一例整合了三联吡啶钌和卟啉锌的金属-有机框架材料用于光催化二氧化碳还原全反应

doi:10.3866/PKU.WHXB202306046

物理化学学报 >> 2024, Vol. 40 >> Issue (4): 2306046.doi: 10.3866/PKU.WHXB202306046

所属专题：二氧化碳资源化

一例整合了三联吡啶钌和卟啉锌的金属-有机框架材料用于光催化二氧化碳还原全反应

陈慧滢, 朱浩林*(), 廖培钦*(), 陈小明*()

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, 广州 510275

收稿日期:2023-06-27 修回日期:2023-07-14 录用日期:2023-07-14 发布日期:2023-07-20
通讯作者: Email: zhuhlin3@mail2.sysu.edu.cn (朱浩林)liaopq3@mail.sysu.edu.cn (廖培钦)cxm@mail.sysu.edu.cn (陈小明)
基金资助:
国家重点研发计划(2021YFA1500401); 国家自然科学基金(21890380); 国家自然科学基金(21821003); 广东省“珠江人才计划”本土创新科研团队项目(2017BT01C161); 广东省科技创新战略专项市县科技创新支撑项目(STKJ2023078)

Integration of Ru(Ⅱ)-Bipyridyl and Zinc(Ⅱ)-Porphyrin Moieties in a Metal-Organic Framework for Efficient Overall CO₂ Photoreduction

Hui-Ying Chen, Hao-Lin Zhu*(), Pei-Qin Liao*(), Xiao-Ming Chen*()

School of Chemistry, MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, Sun Yat-Sen University, Guangzhou 510275, China

Received:2023-06-27 Revised:2023-07-14 Accepted:2023-07-14 Published:2023-07-20
Contact: Email: zhuhlin3@mail2.sysu.edu.cn (Hao-Lin Zhu)liaopq3@mail.sysu.edu.cn (Pei-Qin Liao)cxm@mail.sysu.edu.cn (Xiao-Ming Chen)
Supported by:
the National Key Research and Development Program of China(2021YFA1500401); the National Natural Science Foundation of China(21890380); the National Natural Science Foundation of China(21821003); the Local Innovative and Research Teams Project of the Guangdong Pearl River Talents Program, China(2017BT01C161); the Technology Innovation Strategy Special City and County Science and Technology Innovation Support Project, China(STKJ2023078)

1. WHXB202306046-SI-8p.pdf.pdf(1718KB)

摘要/Abstract

摘要：

利用源源不断的太阳能将CO₂和水转化为增值化学品，是缓解温室效应与能源危机的一种有前途的方法。由于催化体系中的不同功能性部分难以实现氧化与还原反应的耦合，使用水作为还原剂实现光催化CO₂还原是一项具有挑战性的工作。金属有机框架(metal-organic framework，MOF)由于其较大的比表面积、多样化的活性位点和结构可调性，是CO₂光催化还原全反应的良好备选材料。本文中，我们首先整合了具有光活性的锌(Ⅱ)卟啉基元与联吡啶钌(Ⅱ)基元，构建了一种MOF光催化剂，记作PCN-224(Zn)-Bpy(Ru)。为了进行比较，还合成了两种仅具有锌(Ⅱ)卟啉或联吡啶钌(Ⅱ)基元的同构MOF，分别记作PCN-224(Zn)-Bpy和PCN-224-Bpy(Ru)。由测试结果可知，PCN-224(Zn)-Bpy(Ru)在乙腈和水混合溶液中表现出对CO₂还原可观的光催化活性(CO产率为7.6 µmol·g⁻¹·h⁻¹)，无需额外添加助催化剂、光敏剂或牺牲剂。通过质谱仪观测到¹³CO (m/z = 29)、¹³C¹⁸O (m/z = 31)、¹⁶O¹⁸O (m/z =34)和¹⁸O₂ (m/z = 36)信号，表明CO₂和H₂O分别作为CO和O₂的碳源和氧源，这进一步证实了光催化CO₂还原与H₂O氧化的耦合。然而，在相同条件下对PCN-224-Bpy(Ru)与PCN-224(Zn)-Bpy的光催化性能进行测试，CO产率分别仅为1.5与0 µmol·g⁻¹·h⁻¹。机理研究表明，PCN-224(Zn)-Bpy(Ru)的最低未占据分子轨道(LUMO)电位比CO₂/CO的氧化还原电位更负，而最高占据分子轨道(HOMO)电位比H₂O/O₂的氧化还原电位更正，在热力学上满足了光催化CO₂还原全反应的要求。相比之下，不含联吡啶钌(Ⅱ)基元的PCN-224(Zn)-Bpy的HOMO电位更负于H₂O/O₂的氧化还原电位，这表明联吡啶钌(Ⅱ)基元在热力学上是光催化CO₂还原全反应所必需的。此外，光致发光光谱中，荧光几乎被PCN-224(Zn)-Bpy(Ru)猝灭，且平均光致发光寿命比PCN-224(Zn)-Bpy和PCN-224-Bpy(Ru)更长，这表明PCN-224中光生载流子的复合率较低。与PCN-224(Zn)-Bpy和PCN-224-Bpy(Ru)相比，PCN-224的光电流更高，这一现象也支持了中后者光生载流子的复合率较低这一结论。总而言之，在光催化CO₂还原过程中，锌卟啉(Ⅱ)配体既作为光敏单元，又作为CO₂还原活性位点，而联吡啶钌(Ⅱ)基元与锌(Ⅱ)卟啉基元的结合可以优化光催化剂的能带结构，进而促进光催化CO₂还原与H₂O氧化的耦合，从而实现了高效光催化CO₂还原全反应。

关键词: 金属有机框架, 锌(Ⅱ)卟啉衍生物, 联吡啶(Ⅱ)钌配合物, 光生电荷, 光催化CO₂还原

Abstract:

Efficiently converting CO₂ and H₂O into value-added chemicals using solar energy is a viable approach to address global warming and the energy crisis. However, achieving artificial photocatalytic CO₂ reduction using H₂O as the reductant poses challenges is due to the difficulty in efficient cooperation among multiple functional moieties. Metal-organic frameworks (MOFs) are promising candidates for overall CO₂ photoreduction due to their large surface area, diverse active sites, and excellent tailorability. In this study, we designed a metal-organic framework photocatalyst, named PCN-224(Zn)-Bpy(Ru), by integrating photoactive Zn(Ⅱ)-porphyrin and Ru(Ⅱ)-bipyridyl moieties. In comparison, two isostructural MOFs just with either Zn(Ⅱ)-porphyrin or Ru(Ⅱ)-bipyridyl moiety, namely PCN-224-Bpy(Ru) and PCN-224(Zn)-Bpy were also synthesized. As a result, PCN-224(Zn)-Bpy(Ru) exhibited the highest photocatalytic conversion rate of CO₂ to CO, with a production rate of 7.6 µmol·g⁻¹·h⁻¹ in a mixed solvent of CH₃CN and H₂O, without the need for co-catalysts, photosensitizers, or sacrificial agents. Mass spectrometer analysis detected the signals of ¹³CO (m/z = 29), ¹³C¹⁸O (m/z = 31), ¹⁶O¹⁸O (m/z = 34), and ¹⁸O₂ (m/z = 36), confirming that CO₂ and H₂O acted as the carbon and oxygen sources for CO and O₂, respectively, thereby confirming the coupling of photocatalytic CO₂ reduction with H₂O oxidation. In contrast, using PCN-224-Bpy(Ru) or PCN-224(Zn)-Bpy as catalysts under the same conditions resulted in significantly lower CO production rates of only 1.5 and 0 µmol·g⁻¹·h⁻¹, respectively. Mechanistic studies revealed that the lowest unoccupied molecular orbital (LUMO) potential of PCN-224(Zn)-Bpy(Ru) is more negative than the redox potentials of CO₂/CO, and the highest occupied molecular orbital (HOMO) potential is more positive than that of H₂O/O₂, satisfying the thermodynamic requirements for overall photocatalytic CO₂ reduction. In comparison, the HOMO potential of PCN-224(Zn)-Bpy without Ru(Ⅱ)-bipyridyl moieties is less positive than that of H₂O/O₂, indicating that the Ru(Ⅱ)-bipyridyl moiety is thermodynamically necessary for CO₂ reduction coupled with H₂O oxidation. Additionally, photoluminescence spectroscopy revealed that the fluorescence of PCN-224(Zn)-Bpy(Ru) was almost completely quenched, and a longer average photoluminescence lifetime compared to PCN-224(Zn)-Bpy and PCN-224-Bpy(Ru) was observed. These suggest a low recombination rate of photogenerated carriers in PCN-224(Zn)-Bpy(Ru), which also supported by the higher photocurrent observed in PCN-224(Zn)-Bpy(Ru) compared to PCN-224(Zn)-Bpy and PCN-224-Bpy(Ru). In summary, the integrated Zn(Ⅱ)-porphyrin and Ru(Ⅱ)-bipyridyl moieties in PCN-224(Zn)-Bpy(Ru) play important roles of a photosensitizer and CO₂ reduction as well as H₂O oxidation sites, and their efficient cooperation optimizes the band structure, thereby facilitating the coupling of CO₂ reduction with H₂O oxidation and resulting in high-performance artificial photocatalytic CO₂ reduction.

Key words: Metal-organic framework, Zn(Ⅱ) porphyrin, Ru(Ⅱ) bipyridyl complex, Photogenerated charge, CO₂ photoreduction

陈慧滢, 朱浩林, 廖培钦, 陈小明. 一例整合了三联吡啶钌和卟啉锌的金属-有机框架材料用于光催化二氧化碳还原全反应[J]. 物理化学学报, 2024, 40(4), 2306046. doi: 10.3866/PKU.WHXB202306046

Hui-Ying Chen, Hao-Lin Zhu, Pei-Qin Liao, Xiao-Ming Chen. Integration of Ru(Ⅱ)-Bipyridyl and Zinc(Ⅱ)-Porphyrin Moieties in a Metal-Organic Framework for Efficient Overall CO₂ Photoreduction[J]. Acta Phys. -Chim. Sin. 2024, 40(4), 2306046. doi: 10.3866/PKU.WHXB202306046

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB202306046

https://www.whxb.pku.edu.cn/CN/Y2024/V40/I4/2306046

图/表 4

参考文献 41

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一例整合了三联吡啶钌和卟啉锌的金属-有机框架材料用于光催化二氧化碳还原全反应

Integration of Ru(Ⅱ)-Bipyridyl and Zinc(Ⅱ)-Porphyrin Moieties in a Metal-Organic Framework for Efficient Overall CO₂ Photoreduction

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一例整合了三联吡啶钌和卟啉锌的金属-有机框架材料用于光催化二氧化碳还原全反应

Integration of Ru(Ⅱ)-Bipyridyl and Zinc(Ⅱ)-Porphyrin Moieties in a Metal-Organic Framework for Efficient Overall CO2 Photoreduction

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Integration of Ru(Ⅱ)-Bipyridyl and Zinc(Ⅱ)-Porphyrin Moieties in a Metal-Organic Framework for Efficient Overall CO₂ Photoreduction