2D metal-free heterostructure of covalent triazine framework/g-C3N4 for enhanced photocatalytic CO2 reduction with high selectivity

doi:10.1016/S1872-2067(21)63936-0

Abstract

Abstract:

Solar-driven CO₂ conversion to precious fossil fuels has been proved to become a potential way to decrease CO₂ with producing renewable fuels, which mainly relies on photocatalysts with efficient charge separation. In this work, a metal free heterostructure of covalent triazine framework (CTF) and graphite carbon nitride (g-C₃N₄, abbreviated as CN) is applied in the CO₂ photoreduction for the first time. Detailed characterization methods such as photoluminescence (PL) and time-resolved PL (TR-PL) decay are utilized to reveal the photo-induced carries separating process on g-C₃N₄/CTF (CN/CTF) heterostructure. The introduced CTF demonstrated a great boosting photocatalytic activity for CN, bringing about the transform rates of CO₂ to CO reaching 151.1 μmol/(g·h) with a 30 h stabilization time, while negligible CH₄ was detected. The optimal CN/CTF heterostructure could more efficiently separate charges with a lower probability of recombination under visible light irradiation, which made the photoreduction efficiency of CO₂ to CO be 25.5 and 2.5 times higher than that of CTF and CN, respectively. This investigation is expected to offer a new thought for fabricating high-efficiency photocatalyst without metal in solar-energy-driven CO₂ reduction.

Key words: CO₂ reduction, Covalent triazine framework, Graphite carbon nitride, Metal-free heterostructure, Photocatalysis

Jie He, Xuandong Wang, Shangbin Jin, Zhao-Qing Liu, Mingshan Zhu. 2D metal-free heterostructure of covalent triazine framework/g-C₃N₄ for enhanced photocatalytic CO₂ reduction with high selectivity[J]. Chinese Journal of Catalysis, 2022, 43(5): 1306-1315.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63936-0

https://www.cjcatal.com/EN/Y2022/V43/I5/1306

Figures/Tables 9

Fig. 1. The schematic diagram of synthesis and photocatalytic procedure of CN/CTF heterostructure.

Fig. 2. TEM patterns of CN (a), CTF (b) and CN/CTF heterostructure (c); (d) Enlarged TEM image of CN/CTF heterostructure; (e) XRD patterns of CN, CTF and CN/CTF.

Fig. 3. XPS spectra of C 1s (a) and N 1s (b); Raman spectra (c) and UV-Vis DRS (d) of CTF, CN and CN/CTF heterostructure.

Fig. 4. (a) Instantaneous photocurrent of CN and CN/CTF under light on/off; (b) EIS signals of CN and CN/CTF with/without light illumination; PL (c) and TR-PL decay curve (d) of CN and CN/CTF at the excitation light of 360 nm.

Table 1 TR-PL decay parameters of CN and CN/CTF at 360 nm stimulation wavelength.

Sample	τ₁ (ns)	A₁ (%)	τ₂ (ns)	A₂ (%)	τ_av (ns)	k_ET (/s)
CN	2.71	88.94	16.61	11.06	4.25	—
CN/CTF	0.77	70.31	5.85	29.69	2.28	2.04 × 10⁸

Fig. 5. (a) Yield of reduced products with reaction time via CN/CTF (2.5%) heterostructure; (b) The comparison of CO yield for CO2 reduction under 200 mW/cm2 visible light within 3 h with blank, CTF, CN, CN/CTF (1.0%), CN/CTF (2.5%), CN/CTF (5.0%) in acetonitrile/Co(bpy)3Cl2 TEOA system; (c) Cycle runs of photo-catalytic CO2 reduction by CN/CTF (2.5%) heterostructure.

Fig. 6. The GC-MS spectrum (a) and total ion chromatographic spectrum (b) of the isotope experiment using 12CO2 or 13CO2 as gas source with CN/CTF.

Fig. 7. Mott-Schottky plots of CN (a) and CTF (b); (c) Tauc’s plots of CN and CTF based on UV-Vis DRS spectrum; (d) Energy band structure of the as-synthesized CN/CTF heterostructure.

Fig. 8. The mechanism scheme of CN/CTF heterostructure for photocatalytic CO2 reduction.

References

[1]	L. Hao, L. Kang, H. Huang, L. Ye, K. Han, S. Yang, H. Yu, M. Batmunkh, Y. Zhang, T. Ma, Adv. Mater., 2019, 31, 1900546.
[2]	H. Yu, J. Li, Y. Zhang, S. Yang, K. Han, F. Dong, T. Ma, H. Huang, Angew. Chem. Int. Ed., 2019, 58, 3880-3884.
[3]	B. Han, J. Wang, C. Yan, Y. Dong, Y. Xu, R. Nie, H. Jing, Electrochim. Acta, 2018, 285, 23-29.
[4]	J. Hu, C. Zhai, M. Zhu, Chin. Chem. Lett., 2020, 32, 1348-1358.
[5]	M. Zhang, J. He, Y. Chen, P. Y. Liao, Z. Q. Liu, M. Zhu, Chin. Chem. Lett., 2020, 31, 2721-2724.
[6]	X. Chang, T. Wang, J. Gong, Energy Environ. Sci., 2016, 9, 2177-2196.
[7]	S. N. Habisreutinger, L. Schmidt-Mende, J. K. Stolarczyk, Angew. Chem. Int. Ed., 2013, 52, 7372-7408.
[8]	J. Wen, J. Xie, X. Chen, X. Li, Appl. Surf. Sci., 2017, 391, 72-123.
[9]	Z. Zhao, Y. Sun, F. Dong, Nanoscale, 2015, 7, 15-37.
[10]	F. Dong, L. Wu, Y. Sun, M. Fu, Z. Wu, S. C. Lee, J. Mater. Chem., 2011, 21, 15171-15174.
[11]	S. Ye, R. Wang, M. Z. Wu, Y. P. Yuan, Appl. Surf. Sci., 2015, 358, 15-27.
[12]	K. Maeda, R. Kuriki, M. Zhang, X. Wang, O. Ishitani, J. Mater. Chem. A, 2014, 2, 15146-15151.
[13]	J. Fu, B. Zhu, C. Jiang, B. Cheng, W. You, J. Yu, Small, 2017, 13, 1603938.
[14]	K. Wang, Q. Li, B. Liu, B. Cheng, W. Ho, J. Yu, Appl. Catal. B, 2015, 176, 44-52.
[15]	T. Song, X. Yu, N. Tian, H. Huang, Int. J. Hydrogen Energy, 2020, 46, 1857-1878.
[16]	C. Hu, F. Chen, Y. Wang, N. Tian, T. Ma, Y. Zhang, H. Huang, Adv. Mater., 2021, 33, 2101751.
[17]	S. Wang, X. Han, Y. Zhang, N. Tian, T. Ma, H. Huang, Small Structures, 2021, 2, 2000061.
[18]	Z. Zhang, J. Huang, M. Zhang, Q. Yuan, B. Dong, Appl. Catal. B, 2015, 163, 298-305.
[19]	O. Buyukcakir, S. H. Je, S. N. Talapaneni, D. Kim, A. Coskun, ACS Appl. Mater. Interfaces, 2017, 9, 7209-7216.
[20]	S. Hug, L. Stegbauer, H. Oh, M. Hirscher, B. V. Lotsch, Chem. Mater., 2015, 27, 8001-8010.
[21]	T. Xu, Y. Li, Z. Zhao, G. Xing, L. Chen, Macromolecules, 2019, 52, 9786-9791.
[22]	T. Feng, J. M. Wang, S. T. Gao, C. Feng, N. Z. Shang, C. Wang, X. L. Li, Appl. Surf. Sci., 2019, 469, 431-436.
[23]	H. Zhong, Z. Hong, C. Yang, L. Li, Y. Xu, X. Wang, R. Wang, ChemSusChem, 2019, 12, 4493-4499.
[24]	K. Wang, L. M. Yang, X. Wang, L. Guo, G. Cheng, C. Zhang, S. Jin, B. Tan, A. Cooper, Angew. Chem. Int. Ed., 2017, 56, 14149-14153.
[25]	J. He, J. Yang, F. Jiang, P. Liu, M. Zhu, Chemosphere, 2020, 258, 127339.
[26]	P. Kuhn, M. Antonietti, A. Thomas, Angew. Chem. Int. Ed., 2008, 47, 3450-3453.
[27]	M. Wang, J. Cheng, X. Wang, X. Hong, J. Fan, H. Yu, Chin. J. Catal., 2021, 42, 37-45.
[28]	F. Ge, S. Huang, J. Yan, L. Jing, F. Chen, M. Xie, Y. Xu, H. Xu, H. Li, Chin. J. Catal., 2021, 42, 450-459.
[29]	J. Hu, Z. Li, C. Zhai, J. Wang, L. Zeng, M. Zhu, Rare Metals, 2021, 40, 1727-1737.
[30]	Y. He, X. Chen, C. Huang, L. Li, C. Yang, Y. Yu, Chin. J. Catal., 2021, 42, 123-130.
[31]	J. Wang, J. Wang, N. Li, X. Du, J. Ma, C. He, Z. Li, ACS Appl. Mater. Interfaces, 2020, 12, 31477-31485.
[32]	Y. Zhu, X. Chen, Y. Cao, W. Peng, Y. Li, G. Zhang, F. Zhang, X. Fan, Chem. Commun., 2019, 55, 1434-1437.
[33]	L. Hao, J. Ning, B. Luo, B. Wang, Y. Zhang, Z. Tang, J. Yang, A. Thomas, L. Zhi, J. Am. Chem. Soc., 2015, 137, 219-225.
[34]	J. Fu, Q. Xu, J. Low, C. Jiang, J. Yu, Appl. Catal. B, 2019, 243, 556-565.
[35]	Q. Chen, S. Li, H. Xu, G. Wang, Y. Qu, P. Zhu, D. Wang, Chin. J. Catal., 2020, 41, 514-523.
[36]	P. Zhu, X. Yin, X. Gao, G. Dong, J. Xu, C. Wang, Chin. J. Catal., 2021, 42, 175-183.
[37]	F. Li, X. Yue, H. Zhou, J. Fan, Q. Xiang, Chin. J. Catal., 2021, 42, 1608-1616.
[38]	R. Yin, Y. Chen, S. He, W. Li, L. Zeng, W. Guo, M. Zhu, J. Hazard. Mater., 2020, 388, 121996.
[39]	F. Chen, Z. Ma, L. Ye, T. Ma, T. Zhang, Y. Zhang, H. Huang, Adv. Mater., 2020, 32, 1908350.
[40]	M. Li, S. Yu, H. Huang, X. Li, Y. Feng, C. Wang, Y. Wang, T. Ma, L. Guo, Y. Zhang, Angew. Chem. Int. Ed., 2019, 58, 9517-9521.
[41]	Z. Wei, J. Liu, W. Fang, M. Xu, Z. Qin, Z. Jiang, W. Shangguan, Chem. Eng. J., 2019, 358, 944-954.
[42]	S. Cao, B. Shen, T. Tong, J. Fu, J. Yu, Adv. Funct. Mater., 2018, 28, 1800136.
[43]	M. Zhu, C. Zhai, S. Kim, M. Fujitsuka, T. Majima, J. Phys. Chem. Lett., 2019, 10, 4017-4024.
[44]	F. Xu, K. Meng, B. Cheng, S. Wang, J. Xu, J. Yu, Nat. Commun., 2020, 11, 4613.
[45]	S. Hua, D. Qu, L. An, W. Jiang, Y. Wen, X. Wang, Z. Sun, Appl. Catal. B, 2019, 240, 253-261.
[46]	Y. Chen, S. Lan, M. Zhu, Chin. Chem. Lett., 2020, 32, 2052-2056.
[47]	A. A. Dubale, W. N. Su, A. G. Tamirat, C. J. Pan, B. A. Aragaw, H. M. Chen, C. H. Chen, B. J. Hwang, J. Mater. Chem. A, 2014, 2, 18383-18397.
[48]	S. Luo, J. Ke, M. Yuan, Q. Zhang, P. Xie, L. Deng, S. Wang, Appl. Catal. B, 2018, 221, 215-222.
[49]	E. Karamian, S. Sharifnia, Int. J. Hydrogen Energy, 2019, 44, 25717-25729.
[50]	J. Bi, W. Fang, L. Li, J. Wang, S. Liang, Y. He, M. Liu, L. Wu, Macromol. Rapid Comm., 2015, 36, 1799-1805.
[51]	K. Wang, D. Liu, P. Deng, L. Liu, S. Lu, Z. Sun, Y. Ma, Y. Wang, M. Li, B.Y. Xia, Nano Energy, 2019, 64, 103954.
[52]	Y. Wang, N. Lu, M. Luo, L. Fan, K. Zhao, J. Qu, J. Guan, X. Yuan, Appl. Surf. Sci., 2019, 463, 234-243.
[53]	X. Wang, J. He, L. Mao, X. Cai, C. Sun, M. Zhu, Chem. Eng. J., 2021, 416, 128077.
[54]	N.-N. Vu, S. Kaliaguine, T.-O. Do, ACS Appl. Energy Mater., 2020, 3, 6422-6433.
[55]	J. Lin, Y. Hou, Y. Zheng, X. Wang, Chem.-Asian J., 2014, 9, 2468-2474.
[56]	X. Wang, J. He, J. Li, G. Lu, F. Dong, T. Majima, M. Zhu, Appl. Catal. B, 2020, 277, 119230.
[57]	X. Wang, K. Li, J. He, J. Yang, F. Dong, W. Mai, M. Zhu, Nano Energy, 2020, 78, 105388.

2D metal-free heterostructure of covalent triazine framework/g-C₃N₄ for enhanced photocatalytic CO₂ reduction with high selectivity

RichHTML

PDF (PC)

Knowledge

Supporting Information

Abstract

Cite this article

share this article

share this article

Figures/Tables 9

References

Related Articles 15

Recommended Articles

Metrics

[1]	Binbin Zhao, Wei Zhong, Feng Chen, Ping Wang, Chuanbiao Bie, Huogen Yu. High-crystalline g-C₃N₄ photocatalysts: Synthesis, structure modulation, and H₂-evolution application [J]. Chinese Journal of Catalysis, 2023, 52(9): 127-143.
[2]	Xiaolong Tang, Feng Li, Fang Li, Yanbin Jiang, Changlin Yu. Single-atom catalysts for the photocatalytic and electrocatalytic synthesis of hydrogen peroxide [J]. Chinese Journal of Catalysis, 2023, 52(9): 79-98.
[3]	Hui Gao, Gong Zhang, Dongfang Cheng, Yongtao Wang, Jing Zhao, Xiaozhi Li, Xiaowei Du, Zhi-Jian Zhao, Tuo Wang, Peng Zhang, Jinlong Gong. Steering electrochemical carbon dioxide reduction to alcohol production on Cu step sites [J]. Chinese Journal of Catalysis, 2023, 52(9): 187-195.
[4]	Wen Zhang, Cai-Cai Song, Jia-Wei Wang, Shu-Ting Cai, Meng-Yu Gao, You-Xiang Feng, Tong-Bu Lu. Bidirectional host-guest interactions promote selective photocatalytic CO₂ reduction coupled with alcohol oxidation in aqueous solution [J]. Chinese Journal of Catalysis, 2023, 52(9): 176-186.
[5]	Zicong Jiang, Bei Cheng, Liuyang Zhang, Zhenyi Zhang, Chuanbiao Bie. A review on ZnO-based S-scheme heterojunction photocatalysts [J]. Chinese Journal of Catalysis, 2023, 52(9): 32-49.
[6]	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.
[7]	Fei Yan, Youzi Zhang, Sibi Liu, Ruiqing Zou, Jahan B Ghasemi, Xuanhua Li. Efficient charge separation by a donor-acceptor system integrating dibenzothiophene into a porphyrin-based metal-organic framework for enhanced photocatalytic hydrogen evolution [J]. Chinese Journal of Catalysis, 2023, 51(8): 124-134.
[8]	Zhaochun Liu, Xue Zong, Dionisios G. Vlachos, Ivo A. W. Filot, Emiel J. M. Hensen. A computational study of electrochemical CO₂ reduction to formic acid on metal-doped SnO₂ [J]. Chinese Journal of Catalysis, 2023, 50(7): 249-259.
[9]	Min Lin, Meilan Luo, Yongzhi Liu, Jinni Shen, Jinlin Long, Zizhong Zhang. 1D S-scheme heterojunction of urchin-like SiC-W₁₈O₄₉ for enhancing photocatalytic CO₂ reduction [J]. Chinese Journal of Catalysis, 2023, 50(7): 239-248.
[10]	Defa Liu, Bin Sun, Shuojie Bai, Tingting Gao, Guowei Zhou. Dual co-catalysts Ag/Ti₃C₂/TiO₂ hierarchical flower-like microspheres with enhanced photocatalytic H₂-production activity [J]. Chinese Journal of Catalysis, 2023, 50(7): 273-283.
[11]	Han-Zhi Xiao, Bo Yu, Si-Shun Yan, Wei Zhang, Xi-Xi Li, Ying Bao, Shu-Ping Luo, Jian-Heng Ye, Da-Gang Yu. Photocatalytic 1,3-dicarboxylation of unactivated alkenes with CO₂ [J]. Chinese Journal of Catalysis, 2023, 50(7): 222-228.
[12]	Jingxiang Low, Chao Zhang, Ferdi Karadas, Yujie Xiong. Photocatalytic CO₂ conversion: Beyond the earth [J]. Chinese Journal of Catalysis, 2023, 50(7): 1-5.
[13]	Huijie Li, Manzhou Chi, Xing Xin, Ruijie Wang, Tianfu Liu, Hongjin Lv, Guo-Yu Yang. Highly selective photoreduction of CO₂ catalyzed by the encapsulated heterometallic-substituted polyoxometalate into a photo-responsive metal-organic framework [J]. Chinese Journal of Catalysis, 2023, 50(7): 343-351.
[14]	Xuan Li, Xingxing Jiang, Yan Kong, Jianju Sun, Qi Hu, Xiaoyan Chai, Hengpan Yang, Chuanxin He. Interface engineering of a GaN/In₂O₃ heterostructure for highly efficient electrocatalytic CO₂ reduction to formate [J]. Chinese Journal of Catalysis, 2023, 50(7): 314-323.
[15]	Sang Eon Jun, Sungkyun Choi, Jaehyun Kim, Ki Chang Kwon, Sun Hwa Park, Ho Won Jang. Non-noble metal single atom catalysts for electrochemical energy conversion reactions [J]. Chinese Journal of Catalysis, 2023, 50(7): 195-214.