CN113564632B - Heterojunction material with optimized fuel cell performance, preparation method thereof and electrocatalytic carbon dioxide reduction - Google Patents

Heterojunction material with optimized fuel cell performance, preparation method thereof and electrocatalytic carbon dioxide reduction Download PDF

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CN113564632B
CN113564632B CN202110914182.3A CN202110914182A CN113564632B CN 113564632 B CN113564632 B CN 113564632B CN 202110914182 A CN202110914182 A CN 202110914182A CN 113564632 B CN113564632 B CN 113564632B
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copper
oxide
heterojunction
oxide heterojunction
nanobelt
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CN113564632A (en
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陈敏康
林洪栋
周慧彬
汪海涛
王干军
冯国鹏
刘文浩
姜山
陆文伟
梁建辉
黄智勇
陈嘉豪
黄锦坚
刘石
刘志刚
凌彬
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Guangdong Power Grid Co Ltd
Zhongshan Power Supply Bureau of Guangdong Power Grid Co Ltd
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Guangdong Power Grid Co Ltd
Zhongshan Power Supply Bureau of Guangdong Power Grid Co Ltd
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    • 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
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    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C01—INORGANIC CHEMISTRY
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
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    • 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
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    • C25B3/00—Electrolytic production of organic compounds
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    • C—CHEMISTRY; METALLURGY
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    • 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
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    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
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    • C01—INORGANIC CHEMISTRY
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    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/17—Nanostrips, nanoribbons or nanobelts, i.e. solid nanofibres with two significantly differing dimensions between 1-100 nanometer
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention relates to the technical field of electrochemistry, in particular to a copper and copper oxide heterojunction nanobelt, and a preparation method and application thereof. The invention relates to a copper and its oxide heterojunction nano-belt, comprising: copper simple substance and cuprous oxide; the copper simple substance and the cuprous oxide form a heterostructure. The invention discloses a copper and copper oxide heterojunction nanobelt with good reduction catalysis effect on carbon dioxide, which can effectively reduce carbon dioxide selectively 2+ And (3) obtaining the product.

Description

Heterojunction material with optimized fuel cell performance, preparation method thereof and electrocatalytic carbon dioxide reduction
Technical Field
The invention relates to the technical field of electrochemistry, in particular to a copper and copper oxide heterojunction nanobelt, and a preparation method and application thereof.
Background
The hydrogen energy is used as a clean and efficient secondary energy, has the characteristics of zero carbon, large energy density, high combustion heat value, wide source, compressibility, storability and reproducibility, and becomes an important gripper for low-carbon transformation of new-era energy. In recent years, the main countries in the world use hydrogen energy development as an important national strategy, and the development of hydrogen energy is increasingly controlled from the aspects of planning, scientific and technological research and development, industrial cultivation and the like, so that the high-point of hydrogen energy development is quickened in a lot. For example, japan highly attaches importance to the development of hydrogen energy, and has become the country with the earliest breakthrough of hydrogen energy technology, the fastest market development, and the greatest popularization. As an effective method for green chemistry of low-carbon energy, the electrochemical reduction of carbon dioxide has wide market prospect for designing valuable chemicals and fuels, and not only can obtain C2+ products such as ethanol and the like, but also can generate hydrogen and carbon monoxide as sources of fuels in fuel cells. Under these conditions, the structure and chemistry of the catalystThe status is particularly important. Nanostructured Cu catalysts exhibit significantly improved CO compared to polycrystalline Cu electrodes 2 RR performance, which is attributed to grain boundaries, cu (100) planes, increased roughness, defects, low coordination number, and the presence of surface oxygen and Cu (I) groups. Previous studies on Cu single crystals showed improved C-C coupling properties for the (100) crystal plane, which is further confirmed by the high selectivity to ethylene observed on cubic Cu catalysts. However, the presence of the (100) crystal plane is not the only factor leading to excellent activity and selectivity of the cubic Cu catalyst, and surface roughness, subsurface oxygen and Cu (I) group or Cu/Cu (I) interface formation and/or stabilization under reaction conditions play a very important role. Among them, it is reported that the formation of Cu/Cu (I) interface is advantageous for enhancing the selectivity of Cu-based catalyst for C2+ products. For example, william a. Goddard III et al report the MEOM model of partially oxidized copper surfaces and suggest that this model leads to a reasonable mechanism to explain the experimental findings: CO can be generated by using an oxidizing electrode 2 RR is more efficient and selective. Contrary to previous speculations, we found that only surface active Cu + The site cannot increase CO 2 The efficiency of the RR, which actually decreases. Active surface Cu present in MEOM model + And Cu 0 The synergy between the regions can significantly improve CO 2 Kinetics and thermodynamics of the activation and CO dimerization processes, while hindering the C1 pathway, which is the increase of CO 2 RR efficiency and selectivity key steps. When Cu 2 Cu when O is converted from a physisorption structure to a chemisorption structure 2 The main function of O is to dilute CO 2 The negative charge formed thereby positively charging the C atom of CO. The Korean Buxing group reported 3D dendritic Cu-Cu prepared by in situ reduction electrodeposition of copper complexes 2 O composite, reducing carbon dioxide to C2 products (acetic acid and ethanol). In aqueous potassium chloride solution, overpotential is only 0.53V (for acetic acid) and 0.48V (for ethanol), C2 faradaic efficiency is as high as 80%, and current density is 11.5mA cm -2 . The excellent performance of the electrodes for the production of C2 products is mainly due to the close to zero contact resistance between the electrocatalyst and the copper substrate, the high exposed activity in the 3D tree structure of the electrocatalystSites and a suitable Cu (I)/Cu (0) ratio. Oxide/hydroxide derived copper electrode for electrocatalytic reduction of CO 2 Reaction (CO) 2 RR) has excellent selectivity to C2+ products. Under the reaction conditions, it was found that roughening of the surface of the nanocube, (100) face disappearance, pore formation, copper loss and CuOx species reduction all resulted in a polycarbon product (e.g., C) 2 H 4 And ethanol) over CH 4 Is suppressed. With Cu cubes supported on copper foil in CO 2 Under RR condition, the morphological stability and durability of the Cu (I) group are enhanced, the ratio of C2/C1 products is higher, the importance of the active nano-catalyst structure is highlighted, and the active nano-catalyst and a load substrate are supported on CO 2 Interaction in RR selectivity. Furthermore, the use of an inert substrate is also a synthetic strategy that can stabilize Cu (I) groups in Cu valence state. For example, the duschig topic group at the university of tianjin reported a novel electrocatalyst doped with ceria with cuprous ion that can selectively and stably produce ethylene. at-1.1V, the faradaic efficiency of ethylene reached 47.6%. The active sites are cuprous ions, stabilized by ceria, and have long-term durability. Furthermore, theoretical calculations indicate that cuprous ions favor C-C coupling and therefore have high selectivity to ethylene. However, with respect to the valence of Cu at CO 2 Changes in RR conditions and influences on catalytic activity and selectivity lack relevant in-situ test technical support, cu in a specific valence state is stabilized, and the improvement of the stability of the catalyst in long-time operation still needs more exploration and research. In addition to aiding in the rational design of the catalyst, understanding the mechanism of catalyst deactivation also allows the development of strategies to prevent these processes, and even to direct catalyst remodeling to better performing structures. Some work has been done by researchers to stabilize Cu-based catalysts, and the main strategy for these studies is to preserve morphology to maintain reaction selectivity. The Guntern et al study showed that the morphological stability of Ag nanoparticles was increased when covered with aluminum-based MOFs. The authors demonstrate that the synthesis method is generally applicable to other metal nanoparticles, and thus provides a new approach for improving the selectivity and stability of electrocatalysts. Therefore, cu 2 Encapsulation of O in MOFThe method may play a stabilizing role in the morphology of the catalyst and the Cu valence state.
In addition, imparting unique structural and compositional features to the catalyst may further maximize its ability to CO 2 Catalytic performance in RR. For example, dislocation regions on metal catalysts have a large number of under-coordinated step sites for CO formation 2 For the reduced intermediates, their energy barriers are low. Introduction of oxygen vacancies into the catalyst can increase CO 2 Bonding strength of and simplification of CO 2 And (4) activating. The structure of the metal/oxide connection interface can obviously improve CO 2 RR activity, resulting in completely different catalytic performance from the metal or oxide alone. Notably, for Sn/SnS 2 ，Co/Co 3 O 4 And Bi/Bi 2 O 3 It has been revealed that the material composition is responsible for CO in the production of formic acid 2 Synergy of RR selectivity and activity. Therefore, cu/Cu is constructed 2 The O interface has a great research prospect for the research of electrocatalytic carbon dioxide reduction.
In summary, the problems of the prior art are as follows: the C2+ product selectivity of the previously prepared Cu-based electrocatalytic carbon dioxide reduction catalyst is low and it is difficult to reduce the impact of the interpretation of the valence state on the catalytic efficiency. Therefore, an easy-to-prepare method is found for preparing the high-efficiency carbon dioxide reduction electrocatalyst, and the yield of the multi-carbon product can be improved.
Disclosure of Invention
In view of the above, the invention provides a copper and its oxide heterojunction nanobelt, a preparation method and an application thereof, and the copper and its oxide heterojunction nanobelt catalyzes carbon dioxide reduction C by means of nano-electricity 2+ The product selectivity is higher.
The specific technical scheme is as follows:
the invention provides a copper and copper oxide heterojunction nanobelt, which comprises: copper simple substance and cuprous oxide;
the copper simple substance and the cuprous oxide form a heterostructure.
In the invention, the copper and copper oxide heterojunction nanobelt is in a band shape, and the width of the copper and copper oxide heterojunction nanobelt is 50-300nm.
The copper and the oxide heterojunction nanobelt thereof provided by the invention utilize Cu/Cu 2 The hetero-junction structure of O can enhance the CO by utilizing the uneven distribution of charges 2 Adsorption of (2), simultaneous dislocated heterojunction structure, presence of Cu 2 O lowers the energy barrier to C2 production and promotes the formation of C2 products.
In the invention, the mass ratio of the copper simple substance to the cuprous oxide in the copper and oxide heterojunction nanobelt is 1:1 to 2:1, preferably 1:1 or 2:1.
the invention also provides a preparation method of the copper and copper oxide heterojunction nanobelt, which comprises the following steps:
step 1: adding sodium hydroxide into a copper chloride solution, heating to brown, adding an ascorbic acid solution for aging, and drying to obtain cuprous oxide;
step 2: adding the 1,3, 5-trimesic acid solution into a mixed solution of cuprous oxide and copper chloride for aging, centrifuging and drying;
and step 3: and (3) pyrolyzing the dried product in the step (2) in the argon atmosphere to obtain the copper and copper oxide heterojunction nanobelts.
In the invention, copper chloride reacts with sodium hydroxide in alkaline solution to form copper hydroxide which is gradually converted into copper oxide, and then the copper hydroxide is converted into cuprous oxide by utilizing the reducibility of ascorbic acid; cuprous oxide can be re-complexed with trimesic acid in a solution containing copper chloride, and a copper/cuprous oxide heterojunction nanobelt is obtained after pyrolysis.
In the invention, the pyrolysis temperature is 300 ℃ or 400 ℃, the time is 1h, and when the pyrolysis temperature is 300 ℃, the mass ratio of the copper simple substance to the cuprous oxide in the obtained copper and copper oxide heterojunction nanobelt is 1:1; when the pyrolysis temperature is 400 ℃, the mass ratio of the copper simple substance to the cuprous oxide in the obtained copper and copper oxide heterojunction nanobelt is 2:1.
in step 1 of the invention, the mass ratio of the copper chloride to the sodium hydroxide to the ascorbic acid is 0.682:3.2:0.2.
in step 2 of the invention, the mass ratio of the 1,3, 5-trimesic acid to the cuprous oxide to the cupric chloride is 0.263:0.2:0.4262.
the raw materials in the preparation method of the copper and copper oxide heterojunction nanobelt provided by the invention are low in price and easy to obtain, and the preparation cost is effectively reduced.
The invention also provides the application of the copper and the copper oxide heterojunction nano-belt or the copper and the copper oxide heterojunction nano-belt prepared by the preparation method in the electrocatalytic reduction of carbon dioxide.
The invention also provides an electrocatalytic carbon dioxide electrode comprising: the electrode comprises an electrode body, and the copper oxide heterojunction nanobelt coated on the electrode body or the copper and the copper oxide heterojunction nanobelt prepared by the preparation method.
In the invention, the electrode body is a carbon paper electrode.
The invention also provides a method for electrocatalytic reduction of carbon dioxide, which comprises the following steps:
and adding an electrolyte into the electrolytic cell of the three-electrode test system, and introducing carbon dioxide to perform electrocatalytic reaction.
In the invention, the electrolyte is an alkaline solution, preferably a potassium hydroxide solution, and the concentration of the alkaline solution is 1M; the voltage of the electrocatalytic reaction is-0.8 to-1.2V, and the time of the electrocatalytic reaction is 30min.
According to the technical scheme, the invention has the following advantages:
the invention provides a copper and copper oxide heterojunction nanobelt which has good catalytic effect on reduction of carbon dioxide and can effectively reduce carbon dioxide selectively 2+ And (3) obtaining the product.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the description of the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without inventive labor.
FIG. 1 is a flow chart of a method for preparing copper and copper oxide heterojunction nanobelts according to an embodiment of the present invention;
FIG. 2 is a scanning electron microscope image of heterojunction nanobelts (400 ℃ pyrolysis) of copper and copper oxide provided by example 1 of the present invention;
FIG. 3 is an XRD pattern of copper and its oxide heterojunction nanoribbons (400 ℃ C. Pyrolysis) provided in example 1 of the present invention;
FIG. 4 is a Faraday efficiency profile of carbon dioxide reduction products from copper and its oxide heterojunction nanoribbons (400 ℃ C. Pyrolysis) provided in example 1 of the present invention;
FIG. 5 is a scanning electron micrograph of copper and its oxide heterojunction nanobelts (300 ℃ C. Pyrolysis) provided in example 2 of the present invention;
FIG. 6 is an XRD pattern of heterojunction nanoribbons (300 ℃ C. Pyrolysis) of copper and its oxides provided in example 2 of the present invention;
figure 7 is a graph showing the faradaic efficiency distribution of carbon dioxide reduction products of copper and its oxide heterojunction nanoribbons (300 ℃ pyrolysis) provided in example 2 of the present invention.
Detailed Description
In order to make the objects, features and advantages of the present invention more obvious and understandable, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the embodiments described below are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The preparation method of the copper and the copper oxide heterojunction nanobelt comprises the following steps of:
the method comprises the following steps: 0.682g of CuCl 2 Dissolved in 400mL of deionized water, sonicated for 5 minutes (power of sonicator 350W), and stirred at 55 ℃ for 30min.
Step two: 3.2g NaOH was dissolved in 40mL deionized water and the above copper chloride solution was added to convert it to a blue colorCu(OH) 2 Continuously heating until the color turns brown, adding 40mL of ascorbic acid (0.2 g) solution, stirring for 30min, continuously stirring the whole process, and aging for 3h. Filtering, vacuum drying and collecting Cu 2 Ocube。
Step three: taking 200mg of Cu 2 O cube CuCl 2 (0.4262 g) dissolved in 50mL Deionized (DI) water to form solution A.
Step four: 1,3,5-trimesic acid (0.263 g) was dissolved in a mixed solvent of 45mL of deionized water and 5mL of ethanol to form a solution B, which was poured into the solution A with vigorous stirring. Stirring for 10min, and aging for 12h. Three times with deionized water, after centrifugation at once (7000 rpm), and then dried at 50-70 ℃ under vacuum.
Step five: and pyrolyzing the mixture for 1 hour at 400 ℃ in Ar atmosphere to obtain the copper and copper oxide heterojunction nanobelt.
In this embodiment, the mass ratio of the elemental copper to the cuprous oxide in the copper and its oxide heterojunction nanobelt is 2:1.
FIG. 2 is a scanning electron micrograph of copper and its oxide heterojunction nanobelts (400 ℃ C. Pyrolysis) showing a clear nanobelt structure having a width of 50-300nm. From the XRD pattern in fig. 3, the heterojunction structure of copper and its oxide heterojunction nanoribbons (400 ℃ pyrolysis) can be observed.
Example 2
The preparation method of the copper and the copper oxide heterojunction nanobelt comprises the following steps of:
the method comprises the following steps: 0.682g of CuCl 2 Dissolved in 400mL of deionized water, sonicated for 5 minutes (power of sonicator 350W), and stirred at 55 ℃ for 30min.
Step two: 3.2g NaOH was dissolved in 40mL deionized water and converted to blue Cu (OH) by adding the above copper chloride solution 2 Continuously heating until the color turns brown, adding 40mL ascorbic acid (0.2 g) solution, stirring for 30min, continuously stirring the whole process, and aging for 3h. Filtering, vacuum drying and collecting Cu 2 Ocube。
Step three: taking 200mg of Cu 2 O cube and CuCl 2 (0.4262 g) dissolved in 50mL Deionized (DI) water to formAnd (4) solution A.
Step four: 1,3,5-trimesic acid (0.263 g) was dissolved in a mixed solvent of 45mL of deionized water and 5mL of ethanol to form a solution B, which was poured into the solution A with vigorous stirring. Stirring for 10min, and aging for 12h. Three times with deionized water, after centrifugation at once (7000 rpm), and then dried at 50-70 ℃ under vacuum.
Step five: and pyrolyzing the mixture for 1 hour at 300 ℃ in Ar atmosphere to obtain the copper and copper oxide heterojunction nanobelt.
Fig. 5 is a scanning electron micrograph of copper and its oxide heterojunction nanoribbons (300 ℃ pyrolysis), and clear nanoribbon structures can be seen. From the XRD pattern in fig. 6, the heterojunction structure of copper and its oxide heterojunction nanoribbons (300 ℃ pyrolysis) can be observed.
Test examples
The copper and copper oxide heterojunction nanobelts prepared in the examples 1 to 2 are applied to carbon dioxide reduction reaction for comparison of electrocatalytic performance, and the specific steps are as follows:
1) A three-electrode test system is adopted to test the carbon dioxide reduction catalytic capacity (and a CHI750e electrochemical workstation), silver/silver chloride is used as a reference electrode, a platinum wire is used as a counter electrode, and purchased K-100 carbon paper is cut into pieces with the area of 2.5 x 1cm 2 Area size, using the carbon paper electrode modified by the material as a working electrode (the modification process is as follows: 3mg of copper and oxide heterojunction nanobelts thereof are dispersed in 1ml of liquid, 400 muL of the dispersion liquid is absorbed and is dripped on the surface of the carbon paper, and the carbon paper electrode is dried under an infrared lamp (100W)), and the carbon paper electrode modified by the material is prepared as a working electrode (the area is 1 cm) 2 ). The solution is 1mol L -1 Potassium hydroxide solution.
2) Placing the three electrodes in a flow electrolytic cell, introducing high-purity carbon dioxide into the solution, using a constant potential electrolysis method, taking a potential interval of-0.4 to-1.1V (vs. RHE), and carrying out electrocatalytic reaction for 30min, wherein the carbon dioxide reduction catalytic capability of the material is tested.
Figure 4 is a graph showing the faradaic efficiency of the carbon dioxide reduction products of copper and its oxide heterojunction nanoribbons (400 ℃ pyrolysis) in 1M KOH solution provided in example 1 of the present invention. Figure 7 is a graph showing the faradaic efficiency distribution of copper and its oxide heterojunction nanoribbons (300 ℃ pyrolysis) in 1m koh solution provided in example 2 of the present invention. Copper and its oxide heterojunction nanoribbons show higher faradaic efficiency for C2 products and lower hydrogen evolution capability.
The above-mentioned embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (7)

1. A copper and its oxide heterojunction nanoribbon, comprising: copper simple substance and cuprous oxide;
the copper simple substance and the cuprous oxide form a heterostructure;
the preparation method of the copper and copper oxide heterojunction nanobelt comprises the following steps of:
step 1: adding sodium hydroxide into a copper chloride solution, heating to brown, adding an ascorbic acid solution, aging, and drying to obtain cuprous oxide;
and 2, step: adding a 1,3, 5-trimesic acid solution into a mixed solution of cuprous oxide and copper chloride for aging under violent stirring, centrifuging and drying;
and step 3: and (3) pyrolyzing the dried product in the step (2) in the argon atmosphere to obtain the copper and copper oxide heterojunction nanobelts.
2. The copper and its oxide heterojunction nanobelt of claim 1, wherein the mass ratio of the elemental copper to the cuprous oxide in the copper and its oxide heterojunction nanobelt is 1:1 to 1:2.
3. the copper and its oxide heterojunction nanoribbon of claim 1, wherein the width of the copper and its oxide heterojunction nanoribbon is 50-300nm.
4. The copper and its oxide heterojunction nanobelt of claim 1, wherein the temperature of the pyrolysis is 300 ℃ and the time is 1h.
5. Copper and its oxide heterojunction nanoribbons as claimed in claim 1 wherein the temperature of the pyrolysis is 400 ℃ for 1h.
6. Use of the copper and its oxide heterojunction nanoribbons of any one of claims 1 to 5 in the electrocatalytic reduction of carbon dioxide.
7. An electrocatalytic carbon dioxide electrode, comprising: an electrode body and the copper and its oxide heterojunction nanoribbons of any one of claims 1 to 5 coated thereon.
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