparation of sulfur-modified Cu-based MOF material (S-HKUST-1): and (3) adding 100mg of Cu-based MOF material powder prepared in the first step into the solution, and reacting at room temperature for 1-3 hours under the stirring condition to obtain the sulfur-modified Cu-based MOF.
FIG. 1 is an electron photograph of the sulfur-modified Cu-based MOF material prepared in example 1 versus an unmodified Cu-based MOF material, the unmodified Cu-based MOF material (HKUST-1) being a blue powder, and the sulfur-modified Cu-based MOF material (S-HKUST-1) being a dark green powder.
Fig. 2 is a scanning electron micrograph of the sulfur-modified Cu-based MOF material prepared in example 1 and an unmodified Cu-based MOF material. By observing the appearance of the sample, the appearance of the material before and after sulfur modification is not obviously changed, and both the materials are regular octahedron appearance.
FIG. 3 is an X-ray diffraction pattern of the sulfur-modified Cu-based MOF material prepared in example 1 and an unmodified Cu-based MOF material, with a scan rate of 5 min -1 The scanning range is 10-80 degrees, wherein: curve 1 is the unmodified MOF material and curve 2 is the sulfur-modified MOF material prepared in example 1. As can be seen from fig. 3, no phase change was observed after the sulfur modification treatment, indicating that the Cu-based MOF material structure was not destroyed by the elemental sulfur modification.
Fig. 4 is an X-ray photoelectron spectrum of the sulfur-modified Cu-based MOF material prepared in example 1 and an unmodified Cu-based MOF material, wherein: curve 1 is an unmodified MOF material and curve 2 is a sulfur-modified MOF material prepared in example 1. The Cu 2p map proves that signal peaks at 935.1 eV and 933.1eV in the material before and after modification are consistent and have no obvious shift, which indicates that the Cu valence state of the surface of the material is not changed under the action of sulfur modification.
FIG. 5 is an IR spectrum of a sulfur-modified Cu-based MOF material prepared in example 1 and an unmodified Cu-based MOF materialWherein: curve 1 is an unmodified MOF material and curve 2 is a sulfur-modified MOF material prepared in example 1. In the range of 400-2000 cm -1 Within the interval, at 752 and 729cm -1 The sharp absorption peak is located at 1114cm and is attributed to the characteristic peak of benzene ring -1 Sharp absorption peaks at 1645, 1440 and 1370cm and belong to the characteristic peaks of C-O -1 The sharp absorption peak is assigned to the characteristic peak of O = C-O. At the characteristic peaks, the material is not obviously changed before and after sulfur modification, which indicates that the bonding in the Cu-based MOF material is not damaged due to the introduction of trace sulfur elements.
Fig. 6 is an X-ray absorption fine structure near-edge map of the sulfur-modified Cu-based MOF material prepared in example 1 versus an unmodified Cu-based MOF material, wherein: curve 1 is the unmodified MOF material and curve 2 is the sulfur-modified MOF material prepared in example 1. As can be seen from FIG. 6, the Cu K-edge curve of the sulfur-modified material shifts toward a lower energy shoulder, indicating a relative decrease in the oxidation state of Cu in the sulfur-modified material.
Fig. 7 is an in situ X-ray absorption fine structure near-edge map of the sulfur-modified Cu-based MOF material prepared in example 1, wherein: curve 1 is an unmodified MOF material, curve 2 is a sulfur-modified MOF material prepared in example 1, curve 3 is a standard sample cuprous oxide, curve 4 is a standard sample cupric oxide, and curve 5 is a standard sample metallic copper. The spectra were obtained at-1.30V vs RHE operating potential. From fig. 7, it was found that as the time of the applied potential increased, the Cu K-edge curve shoulder of the sulfur-modified material gradually moved to a lower energy, and a shoulder consistent with the copper foil appeared, indicating that Cu in the material was reduced to lower valence Cu.
Fig. 8 is an in situ R spatial pattern of the sulfur-modified Cu-based MOF material prepared in example 1, wherein: curve pre-900s is the sulfur-modified material prepared in example 1, curve 3 is the standard cuprous oxide sample, and curve 5 is the standard metallic copper sample. The spectra were obtained at-1.30V vs RHE operating potential. From fig. 8, the Cu — Cu bond characteristic peak intensity of the sulfur-modified material gradually increases with the increase of the time of the applied potential, and it is also illustrated that Cu in the material is reduced to Cu in a lower valence state.
Enhanced electrocatalytic CO 2 Use of a reduced sulfur-modified Cu-based MOF, comprising the steps of:
electrocatalytic CO 2 Performance test in CO 2 Saturated 0.1M KHCO 3 (pH = 6.8) in solution. The product obtained by catalysis of the prepared material was analyzed by gas chromatography. The electrochemical performance of all materials was tested by an electrochemical workstation (CHI 660E), which is a classical three-electrode cell system. CO is introduced into 2 The gas was continuously delivered to the catholyte at an average rate of 5mL/min, through tubing and into a gas chromatograph (rami, GC 2060). The gas product was then analyzed by GC gas chromatography every 15 minutes.
FIG. 9 shows the sulfur-modified Cu-based MOF material and the unmodified Cu-based MOF material prepared in example 1 on a glassy carbon electrode as the working electrode at 0.1M KHCO 3 Linear scanning curve in electrolyte, curve 1 is unmodified MOF material, curve 2 is sulfur-modified MOF material prepared in example 1, both are used as working electrodes, silver-silver chloride electrode is reference electrode, platinum mesh is counter electrode, CO 2 Saturated 0.1M KHCO 3 The solution is electrolyte, the test temperature is room temperature, the scanning speed is 1mV/s, and the linear scanning curve under the test condition can be seen from figure 9 that the sulfur modified material is in CO 2 The current density in the saturated electrolyte is obviously higher than that of the unmodified material, which proves that the sulfur modified material is more likely to generate CO in the linear scanning process 2 And (4) carrying out reduction reaction.
FIG. 10 is a graph of the sulfur-modified Cu-based MOF material prepared in example 1 loaded on a glassy carbon electrode as a working electrode at 0.1M KHCO 3 Faradaic efficiency plot of ethylene in electrolyte. Curve 1 is an unmodified Cu-based MOF material, curve 2 is the sulfur-modified material prepared in example 1, both are working electrodes, the silver-silver chloride electrode is a reference electrode, the platinum mesh is a counter electrode, and the test temperature is room temperature. It can be seen from figure 10 that the ethylene faradaic efficiency of the sulfur modified Cu-based MOF material is significantly better than that of the unmodified Cu-based MOF material. It has a wide range of working potential of-1.20 to-1.40V, FE C2H4 Higher than 50%. In particular, inMaximum FE at an operating potential of-1.30V C2H4 The content was 60%.
Example 2
The operation steps of example 1 were repeated except that 5mg of thioacetamide was dissolved in 15mL of ethanol solution to prepare a sulfur-containing precursor ethanol solution; and (3) adding 100mg of Cu-based MOF material powder prepared in the first step into the solution, and reacting for 1-3 hours at room temperature under the stirring condition to obtain the sulfur-modified Cu-based MOF material.
Example 3
The operation steps of example 1 were repeated except that 20mg of thioacetamide was dissolved in 15mL of ethanol solution to prepare a sulfur-containing precursor ethanol solution; and (3) adding 100mg of Cu-based MOF material powder prepared in the first step into the solution, and reacting for 1-3 hours at room temperature under the stirring condition to obtain the sulfur-modified Cu-based MOF material.
Example 4
The procedure of example 1 was repeated except that 40mg of thioacetamide was dissolved in 15mL of ethanol solution to prepare a sulfur-containing precursor ethanol solution; and (3) adding 100mg of Cu-based MOF material powder prepared in the first step into the solution, and reacting for 1-3 hours at room temperature under the stirring condition to obtain the sulfur-modified Cu-based MOF material.
Example 5
The operation steps of example 1 are repeated, except that 5mg of thiourea is dissolved in 15mL of ethanol solution to prepare a sulfur-containing precursor ethanol solution; and (3) adding 100mg of Cu-based MOF material powder prepared in the first step into the solution, and reacting for 1-3 hours at room temperature under the stirring condition to obtain the sulfur-modified Cu-based MOF material.
Example 6
The operation steps of example 1 are repeated, except that 10mg of thiourea is dissolved in 15mL of ethanol solution to prepare a sulfur-containing precursor ethanol solution; and (3) adding 100mg of Cu-based MOF material powder prepared in the first step into the solution, and reacting at room temperature for 1-3 hours under the stirring condition to obtain the sulfur-modified Cu-based MOF material.
Example 7
The procedure of example 1 was repeated except that 20mg of thiourea was dissolved in 15mL of ethanol solution to prepare a sulfur-containing precursor ethanol solution; and (3) adding 100mg of Cu-based MOF material powder prepared in the first step into the solution, and reacting for 1-3 hours at room temperature under the stirring condition to obtain the sulfur-modified Cu-based MOF material.
Example 8
The operation steps of example 1 are repeated, except that 40mg of thiourea is dissolved in 15mL of ethanol solution to prepare a sulfur-containing precursor ethanol solution; and (3) adding 100mg of Cu-based MOF material powder prepared in the first step into the solution, and reacting for 1-3 hours at room temperature under the stirring condition to obtain the sulfur-modified Cu-based MOF material.
Example 9
The operation steps of example 1 are repeated, except that 5mg of bisthiourea is dissolved in 15mL of ethanol solution to prepare a sulfur-containing precursor ethanol solution; and (3) adding 100mg of Cu-based MOF material powder prepared in the first step into the solution, and reacting for 1-3 hours at room temperature under the stirring condition to obtain the sulfur-modified Cu-based MOF material.
Example 10
The operation steps of example 1 are repeated, except that 10mg of bisthiourea is dissolved in 15mL of ethanol solution to prepare a sulfur-containing precursor ethanol solution; and (3) adding 100mg of Cu-based MOF material powder prepared in the first step into the solution, and reacting for 1-3 hours at room temperature under the stirring condition to obtain the sulfur-modified Cu-based MOF material.
Example 11
The operation steps of example 1 are repeated, except that 20mg of dithiourea is dissolved in 15mL of ethanol solution to prepare a sulfur-containing precursor ethanol solution; and (3) adding 100mg of Cu-based MOF material powder prepared in the first step into the solution, and reacting at room temperature for 1-3 hours under the stirring condition to obtain the sulfur-modified Cu-based MOF material.
Example 12
The procedure of example 1 was repeated except that 40mg of dithiourea was dissolved in 15mL of ethanol solution to prepare a sulfur-containing precursor ethanol solution; and (3) adding 100mg of Cu-based MOF material powder prepared in the first step into the solution, and reacting for 1-3 hours at room temperature under the stirring condition to obtain the sulfur-modified Cu-based MOF material.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (5)
1. A preparation method of a sulfur-modified Cu-based MOF material is characterized by comprising the following steps:
(1) Preparation of Cu-based MOF material HKUST-1: dissolving copper nitrate trihydrate into deionized water, and dissolving trimesic acid into an ethanol solution; stirring and mixing the two solutions, transferring the mixed solution into a polytetrafluoroethylene lining, sealing the polytetrafluoroethylene lining, putting the polytetrafluoroethylene lining into a high-pressure reaction kettle, reacting in an oven, centrifugally collecting the obtained product, repeatedly washing for several times, and drying to obtain a Cu-based MOF material;
(2) Preparing a sulfur-containing precursor solution: dissolving a sulfur-containing precursor in an ethanol solution to prepare sulfur-containing precursor ethanol solutions with different concentrations;
(3) Preparation of sulfur-modified Cu-based MOF material HKUST-1: and (3) adding the Cu-based MOF material powder prepared in the step (1) into the solution obtained in the step (2), and reacting at room temperature under the stirring condition to obtain the sulfur-modified Cu-based MOF material with different degrees.
2. The method for preparing the sulfur-modified Cu-based MOF material according to claim 1, wherein the stirring and mixing time in the step (1) is 1-3 hours.
3. The method for preparing the sulfur-modified Cu-based MOF material according to claim 1, wherein the in-oven reaction in the step (1) is performed at a temperature of 100 ℃ for 24 hours.
4. The method for preparing the sulfur-modified Cu-based MOF material according to claim 1, wherein the sulfur-containing precursor in the step (2) is one or more of thioacetamide, thiourea and dithiourea.
5. The method for preparing the sulfur-modified Cu-based MOF material according to claim 1, wherein the room temperature reaction time of the step (3) is 1-3 hours.
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