超细氧化铜纳米颗粒修饰二维金属有机框架协同增强二氧化碳电化学还原生成乙烯

doi:10.1016/S1872-2067(21)63947-5

催化学报 ›› 2022, Vol. 43 ›› Issue (4): 1049-1057.DOI: 10.1016/S1872-2067(21)63947-5

超细氧化铜纳米颗粒修饰二维金属有机框架协同增强二氧化碳电化学还原生成乙烯

王琳琳^a, 李欣^a, 郝磊端^a, 洪崧^a, Alex W. Robertson^b, 孙振宇^a^,^c^,^*()

^a北京化工大学有机无机复合物国家重点实验室, 北京100029, 中国
^b牛津大学材料系, 牛津, 英国
^c中国科学院上海高等研究院低碳转化科学与工程重点实验室, 上海201210, 中国

收稿日期:2021-07-15 接受日期:2021-07-15 出版日期:2022-03-05 发布日期:2022-03-01
通讯作者: 孙振宇
基金资助:
国家自然科学基金(21972010);北京市自然科学基金(2192039)

Integration of ultrafine CuO nanoparticles with two-dimensional MOFs for enhanced electrochemical CO₂ reduction to ethylene

Linlin Wang^a, Xin Li^a, Leiduan Hao^a, Song Hong^a, Alex W. Robertson^b, Zhenyu Sun^a^,^c^,^*()

^aState Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029, China
^bDepartment of Materials, University of Oxford, Oxford, OX1 3PH, UK
^cKey Laboratory of Low-Carbon Conversion Science & Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210, China

Received:2021-07-15 Accepted:2021-07-15 Online:2022-03-05 Published:2022-03-01
Contact: Zhenyu Sun
Supported by:
National Natural Science Foundation of China(21972010);Natural Science Foundation of Beijing(2192039)

摘要/Abstract

摘要：

为了促进CO₂电化学还原(ECR)制备燃料和高值化学品, 开发高活性、低成本和高选择性催化剂至关重要. 本文通过简单的溶剂热法一步合成超细氧化铜(CuO)纳米颗粒修饰的二维Cu基金属有机框架(CuO/Cu-MOF)复合催化剂. 并采用X射线衍射、X射线光电子能谱、傅里叶变换红外光谱、高角环形暗场像-扫描透射电镜、N₂吸附/脱附、元素分析谱、CO₂吸附等方法进行表征, 对CuO/Cu-MOF复合材料的组成、形貌和孔结构等进行了系统研究. 结果表明, 超细CuO纳米粒子的尺寸为1.4到3.3 nm, 均匀修饰在二维Cu-BDC MOF表面. 由于其结构中丰富的孔道结构, CuO/Cu-MOF在常压下的CO₂吸附量可达5.0 mg_CO2 g_cat.^-1, 明显优于商业CuO纳米颗粒. 进一步在H型电解池、0.1 mol/L KHCO₃电解质溶液中研究了CuO/Cu-MOF的ECR性能; 结果表明, 在CO₂饱和的0.1 mol/L KHCO₃电解质溶液中, 反应产物包括CO, H₂, HCOOH和C₂H₄. 在-1.0至-1.2 V (相对于可逆氢电极, 下同)电势范围内, ECR占主导地位; 生成C₂H₄的起始电位为-0.85 V, 在-0.9至-1.2 V电势范围内, C₂H₄是主要产物; 电势高于-0.9 V时, CO和HCOOH是主要产物; 电势低于-0.9 V时, 开始生成CH₄, 且其含量随过电势增加而增加. 通过改变材料合成时的前驱体配比、配体种类和反应温度等可调节CuO/Cu-MOF催化剂对ECR产物的活性和选择性, 当对苯二甲酸:硝酸铜摩尔比为3:1、温度为100 °C时, 制得的CuO/Cu-MOF可在-1.1 V电势下将CO₂还原为C₂H₄, 其法拉第效率可达50.0%, 显著优于许多文献报道的Cu基电催化剂以及所合成的纯Cu-MOF和纯CuO, 其在相同电解条件下生成C₂H₄的法拉第效率分别为37.6%和25.5%. 此外, 生成C₂H₄的几何分电流密度约为7.0 mA cm^-2, 生成速率为21.0 μmol mg_cat.^-1h^-1, 阴极能量效率达到27.7%. 催化剂的稳定性测试结果表明, 在连续电解10 h后, C₂H₄的法拉第效率仍保持在45.0%以上. 进一步的机理研究表明, CuO/Cu-MOF复合材料中二维金属铜有机框架主体和超细CuO纳米颗粒在ECR反应过程中可协同实现对CO₂的吸附和活化, 促进C-C耦合, 从而高选择性生成C₂H₄. 本文为提高ECR生成C₂H₄的选择性和活性提供了有效策略.

关键词: 二氧化碳还原, 电催化, 氧化铜, 金属有机骨架, 乙烯

Abstract:

To facilitate the electrochemical CO₂ reduction (ECR) to fuels and valuable chemicals, the development of active, low cost, and selective catalysts is crucial. We report a novel ECR catalyst consisting of CuO nanoparticles with sizes ranging from 1.4 to 3.3 nm anchored on Cu metal-organic framework (Cu-MOF) nanosheets obtained through a one-step facile solvothermal method. The nanocomposites provide multiple sites for efficient ambient ECR, delivering an average C₂H₄ faradaic efficiency (FE) of ~50.0% at -1.1 V (referred to the reversible hydrogen electrode) in 0.1 mol/L aqueous KHCO₃ using a two-compartment cell, in stark contrast to a C₂H₄ FE of 25.5% and 37.6% over individual CuO and Cu-MOF respectively, also surpassing most newly reported Cu-based materials under similar cathodic voltages. The C₂H₄ FE remains at over 45.0% even after 10.0 h of successive polarization. Also, a ~7.0 mA cm^-2C₂H₄ partial geometric current density and 27.7% half-cell C₂H₄ power conversion efficiency are achieved. The good electrocatalytic performance can be attributed to the interface between CuO and Cu-MOF, with accessible metallic moieties and the unique two-dimensional structure of the Cu-MOF enhancing the adsorption and activation of CO₂ molecules. This finding offers a simple avenue to upgrading CO₂ to value-added hydrocarbons by rational design of MOF-based composites.

Key words: Carbon dioxide reduction, Electrocatalysis, Copper oxide, Metal-organic framework, Ethylene

王琳琳, 李欣, 郝磊端, 洪崧, Alex W. Robertson, 孙振宇. 超细氧化铜纳米颗粒修饰二维金属有机框架协同增强二氧化碳电化学还原生成乙烯[J]. 催化学报, 2022, 43(4): 1049-1057.

Linlin Wang, Xin Li, Leiduan Hao, Song Hong, Alex W. Robertson, Zhenyu Sun. Integration of ultrafine CuO nanoparticles with two-dimensional MOFs for enhanced electrochemical CO₂ reduction to ethylene[J]. Chinese Journal of Catalysis, 2022, 43(4): 1049-1057.

图/表 5

Fig. 1. (a) Schematic of the synthesis of CuO/Cu-MOF composite; (b) XRD patterns of CuO/Cu-MOF and simulated Cu-BDC MOF; (c) FT-IR, (d) Cu 2p XPS, and (e) O 1s XPS spectra of CuO/Cu-MOF; (f) N2 adsorption-desorption profiles of CuO/Cu-MOF; (g) CO2 desorption curves of CuO/Cu-MOF and commercial CuO [CuO (coml)].

Fig. 2. Low-magnification (a) and high-magnification (b) HAADF-STEM images of CuO/Cu-MOF composite. EDS elemental maps of Cu (c), O (d), C (e), and N (f) over the region depicted in image (b), along with corresponding EDS spectrum (g). (h,i,k) High-resolution STEM images of CuO/Cu-MOF; The inset in (i) shows size distribution of CuO NPs; (j) Transformed STEM image of (k). (l,m) Enlarged STEM images of the areas enclosed in the dashed squares in (k). (n,o) Corresponding FFT patterns of the regions shown in (l and m).

Fig. 3. (a) LSV profiles of CuO/Cu-MOF in Ar- (black dotted line) or CO2- (red solid line) saturated 0.1 mol/L KHCO3 solution with a scan rate of 5.0 mV s?1; (b) ECR FE (bar) and overall current density (ball) against applied potential over CuO/Cu-MOF electrode in CO2-purged 0.1 mol/L KHCO3; (c) ECR FE (bar) and overall current density (ball) of CuO/Cu-MOF against mole ratio of 1,4-BDC and Cu(NO3)2·3H2O; (d) ECR FE (bar) and partial current density (ball) of CuO/Cu-MOF obtained with distinct copper precursor types together with Cu-MOF and CuO. Data in Fig. 3(b)?(d) are represented as mean ± SE.

Fig. 4. (a) ECR FE (bar) and C2H4 partial geometric current density (ball) of CuO/Cu-MOF obtained at varying conditions (solvothermal temperature, linker type), commercial Cu(OH)2, 1,4-BDC, CuO, Cu2O, and Cu powder; (b) ECR FE (bar) and C2H4 geometric current density (ball) of CuO/Cu-MOF in various electrolytes. The concentration of anions in various mixed electrolytes is 0.1 mol/L while the concentration of K+in all the cases is 0.2 mol/L. The cathodic potential applied is -1.1 V. Data are represented as mean ± SE.

Fig. 5. C2H4 FEs (a) and C2H4 EEs (b) of CuO/Cu-MOF and previously demonstrated Cu-based materials (summarized in Table S1) in an H-type cell; (c) Tafel plots for C2H4 production of CuO/Cu-MOF, neat Cu-MOF, and CuO; (d) Nyquist curves with corresponding fitting profiles for CuO/Cu-MOF, CuO, and Cu-MOF. The inset depicts the equivalent circuit used for fitting the data, where RS shows the combination of the resistance of electrodes and electrolyte, CPE and Rct represent the capacitance and charge transfer resistance of working electrode-electrolyte interface, respectively. (e) C2H4 FEs (bar) and corresponding partial current densities (ball) for CuO/Cu-MOF during cycles at -1.1 V with an interval of 1.0 h in CO2- and Ar-purged 0.1 mol/L KHCO3. Data are represented as mean ± SE. (f) Current density and C2H4 FE as function of time for electrolysis at a controlled cathodic voltage of -1.1 V. The mole ratio of 1,4-BDC and Cu(NO3)2·3H2O and solvothermal temperature used for the synthesis of CuO/Cu-MOF are 3:1 and 100.0 °C unless specified otherwise.

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超细氧化铜纳米颗粒修饰二维金属有机框架协同增强二氧化碳电化学还原生成乙烯

Integration of ultrafine CuO nanoparticles with two-dimensional MOFs for enhanced electrochemical CO₂ reduction to ethylene

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超细氧化铜纳米颗粒修饰二维金属有机框架协同增强二氧化碳电化学还原生成乙烯

Integration of ultrafine CuO nanoparticles with two-dimensional MOFs for enhanced electrochemical CO2 reduction to ethylene

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Integration of ultrafine CuO nanoparticles with two-dimensional MOFs for enhanced electrochemical CO₂ reduction to ethylene