充分稳定和暴露的铜基异质结实现CO2高效电还原制乙醇

doi:10.1016/S1872-2067(23)64604-2

催化学报 ›› 2024, Vol. 58: 216-225.DOI: 10.1016/S1872-2067(23)64604-2

充分稳定和暴露的铜基异质结实现CO₂高效电还原制乙醇

蒋兴星, 赵雨昕, 孔艳, 孙建桔, 冯上照, 胡琪, 杨恒攀^*(), 何传新^*()

深圳大学化学与环境工程学院, 广东深圳518060

收稿日期:2023-12-12 接受日期:2024-01-16 出版日期:2024-03-18 发布日期:2024-03-28
通讯作者: *电子信箱: hpyang@szu.edu.cn (杨恒攀),hecx@szu.edu.cn (何传新).
基金资助:
广东省基础与应用基础研究基金(2023A1515012776);广东省基础与应用基础研究基金(2022B1515120084);国家自然科学基金(22172099);国家自然科学基金(U21A20312)

Adequately stabilized and exposed copper heterostructure for CO₂ electroreduction to ethanol with ultrahigh mass activity

Xingxing Jiang, Yuxin Zhao, Yan Kong, Jianju Sun, Shangzhao Feng, Qi Hu, Hengpan Yang^*(), Chuanxin He^*()

College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen 518060, Guangdong, China

Received:2023-12-12 Accepted:2024-01-16 Online:2024-03-18 Published:2024-03-28
Contact: *E-mail: hpyang@szu.edu.cn (H. Yang),hecx@szu.edu.cn (C. He).
Supported by:
Guangdong Basic and Applied Basic Research Foundation(2023A1515012776);Guangdong Basic and Applied Basic Research Foundation(2022B1515120084);National Natural Science Foundation of China(22172099);National Natural Science Foundation of China(U21A20312)

摘要/Abstract

摘要：

二氧化碳(CO₂)虽然被视为破坏生态环境的温室气体, 但也是储量最丰富的碳资源, 对其进行转化和利用将对社会环境和能源结构产生深远影响. 电化学还原CO₂ (CO₂RR)不仅转化效率高, 而且成本较低, 有望实现规模化生产. 在众多催化剂中, 廉价易得的铜基催化剂被认为是电化学催化还原CO₂生成高附加值产物的理想催化剂之一, 其中铜氧化物的存在是CO₂RR生成高附加值产物的关键. 然而, CO₂RR过程是在负电位下进行的, 当施加电位低于‒0.1 V_RHE时, 铜氧化物很容易被还原为金属态铜. 因此, 催化剂稳定氧化态铜的能力在保持连续、高效和稳定的CO₂RR产多碳产物性能中至关重要.

本文将简单的O₂等离子体处理技术与静电纺丝技术相结合, 合成了多孔碳纳米纤维负载的Cu/Cu_xO异质结催化剂, 并考察了其催化CO₂RR的性能. 在静电纺丝过程中, Cu-ZIF-8前驱体的加入使得热处理后的原丝纤维中形成了丰富的网络贯穿多孔结构, 该结构有效地实现了铜纳米颗粒的均匀分散; 随后, 通过O₂等离子体处理技术, 在碳纳米纤维中构建了大量的开放介孔, 为CO₂的吸附和反应提供了有利环境, 并使Cu/Cu_xO异质结位点暴露于反应界面. 电化学性能测试结果表明, 在400 mA cm^‒2电流密度下, 独特的Cu/Cu_xO异质结活性位点电催化还原CO₂生成乙醇的法拉第效率可达70.7%, 该性能优于未经O₂等离子体处理的多孔铜纳米纤维. 此外, 高暴露的Cu/Cu_xO异质结活性位点显著地增加实际参与反应的活性位点数量, 经计算Cu/Cu_xO异质结CO₂RR产乙醇的质量活性高达8.4 A mg^‒1, 是目前报道生产乙醇的较高质量活性.

多孔碳纳米纤维衬底不仅具有协同电子输运能力, 而且在CO₂RR测试中施加的负电压有助于维持Cu/Cu_xO异质结构的稳定性, 使其在高电流密度下能够保持长时间的催化稳定性. 此外, 本文利用原位拉曼光谱和红外光谱、有限元模拟及密度泛函理论计算等方法深入研究了Cu/Cu_xO异质结的催化机理. 原位拉曼光谱和红外光谱表征结果证实了在CO₂RR过程中Cu_xO的动态稳定状态以及关键信号*CO和C‒C键的存在; 理论计算表明, Cu/Cu_xO异质结的存在促进了关键中间体*CO的溢流, 降低了C‒C耦合过程的反应能垒, 从而提高了还原产物乙醇的产率.

综上, 本文成功地在多孔铜纳米纤维中引入氧化物物种, 并优化了纤维孔结构. 其表现出了较好的电催化还原CO₂性能, 可高选择性生成乙醇, 其独特的多孔碳纤维结构充分暴露了活性位点, 实现了较高的质量活性. 本文所采用的催化剂组分和微观结构的调控策略为提升电催化中催化剂稳定性和催化活性提供了有益的借鉴.

关键词: 二氧化碳电还原, Cu/Cu_xO异质结, 开口孔结构, 质量活性, 乙醇

Abstract:

Adequately exposure of active sites to reactants is crucial in improving the actual catalytic activity in various electrocatalytic reactions. e.g., CO₂ electroreduction. Herein, we construct abundant opening mesopores throughout carbon nanofibers via a simple O₂ plasma treatment, which can simultaneously create a CO₂-rich environment and expose Cu/Cu_xO sites to the reaction interface. The unique Cu/Cu_xO sites can generate a 70.7% Faradaic efficiency of C₂H₅OH at the 400 mA cm^-2 current density. Moreover, this superior structure can significantly increase the number of active sites that actually participated in the reaction, and leads to an exceptional 8.4 A mg^-1 Cu mass activity for C₂H₅OH, which is among the highest mass activity for C₂H₅OH ever reported. The DFT calculation and CO-TPD studies reveal that the created Cu/Cu_xO heterostructure provides adequate *CO coverages and lowers the energy barrier of the C-C coupling process for ethanol formation, in which the key ethanol intermediates are detected via the in-situ spectra investigations. This strategy can be easily applied to construct efficient catalysts in other electrocatalytic reactions.

Key words: CO₂ electroreduction, Copper heterostructure, Opening mesopores, Mass activity, Ethanol

蒋兴星, 赵雨昕, 孔艳, 孙建桔, 冯上照, 胡琪, 杨恒攀, 何传新. 充分稳定和暴露的铜基异质结实现CO₂高效电还原制乙醇[J]. 催化学报, 2024, 58: 216-225.

Xingxing Jiang, Yuxin Zhao, Yan Kong, Jianju Sun, Shangzhao Feng, Qi Hu, Hengpan Yang, Chuanxin He. Adequately stabilized and exposed copper heterostructure for CO₂ electroreduction to ethanol with ultrahigh mass activity[J]. Chinese Journal of Catalysis, 2024, 58: 216-225.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(23)64604-2

https://www.cjcatal.com/CN/Y2024/V58/I3/216

图/表 6

Fig. 1. Production process of Cu-PCNF@O2 via electrospinning and O2 plasma techniques.

Fig. 2. (a) The flexibility tests of Cu-PCNF@O2. Morphological and structural characterization of Cu-PCNF@O2: SEM image (b), TEM images (c,d), HR-TEM image (e), HAADF-STEM image and EDS elemental mappings of C, O, Cu (f).

Fig. 3. XRD patterns (a) and Raman spectra (b) of four samples. (c) N2 adsorption-desorption isotherms curve of Cu-PCNF@O2, insert the related pore size distribution. Survey XPS (d), comparison fitting curves of Cu 2p XPS spectra (e) and Cu LM2 Auger spectra (f) for Cu-CNF, Cu-PCNF, Cu-PCNF@N2 and Cu-PCNF@O2. (g) EPR Spectroscopy of Cu-PCNF and Cu-PCNF@O2. (h) Valence band spectra of Cu-PCNF and Cu-PCNF@O2.

Fig. 4. (a) LSV curves comparison of four samples in CO2-saturated 0.5 mol L?1 KHCO3 electrolyte. (b) Faradaic efficiencies for CO2RR products on Cu-PCNF@O2 at various potentials. C2H5OH partial current densities (c) and C2/C1 products ratios (d) in H-type cell of three samples. C2H5OH Faradaic efficiencies (e) and Cu mass activity (f) of three samples in 1 mol L?1 KOH electrolyte using a flow cell. (g) CO2RR to ethanol performance comparisons of Cu-PCNF@O2 in this work with other reported Cu-based catalysts. (h) Long-term CO2RR performance on Cu-PCNF@O2 at 300 mA cm-2 in 1 mol L?1 KOH.

Fig. 5. Negative charge density distribution on the Simulated Cu-CNF (a), Cu-PCNF (b) and Cu-PCNF@O2 (c) surface. Surface K+ density distribution on the simulated Cu-CNF (d), Cu-PCNF (e) and Cu-PCNF@O2 (f) surface.

Fig. 6. (a,b) In-situ FTIR spectra for CO2RR on Cu-PCNF@O2 from OCP ~?1.2 VRHE. (c) The adsorption energies of *CO and *OCCO on different sites of Cu-PCNF@O2. (d) CO-TPD spectra of Cu-PCNF and Cu-PCNF@O2. (e) Free energy for different pathways of *CO to form C?C coupling intermediate *OCCHO on Cu/CuxO heterostructure surface. (f) Energy diagram of CO2 reduction to *OCCHO on Cu and Cu/CuxO heterostructure surface. (g) Schematic illustration of a plausible CO2RR mechanism to form C2H5OH.

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充分稳定和暴露的铜基异质结实现CO₂高效电还原制乙醇

Adequately stabilized and exposed copper heterostructure for CO₂ electroreduction to ethanol with ultrahigh mass activity

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