六核环状钴配合物用于光催化CO2到CO转化

doi:10.1016/S1872-2067(22)64144-5

催化学报 ›› 2022, Vol. 43 ›› Issue (9): 2414-2424.DOI: 10.1016/S1872-2067(22)64144-5

六核环状钴配合物用于光催化CO₂到CO转化

孟翔宇^a^,^†, 李睿^a^,^†, 杨峻懿^a, 许世明^a, 张辰晨^a, 尤可嘉^a, 马宝春^a, 管红霞^c, 丁勇^a^,^b^,^*()

^a兰州大学化学化工学院, 甘肃省先进催化中心, 功能有机分子化学国家重点实验室, 甘肃兰州730000, 中国
^b中国科学院兰州化学物理研究所, 羰基合成与选择氧化国家重点实验室, 甘肃兰州730000, 中国
^c佐治亚昆内特学院科学技术系, 劳伦斯维尔30043, 美国

收稿日期:2022-04-15 接受日期:2022-06-19 出版日期:2022-09-18 发布日期:2022-07-20
通讯作者: 丁勇
作者简介:第一联系人：
†共同第一作者.
基金资助:
国家自然科学基金(22075119);甘肃省自然科学基金(21JR7RA440);中央高校基本科研业务费专项资金优秀研究生项目(lzujbky-2021-it13)

Hexanuclear ring cobalt complex for photochemical CO₂ to CO conversion

Xiangyu Meng^a^,^†, Rui Li^a^,^†, Junyi Yang^a, Shiming Xu^a, Chenchen Zhang^a, Kejia You^a, Baochun Ma^a, Hongxia Guan^c, Yong Ding^a^,^b^,^*()

^aState Key Laboratory of Applied Organic Chemistry, Key Laboratory of Advanced Catalysis of Gansu Province, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, Gansu, China
^bState Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, Gansu, China
^cSchool of Science and Technology, Georgia Gwinnett College, 1000 University Center Lane, Lawrenceville, GA 30043, USA

Received:2022-04-15 Accepted:2022-06-19 Online:2022-09-18 Published:2022-07-20
Contact: Yong Ding
About author:First author contact:
†Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22075119);Natural Science Foundation of Gansu Province(21JR7RA440);Fundamental Research Funds for Central Universities(lzujbky-2021-it13)

摘要/Abstract

摘要：

自然界中的光合作用被认为是非常重要的生化反应, 它不仅为植物生长提供能量, 为动物提供食物来源, 而且它还维持了大气中CO₂和O₂含量相对稳定. 每年自然界通过光合作用利用的太阳能约是人类生产生活所需能量的10倍. 目前, 人工光合作用越来越引起人们关注. 光合作用主要包括光反应放O₂和暗反应CO₂固定(Calvin循环), 涉及水氧化(6H₂O - 12 e^- → 12 H⁺ + 3 O₂)和CO₂还原反应(6CO₂ + 12H⁺ + 6H₂O + 12e^- → C₆H₁₂O₆ + 3O₂ + 6H₂O). 目前, 为了满足能源需求和减少温室效应, CO₂还原反应(CO₂RR)制备碳氢燃料成为前沿与热点研究方向. 在自然界光合作用中, CO₂RR为多电子、多质子(24e^-, 24H⁺)的转移过程, 目前的技术很难完全模拟自然界光合作用并将CO₂转化为碳水化合物. 因此, 开发光化学CO₂到CO的转化(CO₂ + 2H⁺ + 2e^- → CO + H₂O), 作为人工光合作用的模型用以深入理解光合作用是非常有必要的.

本文开发了均相环状钴配合物{K₂[CoO₃PCH₂N(CH₂CO₂)₂]}₆(Co6配合物)催化CO₂还原为CO的人工光合作用模型反应. 选择Co6配合物用于二氧化碳还原的原因如下:(1) Co6配合物作为水氧化光催化剂已被报道, 说明它对实现光合作用全反应具有更实际的应用; (2)在Co6配合物中, 有四个化学键与N原子相连接, 说明N原子表现出正电性; 从而可以吸附CO₂分子, 这有助于在光催化CO₂还原反应中增加反应物的局部浓度; (3)N原子与Co6配合物中的活性位点Co原子配位, N原子吸附的CO₂接近Co活性位点, 缩短了其传输路径, 使其易于被还原; (4)Co6配合物中含有多个活性位点, 催化过程中可能存在的协同催化作用使其具有较高的光催化CO₂RR活性. 以[Ru(bpy)₃]²⁺为光敏剂, TEOA为电子供体, Co6配合物最佳转化频率为503.3 h^‒1, 表观量子效率为0.81%. Co6配合物与[Ru(bpy)₃]²⁺之间有效的电子转移提高了光敏剂的光生载流子分离效率, 从而使该系统具有良好的光催化CO₂还原性能. j-V曲线、光辅助UV-vis曲线、稳态光致发光光谱和激光闪光光解实验证实了上述结论. 控制实验、水解稳定性实验、硫氰酸钾(KSCN)毒化实验以及对反应前后催化剂元素比例的测定结果表明, Co6配合物在光催化CO₂还原反应过程中具有良好的稳定性. 此外, 通过KSCN毒化实验、Pourbaix图和密度泛函理论计算, 进一步研究了Co6配合物光催化CO₂还原的反应机理. 综上, 基于对Co6配合物的研究发现, 开发在光催化过程中具有协同作用的多核分子催化剂用于CO₂还原, 是实现CO₂高效转化的策略之一.

关键词: 光合作用, 均相催化, CO₂还原反应, 密度泛函理论, 六核环状钴配合物

Abstract:

Photosynthesis in nature has been deemed as the most significant biochemical reaction, which maintains a relatively stable content of O₂ and CO₂ in the atmosphere. Herein, for a deeper comprehension of natural photosynthesis, an artificial photosynthesis model reaction of photochemical CO₂ to CO conversion (CO₂ +2 H⁺ + 2e^- → CO + H₂O) catalyzed by a homogeneous hexanuclear ring cobalt complex {K₂[CoO₃PCH₂N(CH₂CO₂)₂]}₆ (Co6 complex) is developed. Using the [Ru(bpy)₃]²⁺ as a photosensitizer and TEOA as a sacrificial electron donor, an optimal turnover frequency of 503.3 h^‒1 and an apparent quantum efficiency of 0.81% are obtained. The good photocatalytic CO₂ reduction performance is attributed to the efficient electron transfer between Co6 complex and [Ru(bpy)₃]²⁺, which boosts the photogenerated carriers separation of the photosensitizer. It is confirmed by the j-V curves, light-assisted UV-vis curves, steady-state photoluminescence spectra and real-time laser flash photolysis experiments. In addition, the proposed catalytic mechanism for CO₂ reduction reaction catalyzed by the Co6 complex is explored by the potassium thiocyanate poison experiment, Pourbaix diagram and density functional theory calculations.

Key words: Photosynthesis, Homogeneous catalysis, CO₂ reduction reaction, Density functional theory, Hexanuclear ring cobalt complex

孟翔宇, 李睿, 杨峻懿, 许世明, 张辰晨, 尤可嘉, 马宝春, 管红霞, 丁勇. 六核环状钴配合物用于光催化CO₂到CO转化[J]. 催化学报, 2022, 43(9): 2414-2424.

Xiangyu Meng, Rui Li, Junyi Yang, Shiming Xu, Chenchen Zhang, Kejia You, Baochun Ma, Hongxia Guan, Yong Ding. Hexanuclear ring cobalt complex for photochemical CO₂ to CO conversion[J]. Chinese Journal of Catalysis, 2022, 43(9): 2414-2424.

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图/表 8

Fig. 1. Ball and stick model of Co6 complex (K cations and H atoms were omitted for clarity).

Fig. 2. (a) Measured and simulated PXRD patterns. (b-d) XPS survey, high resolution Co 2p and C 1s XPS spectra of Co6 complex.

Fig. 3. (a) Single variable control experiments of CO2RR. (b) Different concentrations of Co6 complex for CO2RR. (c) TOFs for Co6 complex with different concentrations. (d-f) Kinetic curves for gas evolution amount, TONs and CO selectivity over 20 µmol L?1 Co6 complex.

Fig. 4. Proposed photocatalytic CO2RR general mechanism.

Fig. 5. (a,b) Pourbaix diagram of Co6 complex under reduction state and oxidation state. (c) LSV curve of [Ru(bpy)3]2+. (d) Electrode potential comparison.

Fig. 6. Calculated free energy diagram for CO evolution over the single Co site (a,b) and double Co sites (c,d) in the Co6 complex.

Fig. 7. Possible mechanism of Co6 complex for photocatalytic CO2RR.

Fig. 8. (a,b) j-V curves and result. Steady state PL spectra (c) and light assisted UV-vis curves (d) of samples.

参考文献

[1]	M. Johnson, Essays Biochem., 2016, 60, 255-273.
[2]	L. Chen, G. Chen, C. Leung, C. Cometto, M. Robert, T. Lau, Chem. Soc. Rev., 2020, 49, 7271-7283.
[3]	S. Montzka1, E. Dlugokencky, J. Butler, Nature, 2011, 476, 43-50.
[4]	T. Zhang, W. Lin, Chem. Soc. Rev., 2014, 43, 5982-5993.
[5]	E. Romero, V. Novoderezhkin, R. van Grondelle, Nature, 2017, 543, 355-365.
[6]	J. Liu, J. Mantell, M. R. Jones, ACS Nano, 2020, 14, 4536-4549.
[7]	S. Wang, X. Han, Y. Zhang, N. Tian, T. Ma, H. Huang, Small Struct, 2021, 2, 2000061.
[8]	W. Kim, B. McClure, E. Edri, H. Frei, Chem. Soc. Rev., 2016, 45, 3321-3243.
[9]	W. Sun, X. Meng, C. Xu, J. Yang, X. Liang, Y. Dong, C. Dong, Y. Ding, Chin. J. Catal., 2020, 41, 1826-1836.
[10]	Y. Zhao, G. Chen, T. Bian, C. Zhou, G. Waterhouse, L. Wu, C. Tung, L. Smith, D. O’Hare, T. Zhang, Adv. Mater., 2015, 27, 7824-7831.
[11]	H. Rao, L. Schmidt, J. Bonin, M. Robert, Nature, 2017, 548, 74-77.
[12]	J. Low, L. Zhang, T. Tong, B. Shen, J. Yu, J. Catal., 2018, 361, 255-266.
[13]	K. Lu, Y. Li, F. Zhang, M. Qi, X. Chen, Z. Tang, Y. Yamada, M. Anpo, M. Conte, Y. Xu, Nat. Commun., 2020, 11, 5181.
[14]	X. Li, Y. Sun, J. Xu, Y. Shao, J. Wu, X. Xu, Y. Pan, H. Ju, J. Zhu, Y. Xie, Nat. Energy, 2019, 4, 690-699.
[15]	X. Xiong, Y. Zhao, R. Shi, W. Yin, Y. Zhao, G. Waterhouse, T. Zhang, Sci. Bull., 2020, 65, 987-994.
[16]	H. Wu, Y. Li, M. Qi, Q. Lin, Y. Xu, Appl. Catal. B, 2020, 278, 119267.
[17]	K. Zhao, S. Zhao, C. Gao, J. Qi, H. Yin, D. Wei, M. Mideksa, X. Wang, Y. Gao, Z. Tang, R. Yu, Small, 2018, 14, 1800762.
[18]	J. Ren, Y. Zheng, K. Yuan, L. Zhou, K. Wu, Y. Zhang, Nanoscale, 2020, 12, 755-762.
[19]	C. Gao, Q. Meng, K. Zhao, H. Yin, D. Wang, J. Guo, S. Zhao, L. Chang, M. He, Q. Li, H. Zhao, X. Huang, Y. Gao, Z. Tang, Adv. Mater., 2016, 28, 6485-6490.
[20]	Y. Wang, S. Wang, S. Zhang, X. Lou, Angew. Chem. Int. Ed., 2020, 59, 11918-11922.
[21]	Y. Wang, S. Wang, X. W. Lou, Angew. Chem. Int. Ed., 2019, 58, 17236-17240.
[22]	L. Shi, P. Wang, Q. Wang, X. Ren, F. Ichihara, W. Zhou, H. Zhang, Y. Izumi, B. Cao, S. Wang, H. Chen, J. Ye, J. Mater. Chem. A, 2020, 8, 21833-21841.
[23]	J. Nai, S. Wang, X. W. Lou, Sci. Adv., 2019, 5, eaax5095.
[24]	T. Ouyang, H. Huang, J. Wang, D. Zhong, T. Lu, Angew. Chem. Int. Ed., 2017, 56, 738-743.
[25]	T. Ouyang, H. Wang, H. Huang, J. Wang, S. Guo, W. Liu, D. Zhong, T. Lu, Angew. Chem. Int. Ed., 2018, 57, 16480-16485.
[26]	J. Xu, Z. Wang, W. Yu, D. Sun, Q. Zhang, C. Tung, W. Wang, ChemSusChem, 2016, 9, 1146-1152.
[27]	J. Xu, L. Guo, H. Su, X. Gao, X. Wu, W. Wang, C. Tung, D. Sun, Inorg. Chem., 2017, 56, 1591-1598.
[28]	X. Zou, Y. Wu, Y. Liu, D. Liu, W. Li, L. Gu, H. Liu, P. Wang, L. Sun, Y. Zhang, Chem, 2018, 4, 1139-1152.
[29]	B. Qin, Y. Li, Q. Zhang, G. Yang, H. Liang, F. Peng, Nano Energy, 2020, 68, 104374
[30]	C. Zhang, C. D. Chen, H. J. Shen, H. Dau, J. Zhao, Science, 2015, 348, 690-693.
[31]	J. Lin, X. Meng, M. Zheng, B. Ma, Y. Ding, Appl. Catal. B, 2019, 241, 351-358
[32]	Y. Dong, R. Nie, J. Wang, X. Yu, P. Tu, J. Chen, H. Jing, Chin. J. Catal., 2019, 40, 1222-1230.
[33]	X. Meng, Y. Dong, Q. Hu, Y. Ding, ACS Sustain. Chem. Eng., 2019, 7, 1753-1759.
[34]	S. Wang, Y. Hou, X. Wang, ACS Appl. Mater. Interfaces, 2015, 7, 4327-4335.
[35]	D. Liu, H. Wang, T. Ouyang, J. Wang, L. Jiang, D. Zhong, T. Lu, ACS Appl. Energy Mater., 2018, 1, 2452-2459.
[36]	L. Zhang, S. Li, H. Liu, Y. Cheng, X. Wei, X. Chai, G. Yuan, Inorg. Chem., 2020, 59, 17464-17472.
[37]	A. Call, M. Cibian, K. Yamamoto, T. Nakazono, K. Yamauchi, K. Sakai, ACS Catal., 2019, 9, 4867-4874.
[38]	M. F. Kuehnel, C. D. Sahm, G. Neri, J. R. Lee, K. L. Orchard, A. J. Cowan, E. Reisner, Chem. Sci., 2018, 9, 2501-2509.
[39]	D. Liu, H. Huang, J. Wang, L. Jiang, D. Zhong, T. Lu, ChemCatChem, 2018, 10, 3435-3440.
[40]	Z. Pan, P. Niu, M. Liu, G. Zhang, Z. Zhu, X. Wang, ChemSusChem, 2020, 13, 888-892.
[41]	M. Sun, C. Wang, C. Sun, M. Zhang, X. Wang, Z. Su, J. Catal., 2020, 385, 70-75.
[42]	B. Ma, M. Blanco, L. Calvillo, L. Chen, G. Chen, T. Lau, G. Drazic, J. Bonin, M. Robert, G. Granozzi, J. Am. Chem. Soc., 2021, 143, 8414-8425.
[43]	B. Ma, G. Chen, C. Fave, L. Chen, R. Kuriki, K. Maeda, O. Ishitani, T. Lau, J. Bonin, M. Robert, J. Am. Chem. Soc., 2020, 142, 6188-6195
[44]	Z. Guo, S. Cheng, C. Cometto, E. Mallart, S. Ng, C. Ko, G. Liu, L. Chen, M. Robert, T. Lau, J. Am. Chem. Soc., 2016, 138, 9413-9416.
[45]	M. Zheng, X. Cao, Y. Ding, T. Tian, J. Lin, J. Catal., 2018, 363, 109-116
[46]	J. Lin, B. Ma, M. Chen, Y. Ding, Chin. J. Catal., 2018, 39, 463-471.
[47]	J. Lin, X. Liang, X. Cao, N. Wei, Y. Ding, Chem. Commun., 2018, 54, 12515-12518.
[48]	Y. Meng, J. Yang, C. Zhang, Y. Fu, K. Li, M. Sun, X. Wang, C. Dong, B. Ma, Y. Ding, ACS Catal., 2022, 12, 89-100.
[49]	J. Lin, P. Kang, X. Liang, B. Ma, Y. Ding, Electrochim. Acta, 2017 258, 353-359.
[50]	Z. Wang, J. Yang, J. Cao, W. Chen, G. Wang, F. Liao, X. Zhou, F. Zhou, R. Li, Z. Yu, G. Zhang, X. Duan, Y. Wu, ACS Nano, 2020, 14, 6164-6172.
[51]	J. Yin, Q. Fan, Y. Li, F. Cheng, P. Zhou, P. Xi, S. Sun, J. Am. Chem. Soc., 2016, 138, 14546-14549.
[52]	P. Yang, R. Wang, H. Zhuzhang, M.-M. Titirici, X. Wang, ACS Catal., 2020, 10, 12706-12715.
[53]	X. Meng, J. Yang, S. Xu, C. Zhang, B. Ma, Y. Ding, Chem. Eng. J., 2021, 410, 128339.
[54]	X. Meng, C. Zhang, C. Dong, W. Sun, D. Ji, Y. Ding, Chem. Eng. J., 2020, 389, 124432.

六核环状钴配合物用于光催化CO₂到CO转化

Hexanuclear ring cobalt complex for photochemical CO₂ to CO conversion

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