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

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

Abstract

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

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.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64433-X

https://www.cjcatal.com/EN/Y2023/V49/I6/160

Figures/Tables 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.

References

[1]	E. A. Reyes Cruz, D. Nishiori, B. L. Wadsworth, N. P. Nguyen, L. K. Hensleigh, D. Khusnutdinova, A. M. Beiler, G. F. Moore, Chem. Rev., 2022, 122, 16051-16109.
[2]	W. Sun, J. Zhu, M. Zhang, X. Meng, M. Chen, Y. Feng, X. Chen, Y. Ding, Chin. J. Catal., 2022, 43, 2273-2300.
[3]	J.-W. Wang, L.-Z. Qiao, H.-D. Nie, H.-H. Huang, Y. Li, S. Yao, M. Liu, Z.-M. Zhang, Z.-H. Kang, T.-B. Lu, Nat. Commun., 2021, 12, 813.
[4]	D.-C. Liu, D.-C. Zhong, T.-B. Lu, EnergyChem, 2020, 2, 100034.
[5]	I. Bhugun, D. Lexa, J.-M. Saveant, J. Am. Chem. Soc., 1996, 118, 1769-1776.
[6]	E. Boutin, M. Robert, Trends Chem., 2021, 3, 359-372.
[7]	N. W. Kinzel, C. Werle, W. Leitner, Angew. Chem. Int. Ed., 2021, 60, 11628-11686.
[8]	J. W. Wang, H. H. Huang, P. Wang, G. Yang, S. Kupfer, Y. Huang, Z. Li, Z. Ke, G. Ouyang, JACS Au, 2022, 2, 1359-1374.
[9]	H. Takeda, C. Cometto, O. Ishitani, M. Robert, ACS Catal., 2016, 7, 70-88.
[10]	X. Meng, R. Li, J. Yang, S. Xu, C. Zhang, K. You, B. Ma, H. Guan, Y. Ding, Chin. J. Catal., 2022, 43, 2414-2424.
[11]	J. W. Wang, F. Ma, T. Jin, P. He, Z. M. Luo, S. Kupfer, M. Karnahl, F. Zhao, Z. Xu, T. Jin, T. Lian, Y. L. Huang, L. Jiang, L. Z. Fu, G. Ouyang, X. Y. Yi, J. Am. Chem. Soc., 2023, 145, 676-688.
[12]	X. Zhang, Y. Wang, M. Gu, M. Wang, Z. Zhang, W. Pan, Z. Jiang, H. Zheng, M. Lucero, H. Wang, G. E. Sterbinsky, Q. Ma, Y.-G. Wang, Z. Feng, J. Li, H. Dai, Y. Liang, Nat. Energy, 2020, 5, 684-692.
[13]	J. W. Wang, L. Jiang, H. H. Huang, Z. Han, G. Ouyang, Nat. Commun., 2021, 12, 4276.
[14]	J. W. Wang, H. H. Huang, J. K. Sun, T. Ouyang, D. C. Zhong, T. B. Lu, ChemSusChem, 2018, 11, 1025-1031.
[15]	J.-W. Wang, M. Gil-Sepulcre, H.-H. Huang, E. Solano, Y.-F. Mu, A. Llobet, G. Ouyang, Cell Rep. Phys. Sci., 2021, 2, 100681.
[16]	Y. Huang, H. Dai, D. Moonshiram, Z. Li, Z.-M. Luo, J.-H. Zhang, W. Yang, Y. Shen, J.-W. Wang, G. Ouyang, J. Mater. Chem. A, 2023, 11, 2969-2978.
[17]	M. H. Ronne, D. Cho, M. R. Madsen, J. B. Jakobsen, S. Eom, E. Escoude, H. C. D. Hammershoj, D. U. Nielsen, S. U. Pedersen, M. H. Baik, T. Skrydstrup, K. Daasbjerg, J. Am. Chem. Soc., 2020, 142, 4265-4275.
[18]	S. S. Roy, K. Talukdar, J. W. Jurss, ChemSusChem, 2021, 14, 662-670.
[19]	D. J. Martin, J. M. Mayer, J. Am. Chem. Soc., 2021, 143, 11423-11434.
[20]	I. Azcarate, C. Costentin, M. Robert, J. M. Saveant, J. Am. Chem. Soc., 2016, 138, 16639-16644.
[21]	W. Choi, D. H. Won, Y. J. Hwang, J. Mater. Chem. A, 2020, 8, 15341-15357.
[22]	K. Elouarzaki, V. Kannan, V. Jose, H. S. Sabharwal, J.-M. Lee, Adv. Energy Mater., 2019, 9, 1900090.
[23]	Z. Yue, C. Ou, N. Ding, L. Tao, J. Zhao, J. Chen, ChemCatChem, 2020, 12, 6103-6130.
[24]	Z. Jiang, Y. Wang, X. Zhang, H. Zheng, X. Wang, Y. Liang, Nano Res., 2019, 12, 2330-2334.
[25]	Z. Zhang, J. Xiao, X.-J. Chen, S. Yu, L. Yu, R. Si, Y. Wang, S. Wang, X. Meng, Y. Wang, Z.-Q. Tian, D. Deng, Angew. Chem. Int. Ed., 2018, 57, 16339-16342.
[26]	N. Han, Y. Wang, L. Ma, J. Wen, J. Li, H. Zheng, K. Nie, X. Wang, F. Zhao, Y. Li, J. Fan, J. Zhong, T. Wu, D. J. Miller, J. Lu, S.-T. Lee, Y. Li,, Chem, 2017, 3, 652-664.
[27]	M. Wang, K. Torbensen, D. Salvatore, S. Ren, D. Joulie, F. Dumoulin, D. Mendoza, B. Lassalle-Kaiser, U. Isci, C. P. Berlinguette, M. Robert, Nat. Commun., 2019, 10, 3602.
[28]	J. Su, J.-J. Zhang, J. Chen, Y. Song, L. Huang, M. Zhu, B. I. Yakobson, B. Z. Tang, R. Ye, Energy Environ. Sci., 2021, 14, 483-492.
[29]	A. Kumar, P. K. Prajapati, M. S. Aathira, A. Bansiwal, R. Boukherroub, S. L. Jain, J. Colloid Interface Sci., 2019, 543, 201-213.
[30]	S.-P. Luo, E. Mejia, A. Friedrich, A. Pazidis, H. Junge, A.-E. Surkus, R. Jackstell, S. Denurra, S. Gladiali, S. Lochbrunner, M. Beller, Angew. Chem. Int. Ed., 2013, 52, 419-423.
[31]	Z. Bao, A. J. Lovinger, J. Brown, J. Am. Chem. Soc., 1998, 120, 207-208.
[32]	H. H. Huang, J. H. Zhang, M. Dai, L. Liu, Z. Ye, J. Liu, D. C. Zhong, J. W. Wang, C. Zhao, Z. Ke, Proc. Natl. Acad. Sci. USA, 2022, 119, e2119267119.
[33]	J.-W. Wang, Z. Li, Z.-M. Luo, Y. Huang, F. Ma, S. Kupfer, G. Ouyang, Proc. Natl. Acad. Sci. U. S. A., 2023, 120, e2221219120.
[34]	H. Takeda, H. Kamiyama, K. Okamoto, M. Irimajiri, T. Mizutani, K. Koike, A. Sekine, O. Ishitani, J. Am. Chem. Soc., 2018, 140, 17241-17254.
[35]	J.-W. Wang, H.-H. Huang, J.-K. Sun, D.-C. Zhong, T.-B. Lu, ACS Catal., 2018, 8, 7612-7620.
[36]	J. D. Froehlich, C. P. Kubiak, J. Am. Chem. Soc., 2015, 137, 3565-3573.
[37]	X. Zhang, M. Cibian, A. Call, K. Yamauchi, K. Sakai, ACS Catal., 2019, 9, 11263-11273.
[38]	C. Steinlechner, A. F. Roesel, E. Oberem, A. Päpcke, N. Rockstroh, F. Gloaguen, S. Lochbrunner, R. Ludwig, A. Spannenberg, H. Junge, R. Francke, M. Beller, ACS Catal., 2019, 9, 2091-2100.

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

RichHTML

PDF (PC)

Knowledge

Supporting Information

Abstract

Cite this article

share this article

share this article

Figures/Tables 5

References

Related Articles 15

Recommended Articles

Metrics

[1]	Mingming Song, Xianghai Song, Xin Liu, Weiqiang Zhou, Pengwei Huo. Enhancing photocatalytic CO₂ reduction activity of ZnIn₂S₄/MOF-808 microsphere with S-scheme heterojunction by in situ synthesis method [J]. Chinese Journal of Catalysis, 2023, 51(8): 180-192.
[2]	Houwei He, Zhongliao Wang, Kai Dai, Suwen Li, Jinfeng Zhang. LSPR-enhanced carbon-coated In₂O₃/W₁₈O₄₉ S-scheme heterojunction for efficient CO₂ photoreduction [J]. Chinese Journal of Catalysis, 2023, 48(5): 267-278.
[3]	Chengcheng Chen, Fangting Liu, Qiaoyu Zhang, Zhengguo Zhang, Qiong Liu, Xiaoming Fang. Theoretical design and experimental study of pyridine-incorporated polymeric carbon nitride with an optimal structure for boosting photocatalytic CO₂ reduction [J]. Chinese Journal of Catalysis, 2023, 46(3): 91-102.
[4]	Lijing Wang, Tianyi Yang, Bo Feng, Xiangyu Xu, Yuying Shen, Zihan Li, Arramel , Jizhou Jiang. Constructing dual electron transfer channels to accelerate CO₂ photoreduction guided by machine learning and first-principles calculation [J]. Chinese Journal of Catalysis, 2023, 54(11): 265-277.
[5]	Ruiyu Zhong, Yujie Liang, Fei Huang, Shinuo Liang, Shengwei Liu. Regulating interfacial coupling of 1D crystalline g-C₃N₄ nanorods with 2D Ti₃C₂T_x MXene for boosting photocatalytic CO₂ reduction [J]. Chinese Journal of Catalysis, 2023, 53(10): 109-122.
[6]	Ke Wang, Miao Cheng, Nan Wang, Qianyi Zhang, Yi Liu, Junwei Liang, Jie Guan, Maochang Liu, Jiancheng Zhou, Naixu Li. Inter-plane 2D/2D ultrathin La₂Ti₂O₇/Ti₃C₂ MXene Schottky heterojunctions toward high-efficiency photocatalytic CO₂ reduction [J]. Chinese Journal of Catalysis, 2023, 44(1): 146-159.
[7]	Lei Cheng, Peng Zhang, Qiye Wen, Jiajie Fan, Quanjun Xiang. Copper and platinum dual-single-atoms supported on crystalline graphitic carbon nitride for enhanced photocatalytic CO₂ reduction [J]. Chinese Journal of Catalysis, 2022, 43(2): 451-460.
[8]	Pan Zeng, Cheng Yuan, Genlin Liu, Jiechang Gao, Yanguang Li, Liang Zhang. Recent progress in electronic modulation of electrocatalysts for high-efficient polysulfide conversion of Li-S batteries [J]. Chinese Journal of Catalysis, 2022, 43(12): 2946-2965.
[9]	Yue Huang, Kai Dai, Jinfeng Zhang, Graham Dawson. Photocatalytic CO₂ conversion of W₁₈O₄₉/CdSe-Diethylenetriamine with high charge transfer efficiency: Synergistic effect of LSPR effect and S-scheme heterojunction [J]. Chinese Journal of Catalysis, 2022, 43(10): 2539-2547.
[10]	Jiaqi Wang, Hao Cheng, Dingqiong Wei, Zhaohui Li. Ultrasonic-assisted fabrication of Cs₂AgBiBr₆/Bi₂WO₆ S-scheme heterojunction for photocatalytic CO₂ reduction under visible light [J]. Chinese Journal of Catalysis, 2022, 43(10): 2606-2614.
[11]	Xiaoxue Zhao, Mengyang Xu, Xianghai Song, Weiqiang Zhou, Xin Liu, Pengwei Huo. 3D Fe-MOF embedded into 2D thin layer carbon nitride to construct 3D/2D S-scheme heterojunction for enhanced photoreduction of CO₂ [J]. Chinese Journal of Catalysis, 2022, 43(10): 2625-2636.
[12]	Zhichao Lin, Zhan Jiang, Yubo Yuan, Huan Li, Hongxuan Wang, Yirong Tang, Chunchen Liu, Yongye Liang. Cobalt-N₄ macrocyclic complexes for heterogeneous electrocatalysis of the CO₂ reduction reaction [J]. Chinese Journal of Catalysis, 2022, 43(1): 104-109.
[13]	Fang Li, Xiaoyang Yue, Haiping Zhou, Jiajie Fan, Quanjun Xiang. Construction of efficient active sites through cyano-modified graphitic carbon nitride for photocatalytic CO₂ reduction [J]. Chinese Journal of Catalysis, 2021, 42(9): 1608-1616.
[14]	Libo Wang, Bicheng Zhu, Bei Cheng, Jianjun Zhang, Liuyang Zhang, Jiaguo Yu. In-situ preparation of TiO₂/N-doped graphene hollow sphere photocatalyst with enhanced photocatalytic CO₂ reduction performance [J]. Chinese Journal of Catalysis, 2021, 42(10): 1648-1658.
[15]	Qinghe Zhang, Yang Xia, Shaowen Cao. “Environmental phosphorylation” boosting photocatalytic CO₂ reduction over polymeric carbon nitride grown on carbon paper at air-liquid-solid joint interfaces [J]. Chinese Journal of Catalysis, 2021, 42(10): 1667-1676.