钴(II)酞菁全氟化策略用于提升非贵金属体系中光催化还原CO2性能

doi:10.1016/S1872-2067(23)64433-X

催化学报 ›› 2023, Vol. 49: 160-167.DOI: 10.1016/S1872-2067(23)64433-X

钴(II)酞菁全氟化策略用于提升非贵金属体系中光催化还原CO₂性能

李孜孜^a, 王嘉蔚^a^,^b^,^*(), 黄衍钧^a, 欧阳钢锋^a^,^c^,^d^,^*()

^a中山大学化学学院环境与能源化学广东普通高校重点实验室, 广东广州 510275, 中国
^b西班牙加泰罗尼亚化学研究所, 塔拉戛纳, 西班牙
^c郑州大学化学院, 高级分析与基因测序中心, 河南郑州 450001, 中国
^d广东省化学危害应急检测技术重点实验室, 广东省科学院测试分析研究所(中国广州分析测试中心), 广东广州 510070, 中国

收稿日期:2023-03-01 接受日期:2023-03-16 出版日期:2023-06-18 发布日期:2023-04-04
通讯作者: ^*电子信箱: wangjw25@mail2.sysu.edu.cn (王嘉蔚), cesoygf@mail.sysu.edu.cn (欧阳钢锋).
基金资助:
国家自然科学基金(21737006);国家自然科学基金(22076222);国家自然科学基金(22036003);广东省自然科学基金(2020A1515110017);广东省自然科学基金(2021A1515012033)

Enhancing CO₂ photoreduction via the perfluorination of Co(II) phthalocyanine catalysts in a noble-metal-free system

Zizi Li^a, Jia-Wei Wang^a^,^b^,^*(), Yanjun Huang^a, Gangfeng Ouyang^a^,^c^,^d^,^*()

^aKLGHEI of Environment and Energy Chemistry, School of Chemistry, Sun Yat-sen University, Guangzhou 510275, Guangdong, China
^bInstitute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology (BIST), Avinguda Paisos Catalans 16, Tarragona 43007, Spain
^cChemistry College, Center of Advanced Analysis and Gene Sequencing, Zhengzhou University, Zhengzhou 450001, Henan, China
^dGuangdong Provincial Key Laboratory of Emergency Test for Dangerous Chemicals, Guangdong Institute of Analysis (China National Analytical Center Guangzhou), Guangzhou 510070, Guangdong, China

Received:2023-03-01 Accepted:2023-03-16 Online:2023-06-18 Published:2023-04-04
Contact: ^*E-mail: wangjw25@mail2.sysu.edu.cn (J.-W. Wang),cesoygf@mail.sysu.edu.cn (G. Ouyang).
Supported by:
National Natural Science Foundation of China(21737006);National Natural Science Foundation of China(22076222);National Natural Science Foundation of China(22036003);Guangdong Basic and Applied Basic Research Foundation(2020A1515110017);Guangdong Basic and Applied Basic Research Foundation(2021A1515012033)

摘要/Abstract

摘要：

将CO₂还原成含碳能源或化学品, 不仅能够缓解温室气体造成的危害, 也是实现“双碳”目标的有效途径. 为了有效避免竞争性的产氢反应和克服CO₂的惰性, 需要合适的催化剂提高还原产物CO₂的选择性, 并促进反应的快速进行. 由于以过渡金属配合物为主的分子型催化剂具备已知的清晰结构, 且具有丰富多变的氧化还原性质, 有助于进行结构优化、分离催化中间体和机理分析, 分子型CO₂还原催化剂目前受到了广泛关注. 另一方面, 利用地壳储量丰富的非贵金属替代珍贵的4d和5d过渡金属来制备分子催化剂有利于降低制备成本, 实现大规模应用. 因此, 设计和优化非贵金属分子催化剂用于光催化CO₂还原是非常有必要的. 目前主要的优化方法包括调控电子效应、调控配体共轭程度、设置质子传递中心和设置库仑相互作用等. 其中, 通过添加给电子/吸电子取代基团来调节配体骨架的电子性质, 可以有效调节金属中心的电子密度, 从而改善分子催化剂的氧化还原性质. 然而, 采取该策略可能会导致催化活性和过电位间的此消彼长, 限制了催化剂的提升空间. 因此, 电子效应调控策略在高效CO₂光还原分子催化剂上的合理应用仍需系统性的机理研究.

本文采用一种全氟化的配体优化策略, 发现在原始的酞菁钴(CoPc)结构上修饰多个氟取代基所得的全氟酞菁钴(CoFPc)能够高效光催化CO₂还原为CO. 相比于CoPc, CoFPc体系的表观量子产率Φ从19.0%增加到58.2%, 最大转换数达到9185, 最高选择性接近100%, 且优于平行的贵金属光敏剂体系. 电化学与理论计算结果表明, 氟取代基的吸电子效应降低了驱动催化剂所需的过电位, 并降低了Co(Ⅲ)-COOH形成决速步骤的吉布斯自由能. 通过光谱电化学与理论计算初步表征了Co(Ⅲ)-COOH中间体, 最后结合计算结果以及荧光猝灭实验, 初步提出了CuBCP/CoFPc体系的催化机理.

综上, 本文展示了全氟化策略是一种很有前景的CO₂还原催化剂电子效应调控方法, 为设计更高性能的CO₂还原光催化体系提供思路.

关键词: 酞菁钴, 光催化二氧化碳还原, 铜基光敏剂, 全氟化, 电子调控

Abstract:

The manufacture of high-performance photocatalytic systems based on earth-abundant elements remains a key challenge, urging operative strategies for catalyst design. Herein, we present the construction of an efficient and noble-metal-free molecular system for the photoreduction of CO₂to CO using a Cu(I) photosensitizer and Co(II) phthalocyanine catalysts. It was found that the perfluorination of Co(II) phthalocyanine shows enhanced catalytic performance for CO₂-to-CO conversion compared with pristine Co(II) phthalocyanines, achieving a remarkable apparent quantum yield of 58.2% at 425 nm, which is three times that of the pristine one (19.0%). The Cu(I)/Co(II) system also achieved a maximum turnover number of 9185 and near-unity selectivity. These improvements can be attributed to the electron-withdrawing effect of the fluorine substituents, which lowers the catalytic overpotential for catalysis and decreases the Gibbs free energy of the rate-determining Co-carboxylate-forming step. This work indicates that perfluorination is an effective approach to optimize the catalytic performance of molecular catalysts.

Key words: Cobalt phthalocyanine, Photocatalytic CO₂ reduction, Copper photosensitizer Perfluorination, Electronic modification

李孜孜, 王嘉蔚, 黄衍钧, 欧阳钢锋. 钴(II)酞菁全氟化策略用于提升非贵金属体系中光催化还原CO₂性能[J]. 催化学报, 2023, 49: 160-167.

Zizi Li, Jia-Wei Wang, Yanjun Huang, Gangfeng Ouyang. Enhancing CO₂ photoreduction via the perfluorination of Co(II) phthalocyanine catalysts in a noble-metal-free system[J]. Chinese Journal of Catalysis, 2023, 49: 160-167.

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图/表 5

Scheme 1. Molecular structures of the catalysts (CoFPc & CoPc), photosensitizer (CuBCP) and sacrificial agent (1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole, BIH) used in this study.

Table 1 The Hirshfeld population (e), HOMO, LUMO energy levels (eV) of CoFPc and CoPc, and the Gibbs free energy (eV) of CoFPc, Co8FPc and CoPc involved in CO2 reduction.

Molecule	Hirshfeld population (e)	HOMO (eV)	LUMO (eV)	*COOH (eV)	*CO (eV)
CoFPc	0.2127	-5.64	-3.29	1.080	-0.161
CoPc	0.2038	-5.31	-2.89	1.129	-0.114
Co8FPc	N.A.	N.A.	N.A.	1.089	-0.155

Fig. 1. (a) Time profiles of photocatalytic CO (star) and H2 (diamond) formation with CuBCP/CoFPc (red) or CuBCP/CoPc (blue) system. (b) Φ values for CO (gray) and H2 (pale gray) formation in CuBCP/CoFPc and CuBCP/CoPc systems. (c) Mass spectra via gas chromatography of the generated gas from a mixture of CoFPc (0.05 mmol L?1), CuBCP (0.5 mmol L?1), xantphos (1.0 mmol L?1), PhOH (5.0 vol%), and BIH (20 mmol L?1) in 4 mL CH3CN/TEA (v:v = 5:1) within 1 h of 425 nm irradiation under 1 atm 13CO2. (d) Comparison of CO (red) and H2 (pale red) with noble-metal benchmarking PSs (0.50 mmol L?1 PS/0.05 mmol L?1 catalyst).

Fig. 2. CVs of 0.5 mmol L?1 CoFPc (a) and CoPc (b) under N2 (violet), CO2 (blue) or CO2 with 5 vol% PhOH added in CH3CN/NMP (red). (c) Calculated electron density distribution of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of CoFPc and CoPc, at PBE0/def2-SVP level. (d) Gibbs free energy profiles of CoFPc and CoPc.

Fig. 3. Overview (a) and magnified (b) IR-SEC spectra of 1.0 mmol L?1 of CoFPc in THF/CD3CN (v:v = 1:1) under CO2 under different applied potentials. Inset in (b) shows the calculated structure of the Co(III)-COOH species in CoFPc and the C=O stretching frequency, which is consistent with the IR-SEC results.

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钴(II)酞菁全氟化策略用于提升非贵金属体系中光催化还原CO₂性能

Enhancing CO₂ photoreduction via the perfluorination of Co(II) phthalocyanine catalysts in a noble-metal-free system

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