Bipolar photocatalysis for CO generation via biopolyol oxidation and CO2 reduction over brown polymeric carbon nitride nanowires

doi:10.1016/S1872-2067(25)64928-X

Abstract

Abstract:

Harnessing a single system capable of both oxidizing biopolyols and reducing carbon dioxide (CO₂) into carbon monoxide (CO) provides a sustainable pathway for simultaneous biomass conversion and CO₂ reduction. Traditional systems, however, are often limited by sluggish kinetics, requiring UV light or strongly alkaline media, which hampers their applicability under mild, visible-light conditions. In this study, we report an alkali- and metal-free photocatalytic CO production system operating at ambient temperature, employing brown polymeric carbon nitride nanowires (CNW) as the sole photocatalyst. The extended light-harvesting capacity of CNW enables efficient activity even under long-wavelength irradiation beyond 700 nm. The reaction pathways for biopolyol oxidative decarbonylation and CO₂-to-CO reduction were elucidated through a combination of in-situ spectroscopy and theoretical calculations. This visible-light-responsive dual-reaction platform directs photogenerated holes toward biopolyol oxidation and electrons toward CO₂ reduction, achieving efficient CO generation from renewable resources under mild conditions.

Key words: Bipolar CO production system, Biopolyols oxidation, Photocatalytic CO₂ reduction, Brown polymeric carbon nitride nanowire

Yanglin Chen, Ruiming Fang, Huibo Zhao, Minjun Feng, Weidong Hou, Tze Chien Sum, Wen Liu, Liang Wang, Lydia Helena Wong, Can Xue. Bipolar photocatalysis for CO generation via biopolyol oxidation and CO₂ reduction over brown polymeric carbon nitride nanowires[J]. Chinese Journal of Catalysis, 2026, 84: 214-225.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64928-X

https://www.cjcatal.com/EN/Y2026/V84/I5/214

Figures/Tables 7

Scheme 1. Producing CO from biomass pathways. (a) Traditional thermal gasification. Previous reported photocatalytic CO production system (b) and this bipolar photocatalytic CO production system (c).

Fig. 1. The conception of bipolar CO production system and basic characterization of photocatalysts. (a) Schematic illustration of photocatalytic bipolar CO production system via integrating oxidative decarbonylation of biopolyols with CO2 reduction. (b) SEM image of CNW. (c) TEM image of CNW. (d) EDS elemental mapping images of CNW. (e) High-resolution XPS spectra of C 1s of CN and CNW. (f) High-resolution XPS spectra of O 1s of CN and CNW. (g) solid-state 13C MAS NMR spectra of CN and CNW.

Fig. 2. Characterization of the photo-electro properties of photocatalysts. (a) UV-vis-NIR DRS spectra of CN and CNW, the insets show the digital pictures of CN and CNW. (b) Band structures of CN and CNW. (c) TR-PL decay plots of CN and CNW. (d) fs-TA spectra for CNW. (e) The corresponding decay kinetic at 550 nm for CNW. (f) Schematic representation of proposed exciton dissociation model in CNW. (g) Transient photocurrent response of CN and CNW under full spectrum irradiation. (h) Transient open-circuit potential decay curves of CN and CNW under full spectrum irradiation. (i) Transient photocurrent response under light with λ > 700 nm irradiation.

Fig. 3. Photocatalytic Performance. (a) Photocatalytic activity of CN and CNW under light irradiation using glycerol as a model biopolyol in a CO2-saturated environment. (b) The average generation rate of photocatalytic products under multiple experiments of control conditions by using CNW. (c) The mass spectra of CO peak driven from CNW under full spectrum irradiation using 13CO2 as CO2 source. (d) Comparing the photocatalytic performance of CNW with the presentative polymeric carbon nitride-based photocatalysts reported in the literature [10,42-50]. (e) The average generation rate of photocatalytic production driven from CNW with CO2. (f) The average generation rate of photocatalytic production driven from CNW with Ar.

Fig. 4. Photocatalytic CO2 reduction mechanism investigation. (a) Charge difference density distribution of CN and CNW with the adsorption of CO2 molecule. (The yellow and cyan isosurfaces represent electron accumulation and depletion with 0.002 e ??3, respectively). (b,c) In-situ DRIFTS spectra of CN under full spectrum irradiation for different durations at 298 K. (d,e) In-situ DRIFTS spectra of CNW under full spectrum irradiation for different durations at 298 K. (f) Gibbs free energy diagrams of photocatalytic CO2 reduction pathways on CN and CNW.

Fig. 5. Photocatalytic oxidative decarbonylation of biopolyols mechanism investigation. (a) HPLC data for the photocatalytic oxidative decarbonylation of glycerol over CNW under Ar atmosphere condition. (b) Photocatalytic activity of oxidative decarbonylation of glycerol, glyceraldehyde, propanol and propanal over CNW under Ar atmosphere condition. (c) GC data for liquid production of the photocatalytic oxidative decarbonylation of propanal with TEMPO under Ar atmosphere condition. (d) The mass spectrum of TEMPO-propanal adduct. (e) The proposed pathway for the photocatalytic oxidative decarbonylation of propanol and glycerol.

Scheme 2. Illustration of photocatalytic bipolar CO production system mechanism. Photocatalytic mechanism of the bipolar CO production system by integrating of photocatalytic CO2 reduction with oxidative decarbonylation reactions.

References

[1]	F. Jiao, J. Li, X. Pan, J. Xiao, H. Li, H. Ma, M. Wei, Y. Pan, Z. Zhou, M. Li, S. Miao, J. Li, Y. Zhu, D. Xiao, T. He, J. Yang, F. Qi, Q. Fu, X. Bao, Science, 2016, 351, 1065-1068.
[2]	Y. Li, B. Liu, D. Yuan, H. Wang, Q. Wu, Y. Wang, J. Wang, X. San, Y. Luo, J. Ye, Nat. Catal., 2024, 7, 1350-1358.
[3]	M. L. Valderrama Rios, A. M. González, E. E. S. Lora, O. A. Almazán del Olmo, Biomass Bioenergy, 2018, 108, 345-370.
[4]	G. W. Huber, S. Iborra, A. Corma, Chem. Rev., 2006, 106, 4044-4098.
[5]	H. Zhou, M. Wang, F. Kong, Z. Chen, Z. Dou, F. Wang, J. Am. Chem. Soc., 2022, 144, 21224-21231.
[6]	X.-Y. Yu, J.-R. Chen, W.-J. Xiao, Chem. Rev., 2021, 121, 506-561.
[7]	Z. Liu, J. Ma, M. Hong, R. Sun, ACS Catal., 2023, 13, 2106-2117.
[8]	M. Wang, M. Liu, J. Lu, F. Wang, Nat. Commun., 2020, 11, 1083.
[9]	Z. Zhang, M. Wang, H. Zhou, F. Wang, J. Am. Chem. Soc., 2021, 143, 6533-6541.
[10]	Y. Wei, L. Chen, H. Chen, L. Cai, G. Tan, Y. Qiu, Q. Xiang, G. Chen, T.-C. Lau, M. Robert, Angew. Chem. Int. Ed., 2022, 61, e202116832.
[11]	G. Liao, Y. Gong, L. Zhang, H. Gao, G.-J. Yang, B. Fang, Energy Environ. Sci., 2019, 12, 2080-2147.
[12]	Y. Wang, H. Wang, S. Wang, Y. Fang, Angew. Chem. Int. Ed., 2024, 63, e202413768.
[13]	Z.-K. Xie, Y.-J. Jia, Y.-Y. Huang, D.-B. Xu, X.-J. Wu, M. Chen, W.-D. Shi, ACS Catal., 2023, 13, 13768-13776.
[14]	Y. Xu, M. Fan, W. Yang, Y. Xiao, L. Zeng, X. Wu, Q. Xu, C. Su, Q. He, Adv. Mater., 2021, 33, 2101455.
[15]	Q. Gu, Z. Gao, C. Xue, Small, 2016, 12, 3543-3549.
[16]	Y. Chen, M. Zheng, J. Sun, J. Xu, C. Wu, J. Liu, L. He, S. Xi, S. Li, C. Xue, ACS Catal., 2024, 14, 17321-17330.
[17]	H. Wang, S. Jiang, S. Chen, D. Li, X. Zhang, W. Shao, X. Sun, J. Xie, Z. Zhao, Q. Zhang, Y. Tian, Y. Xie, Adv. Mater., 2016, 28, 6940-6945.
[18]	Y. Li, X. Zhang, W. Hou, Z. Zhou, S. Zhang, H. Guo, J. Zhang, J. Xu, L. Wang, Appl. Catal. B, 2026, 380, 125758.
[19]	H. Ou, S. Ning, P. Zhu, S. Chen, A. Han, Q. Kang, Z. Hu, J. Ye, D. Wang, Y. Li, Angew. Chem. Int. Ed., 2022, 61, e202206579.
[20]	P. Qiu, C. Xu, H. Chen, F. Jiang, X. Wang, R. Lu, X. Zhang, Appl. Catal. B, 2017, 206, 319-327.
[21]	X. Li, I. V. Sergeyev, F. Aussenac, A. F. Masters, T. Maschmeyer, J. M. Hook, Angew. Chem. Int. Ed., 2018, 57, 6848-6852.
[22]	Z. Wei, M. Liu, Z. Zhang, W. Yao, H. Tan, Y. Zhu, Energy Environ. Sci., 2018, 11, 2581-2589.
[23]	Y. Chen, Y. Qu, P. Xu, X. Zhou, J. Sun, J. Colloid Interface Sci., 2021, 601, 326-337.
[24]	Y. Gao, Y. Zhu, L. Lyu, Q. Zeng, X. Xing, C. Hu, Environ. Sci. Technol., 2018, 52, 14371-14380.
[25]	H. Guo, L. Zhou, K. Huang, Y. Li, W. Hou, H. Liao, C. Lian, S. Yang, D. Wu, Z. Lei, Z. Liu, L. Wang, Adv. Funct. Mater., 2024, 34, 2402650.
[26]	Y. Wang, R. Godin, J. R. Durrant, J. Tang, Angew. Chem. Int. Ed., 2021, 60, 20811-20816.
[27]	D. Zhao, Y. Wang, C.-L. Dong, Y.-C. Huang, J. Chen, F. Xue, S. Shen, L. Guo, Nat. Energy, 2021, 6, 388-397.
[28]	H. Guo, Y. Lu, Z. Lei, H. Bao, M. Zhang, Z. Wang, C. Guan, B. Tang, Z. Liu, L. Wang, Nat. Commun., 2024, 15, 4843.
[29]	Y. Chen, X. Liu, L. Hou, X. Guo, R. Fu, J. Sun, Chem. Eng. J., 2020, 383, 123132.
[30]	B. Zhai, H. Li, G. Gao, Y. Wang, P. Niu, S. Wang, L. Li, Adv. Funct. Mater., 2022, 32, 2207375.
[31]	Y. Chen, L. He, H.-R. Tan, X. Lin, S. Jaenicke, G.-K., Chuah, J. Mater. Chem. A, 2023, 11, 12342-12353.
[32]	P. Xia, S. Cao, B. Zhu, M. Liu, M. Shi, J. Yu, Y. Zhang, Angew. Chem. Int. Ed., 2020, 59, 5218-5225.
[33]	G. Zhou, C. Bi, X. Qian, Y. Chen, H. Liu, X. Ning, C. Xue, P. Ding, X. Wang, X. Zhu, ACS Catal., 2025, 15, 15972-15981.
[34]	P. Liu, Z. Huang, X. Gao, X. Hong, J. Zhu, G. Wang, Y. Wu, J. Zeng, X. Zheng, Adv. Mater., 2022, 34, 2200057.
[35]	S. Wang, T. He, P. Chen, A. Du, K. K. Ostrikov, W. Huang, L. Wang, Adv. Mater., 2020, 32, 2001385.
[36]	Y. Guo, J. Li, Y. Yuan, L. Li, M. Zhang, C. Zhou, Z. Lin, Angew. Chem. Int. Ed., 2016, 55, 14693-14697.
[37]	Q. Ruan, T. Miao, H. Wang, J. Tang, J. Am. Chem. Soc., 2020, 142, 2795-2802.
[38]	W. Li, Z. Wei, K. Zhu, W. Wei, J. Yang, J. Jing, D. L. Phillips, Y. Zhu, Appl. Catal. B, 2022, 306, 121142.
[39]	M. Qian, X.-L. Wu, M. Lu, L. Huang, W. Li, H. Lin, J. Chen, S. Wang, X. Duan, Adv. Funct. Mater., 2023, 33, 2208688.
[40]	Z. Jiang, W. Wan, H. Li, S. Yuan, H. Zhao, P. K. Wong, Adv. Mater., 2018, 30, 1706108.
[41]	Y. Li, Y. Guo, D. Luan, X. Gu, X. W. D. Lou, Angew. Chem. Int. Ed., 2023, 62, e202310847.
[42]	S. Hu, P. Qiao, X. Yi, Y. Lei, H. Hu, J. Ye, D. Wang, Angew. Chem. Int. Ed., 2023, 62, e202304585.
[43]	P. Chen, B. Lei, X.-A. Dong, H. Wang, J. Sheng, W. Cui, J. Li, Y. Sun, Z. Wang, F. Dong, ACS Nano, 2020, 14, 15841-15852.
[44]	C. Cometto, R. Kuriki, L. Chen, K. Maeda, T.-C. Lau, O. Ishitani, M. Robert, J. Am. Chem. Soc., 2018, 140, 7437-7440.
[45]	W. Zhen, J. Sun, X. Ning, X. Shi, C. Xue, Appl. Catal. B, 2021, 298, 120568.
[46]	R. Kuriki, O. Ishitani, K. Maeda, ACS Appl. Mater. Interfaces, 2016, 8, 6011-6018.
[47]	S. Gong, X. Teng, Y. Niu, X. Liu, M. Xu, C. Xu, L. Ji, Z. Chen, Appl. Catal. B, 2021, 298, 120521.
[48]	J. Zhou, W. Chen, C. Sun, L. Han, C. Qin, M. Chen, X. Wang, E. Wang, Z. Su, ACS Appl. Mater. Interfaces, 2017, 9, 11689-11695.
[49]	Q. Liu, Z. Chen, W. Tao, H. Zhu, L. Zhong, F. Wang, R. Zou, Y. Lei, C. Liu, X. Peng, J. Mater. Chem. A, 2020, 8, 11761-11772.
[50]	H. Yu, E. Haviv, R. Neumann, Angew. Chem. Int. Ed., 2020, 59, 6219-6223.
[51]	Y. Chen, Y. Qu, X. Zhou, D. Li, P. Xu, J. Sun, ACS Appl. Mater. Interfaces, 2020, 12, 41527-41537.
[52]	X. Sun, L. Sun, G. Li, Y. Tuo, C. Ye, J. Yang, J. Low, X. Yu, J. H. Bitter, Y. Lei, D. Wang, Y. Li, Angew. Chem. Int. Ed., 2022, 61, e202207677.
[53]	J. Cheng, Y. Hou, K. Lian, H. Xiao, S. Lin, X. Wang, ACS Catal., 2022, 12, 1797-1808.
[54]	H.-B. Zhao, J.-N. Huang, Q. Qin, H.-Y. Chen, D.-B. Kuang, Small, 2023, 19, 2302022.
[55]	J. Zhou, B. Gao, D. Wu, C. Tian, H. Ran, W. Chen, Q. Huang, W. Zhang, F. Qi, N. Zhang, Y. Pu, J. Qiu, Z. Hu, J. Du, Z. Liu, Y. Leng, X. Tang, Adv. Funct. Mater., 2024, 34, 2308411.
[56]	Y. Ma, X. Yi, S. Wang, T. Li, B. Tan, C. Chen, T. Majima, E. R. Waclawik, H. Zhu, J. Wang, Nat. Commun., 2022, 13, 1400.
[57]	W. Shangguan, Q. Liu, Y. Wang, N. Sun, Y. Liu, R. Zhao, Y. Li, C. Wang, J. Zhao, Nat. Commun., 2022, 13, 3894.
[58]	X. Li, L. Li, G. Chen, X. Chu, X. Liu, C. Naisa, D. Pohl, M. Löffler, X. Feng, Nat. Commun., 2023, 14, 4034.
[59]	H. Zhou, M. Wang, F. Wang, Chem, 2022, 8, 465-479.
[60]	H. Lu, T.-Y. Yu, P.-F. Xu, H. Wei, Chem. Rev., 2021, 121, 365-411.
[61]	F. Kong, H. Zhou, Z. Chen, Z. Dou, M. Wang, Angew. Chem. Int. Ed., 2022, 61, e202210745.
[62]	H.-A. Ho, K. Manna, A. D. Sadow, Angew. Chem. Int. Ed., 2012, 51, 8607-8610.

Bipolar photocatalysis for CO generation via biopolyol oxidation and CO₂ reduction over brown polymeric carbon nitride nanowires

RichHTML

PDF (PC)

Knowledge

Supporting Information

Abstract

Cite this article

share this article

share this article

Figures/Tables 7

References

Related Articles 15

Recommended Articles

Metrics

[1]	Fuhao Yin, Qianyu Zhang, Mao Xu, Shupeng Wei, Yi Li, Pengzuo Chen, Yanying Zhao, Benxia Li. Synergistic Pd species anchored in ordered macroporous In₂O₃ boosting solar-driven CO₂ and H₂O conversion [J]. Chinese Journal of Catalysis, 2026, 82(3): 238-250.
[2]	Haopeng Jiang, Jinhe Li, Xiaohui Yu, Huilong Dong, Weikang Wang, Qinqin Liu. Interface engineering of covalent β-ketoenamine-bridged S-scheme heterojunction for synergistic solar-powered CO₂-to-CO conversion paired with selective alcohol oxidation [J]. Chinese Journal of Catalysis, 2026, 80(1): 113-122.
[3]	Chen Hongjing, Li Yueying, Chen Min, Xie Zhongkai, Shi Weidong. Sulfur electron bridge mediating CuInS₂/CuS heterostructure for highly selective CO₂ photoreduction to C₂H₄ [J]. Chinese Journal of Catalysis, 2025, 75(8): 180-191.
[4]	Lin Zhang, Hui Zhang, Jinghong Fang, Jialin Cui, Jie Liu, Hui Liu, Lishui Sun, Qiong Sun, Lifeng Dong, Yingjie Zhao. Highly conjugated and chemically stable three-dimensional covalent organic frameworks for efficient photocatalytic CO₂ reduction [J]. Chinese Journal of Catalysis, 2025, 74(7): 144-154.
[5]	Ya-Hui Li, Yu Chen, Jin-Yu Guo, Rui Wang, Shu-Na Zhao, Gang Li, Shuang-Quan Zang. Engineering coordination microenvironments of polypyridine Ni catalysts embedded in covalent organic frameworks for efficient CO₂ photoreduction [J]. Chinese Journal of Catalysis, 2025, 74(7): 155-166.
[6]	Rui Li, Pengfei Feng, Bonan Li, Jiayu Zhu, Yali Zhang, Ze Zhang, Jiangwei Zhang, Yong Ding. Photocatalytic reduction of CO₂ over porous ultrathin NiO nanosheets with oxygen vacancies [J]. Chinese Journal of Catalysis, 2025, 73(6): 242-251.
[7]	Dongxiao Wen, Nan Wang, Jiahe Peng, Tetsuro Majima, Jizhou Jiang. Collaborative photocatalytic C-C coupling with Cu and P dual sites to produce C₂H₄ over Cu_xP/g-C₃N₄ heterojunction [J]. Chinese Journal of Catalysis, 2025, 69(2): 58-74.
[8]	Lingkun Yang, Zongjun Li, Xin Wang, Lingling Li, Zhe Chen. Facile electrospinning synthesis of S-scheme heterojunction CoTiO₃/g-C₃N₄ nanofiber with enhanced visible light photocatalytic activity [J]. Chinese Journal of Catalysis, 2024, 59(4): 237-249.
[9]	Xiaotian Wang, Bo Hu, Yuan Li, Zhixiong Yang, Gaoke Zhang. Dipole moment regulation by Ni doping ultrathin Bi₄O₅Br₂ for enhancing internal electric field toward efficient photocatalytic conversion of CO₂ to CO [J]. Chinese Journal of Catalysis, 2024, 66(11): 257-267.
[10]	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.
[11]	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(6): 160-167.
[12]	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.
[13]	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.
[14]	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.
[15]	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.