调节金属有机框架的配体场实现在工业电流密度下将CO2高选择性还原为碳氢化合物

doi:10.1016/S1872-2067(23)64519-X

催化学报 ›› 2023, Vol. 53: 102-108.DOI: 10.1016/S1872-2067(23)64519-X

调节金属有机框架的配体场实现在工业电流密度下将CO₂高选择性还原为碳氢化合物

薛欢^a, 黄嘉润^a, 王志烁^a, 赵振华^a, 石文^b, 廖培钦^a^,^*(), 陈小明^a

^a中山大学化学学院, 生物无机与合成化学教育部重点实验室, 广东广州510275
^b中山大学化学学院, 广东广州510275

收稿日期:2023-07-05 接受日期:2023-09-20 出版日期:2023-10-18 发布日期:2023-10-25
通讯作者: *电子邮箱: liaopq3@mail.sysu.edu.cn (廖培钦).
基金资助:
国家重点研究发展计划(2021YFA1500401);国家自然科学基金(21890380);国家自然科学基金(21821003);国家自然科学基金(22371304);广东省科技创新战略专项市县科技创新支撑项目(STKJ2023078);广东省科技重点项目(2020B010188002);广东省珠江人才计划地方创新研究团队项目(2017BT01C161)

Tailoring ligand fields of metal-azolate frameworks for highly selective electroreduction of CO₂ to hydrocarbons at industrial current density

Huan Xue^a, Jia-Run Huang^a, Zhi-Shuo Wang^a, Zhen-Hua Zhao^a, Wen Shi^b, Pei-Qin Liao^a^,^*(), Xiao-Ming Chen^a

^aMOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat−Sen University, Guangzhou 510275, Guangdong, China
^bSchool of Chemistry, Sun Yat-Sen University, Guangzhou 510275, Guangdong, China

Received:2023-07-05 Accepted:2023-09-20 Online:2023-10-18 Published:2023-10-25
Contact: *E-mail: liaopq3@mail.sysu.edu.cn (P.-Q. Liao).
Supported by:
The National Key Research and Development Program of China(2021YFA1500401);The National Nature Science Foundation of China(21890380);The National Nature Science Foundation of China(21821003);The National Nature Science Foundation of China(22371304);Science and Technology Innovation Special Support Project of Guangdong Province City County, China(STKJ2023078);Science and Technology Key Project of Guangdong Province, China(2020B010188002);Local Innovative and Research Teams Project of Guangdong Pearl River Talents Program(2017BT01C161)

摘要/Abstract

摘要：

电化学CO₂还原反应(eCO₂RR)利用可再生能源将CO₂转化为增值化学品, 因而得到广泛关注. 然而, 目前已报道的电催化剂倾向于将CO₂转化为HCOOH和CO, 而不是增值化学品. 金属有机框架(MOF)由于具有较大的比表面积、可调的结构和丰富的活性位点, 已被广泛应用于多相催化、气体储存和气体分离等领域. MOF是研究结构-性能关系的理想平台. 金属多氮唑框架(MAF)是一类具有较好化学稳定性的MOF, 但在电催化方面的研究很少.

本文合成了三种具有相同四铜(II)簇单元的金属多氮唑框架(Cu-BTP, Cu-BTTri和Cu-BTT), 分别由吡唑、三氮唑和四氮唑衍生配体构成. 配体的pKa值依次为H₃BTP (pKa = 19.8) > H₃BTTri (pKa = 13.9) > H₃BTT (pKa = 4.9), 表明与BTTri³⁻和BTT³⁻相比, BTP³⁻具有最高的配体场强或配位能力. 在相同条件下, 对三种MAFs材料进行了电催化CO₂还原性能测试. 其中, 基于吡唑配体的Cu-BTP在流动电解池中电流密度可达1.25 A cm^-2, 碳氢产物的选择性达到82% (CH₄为60%, C₂H₄为22%). 在1.25 A cm⁻²下连续运行60 h后, 催化剂性能未见明显变化. 三种MAFs材料对碳氢产物选择性的顺序为Cu-BTP (81%) > Cu-BTTri (60%) > Cu-BTT (49%), 与配体的pKa顺序一致, 说明配体场的场强对eCO₂RR的烃类产物选择性有重要影响. ¹³CO₂同位素电化学实验证实了气液产物中的碳来自于CO₂. X射线衍射图谱、扫描电镜、透射电镜、X射线吸收光谱和X射线光电子能谱结果表明, Cu-BTP具有较好的稳定性. 密度泛函理论(DFT)计算揭示了三种MAFs的eCO₂RR反应机制. Cu-BTP (Cu: +0.95, N: −0.75)中铜离子和配位氮原子的电荷均低于Cu-BTTri (Cu: +0.99, N: −0.28)和Cu-BTT (Cu: +1.02, N: −0.16), 该结果归因于配位N原子周围的电子密度与pKa数值呈正相关. 最强的路易斯碱度和配体场场强导致Cu-BTP中金属簇的Cu-N₄位点上电子密度最大, 因此金属中心的路易斯碱度增强最多. 相应地, Cu(II)在Cu-BTP中的晶体场稳定化能值(218.48 kJ mol⁻¹)大于Cu-BTTri (215.59 kJ mol⁻¹)和Cu-BTT (208.23 kJ mol⁻¹), Cu-BTP的价带最大值(VBM)和导带最小值(CBM)的能级也最高. 根据Koopmans定理, VBM越高说明催化剂的供电子能力越强, 越高的VBM能级越靠近^*CO的π^*未占据轨道, 这不仅有利于Lewis酸CO₂的吸附和活化, 也有利于^*CO和^*CHO中间体通过π反键相互作用的吸附和活化. 因此, ^*CO和^*CHO在Cu-BTP, Cu-BTTri和Cu-BTT上的吸附能依次降低. 总体而言, 三种MAF金属中心的路易斯碱度依次为Cu-BTP > Cu-BTTri > Cu-BTT, 与它们的eCO₂RR催化性能一致.

综上, 本文通过调节MAF的有机配体的场强度来调控eCO₂RR中金属活性位点与关键中间体(^*CO, ^*CHO和^*COCHO)的相互作用, 进而生成碳氢化合物. 其中, 具有最强路易斯碱配体的MAF材料在安培级电流密度下对CO₂深度还原为碳氢化合物具有较高的选择性, 为理性开发设计MOF及相应高性能电催化剂提供了新思路.

关键词: 金属有机框架, 金属氮酸盐框架, 碳氢化合物, 电催化, 铜

Abstract:

The catalytic activity of a metal complex is often contingent upon factors such as its valence state, coordination configuration of the metal ion, and coordination ability of the ligand. Hence, revealing the influence of the ligand field of the active metal center on the selectivity of the product for electrochemical CO₂ reduction is crucial. Herein, three isostructural metal-azolate frameworks (MAFs) (Cu-BTP, Cu-BTTri, and Cu-BTT) with the same cyclic tetracopper(II) cluster units, namely [Cu₃(BTP)₂] (Cu-BTP, H₃BTP = 1,3,5-tris(1H-pyrazol-4-yl)benzene), [Cu₃(BTTri)₂] (Cu-BTTri, H₃BTTri = 1,3,5-tris(1H-1,2,3-triazol-5-yl)benzene), and [Cu₃(BTT)₂] (Cu-BTT, H₃BTT = 1,3,5-tris(2H-tetrazol-5-yl)benzene) were synthesized using pyrazolate-, triazolate-, and tetrazolate-based ligands, respectively. The synthesized MAFs were subjected to analysis to evaluate their electrochemical capabilities for reducing CO₂ under identical reaction conditions. Among them, the pyrazolate MAF, Cu-BTP, delivers a current density of 1.25 A cm⁻² in a flow cell device with the highest Faradiac efficiency for hydrocarbons (CH₄, 60%; C₂H₄, 22%). Furthermore, the system shows no obvious degradation over 60 h of continuous operation. The order of selectivity of the three MAFs for hydrocarbon production is consistent with the corresponding pK_a values of the azolate ligands. Theoretical calculations show that a stronger Lewis basicity of the organic ligand, resulting in a stronger ligand field strength, is conducive to strengthening the binding of metal centers with key intermediates, such as *CO and *CHO. This ultimately leads to the deep reduction of CO₂ to hydrocarbons.

Key words: Metal-organic framework, Metal-azolate framework, Hydrocarbons, Electrocatalysis, Copper

薛欢, 黄嘉润, 王志烁, 赵振华, 石文, 廖培钦, 陈小明. 调节金属有机框架的配体场实现在工业电流密度下将CO₂高选择性还原为碳氢化合物[J]. 催化学报, 2023, 53: 102-108.

Huan Xue, Jia-Run Huang, Zhi-Shuo Wang, Zhen-Hua Zhao, Wen Shi, Pei-Qin Liao, Xiao-Ming Chen. Tailoring ligand fields of metal-azolate frameworks for highly selective electroreduction of CO₂ to hydrocarbons at industrial current density[J]. Chinese Journal of Catalysis, 2023, 53: 102-108.

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图/表 4

Fig. 1. Chemical structures of H3BTP, H3BTTri, and H3BTT ligands (a), the cyclic tetracopper(II) units (b), and corresponding 3D frameworks (c) of Cu-BTP, Cu-BTTri and Cu-BTT. Color codes: Cu, purple; C, gray; N, blue. Note: the hydrogen atoms were omitted for clarity.

Fig. 2. Electrocatalytic performances. (a) LSV curves of Cu-BTP recorded under CO2 and Ar in a flow cell. (b) Long-time durability test of Cu-BTP in flow cell. (c) FEs (hydrocarbons) of Cu-BTP, Cu-BTTri, and Cu-BTT, respectively, at different potentials in an H-type cell. (d) Comparison of FEs (hydrocarbons) and partial current densities of Cu-BTP and other reported electrocatalysts.

Fig. 3. Cu K-edge EXAFS fitting curves (a) before and (b) after electrocatalysis. Wavelet transforms (WT) contour plots of Cu-BTP (c) before and (d) after electrocatalysis.

Fig. 4. (a) Charge density differences of Cu-BTP with an isosurface level of 0.004 e bohr?3. The blue and yellow indicate electron depletion and accumulation. (b) Schematic illustration of d-orbital splitting of Cu(II) ion in Cu-BTP. (c) The energy levels of the VBMs and CBMs of the MAFs. (d) Operando ATR-FTIR spectra of Cu-BTP. (e) Comparison of the CO adsorption energies of the Cu(II) ions in the cyclic tetracopper(II) cluster with and without another intermediate. (f) Comparison of the free energies for the formation of *COCHO through the coupling of CO and *CHO intermediates. (g) Proposed pathways of Cu-BTP for the formation of CH4, CH3OH, C2H4, and C2H5OH. Color codes: Cu, purple; C, gray; N, blue.

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调节金属有机框架的配体场实现在工业电流密度下将CO₂高选择性还原为碳氢化合物

Tailoring ligand fields of metal-azolate frameworks for highly selective electroreduction of CO₂ to hydrocarbons at industrial current density

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