Pt0.01Fe0.05-g-C3N4催化剂高效光热催化二氧化碳还原

doi:10.6023/A21030118

摘要/Abstract

光热催化是一种高效利用太阳光, 将二氧化碳转化为高价值产物的方法. 本工作以石墨相氮化碳为载体, 通过水热-浸渍两步法制备了负载铂、铁氧化物的石墨相氮化碳催化剂. 该催化剂具备优异的光热转换性能, 可实现7.36 mmol•h^-1•g_cat^-1的二氧化碳还原活性和97%的一氧化碳选择性. 使用X射线晶体衍射(XRD)、配备能量色散X射线谱(EDS)的球差校正扫描透射电子显微镜(Cs-S/TEM)、X射线光电子能谱(XPS)、紫外可见漫反射光谱(DRS)等表征手段从催化剂物相、微观结构、表面状态、光学性能等方面对催化剂进行了表征. 结果显示, 催化剂能吸收全谱太阳光, 且具备较高的载流子分离效率. 基于原位傅里叶变换红外光谱(DRIFTS)表征结果, 提出了二氧化碳在催化剂表面的可能的反应机理, 并对铂在铁氧化物表面的氢溢流效应进行了表征. 结果表明二氧化碳和氢气分别在铁氧化物、铂位点被活化, 参与催化反应. 本工作对后续光热二氧化碳还原催化剂的设计、合成与机理研究具有一定的参考作用.

关键词: 石墨相氮化碳, 光热催化, 二氧化碳还原, 原位傅里叶变换红外光谱

Converting CO₂ into value-added compounds via photothermal catalysis is a promising strategy to reduce CO₂ emission and might be a sustainable alternative to traditional fossil fuels. Here, we report nano-structured a Pt_0.01Fe_0.05-g-C₃N₄ hybrid catalyst synthesized via hydrothermal-method and further reduced under reaction condition for the reverse water gas shift (RWGS) reaction. Taking advantage of the photo-thermal effect caused by the near-infrared (NIR) and visible light responsive, the hybrid catalyst produces a remarkable activity (7.36 mmol•h^-1•g_cat^-1) for CO₂ reduction with CO selectivity (97%) under 300 W Xe lamp irradiation and CO₂/H₂ (V/V, 1/1) feed gas. The apparent activation energy of reaction decreases from 238.59 kJ/mol to 48.88 kJ/mol calculated by Arrhenius formula. In order to comprehend the good catalytic activity of Pt_0.01Fe_0.05-g-C₃N₄in the RWGS reaction, the catalyst is characterized with powder X-ray diffraction (XRD), spherical-aberration-corrected scanning transmission electron microscopy (Cs-S/TEM) integrated with X-ray energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), UV-vis-NIR diffuse reflectance spectroscopy (DRS),etc. for investigating the structural information, surface state, optical properties and so on. Results show that the presence of FeO _x and Pt exhibits strong absorption in a wide range from UV to NIR regions. Low photoluminescence (PL) intensity at about 460 nm shows the suppressed photogenerated carrier recombination process of Pt_0.01Fe_0.05-g-C₃N₄ due to the heterojunction between FeO _x and g-C₃N₄. Operando diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) under different reaction conditions is employed to investigate surface species and their evolution during the conversion of CO₂ into CO and a broad IR absorption is observed due to hydrogen spillover from Pt to Fe₃O₄. Therefore, we propose a possible mechanism of photothermal catalytic CO₂ reduction, involving separate activation of CO₂ and H₂ over Fe and Pt acitve sites. Our work present a high-performance Pt_0.01Fe_0.05-g-C₃N₄ catalyst for RWGS reaction and open a new vista of the design, synthesis and mechanism research of photothermal catalytic CO₂ conversion in the future.

Key words: g-C₃N₄, photothermal catalysis, CO₂ reduction reaction, operando diffuse reflectance infrared Fourier transform spectroscopy

引用此文

王瑞兆, 邹云杰, 洪晟, 徐铭楷, 凌岚. Pt_0.01Fe_0.05-g-C₃N₄催化剂高效光热催化二氧化碳还原[J]. 化学学报, 2021, 79(7): 932-940.

Ruizhao Wang, Yunjie Zou, Sheng Hong, Mingkai Xu, Lan Ling. High-performance Pt_0.01Fe_0.05-g-C₃N₄ Catalyst for Photothermal Catalytic CO₂ Reduction[J]. Acta Chimica Sinica, 2021, 79(7): 932-940.

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图/表 11

图1. 5Fe1Pt AR, 5Fe1Pt BR和5Fe0Pt样品的XRD谱图

Figure 1. XRD patterns of 5Fe1Pt AR, 5Fe1Pt BR and 5Fe0Pt

图2. 5Fe1Pt AR, 5Fe0Pt和g-C3N4的XPS总谱(a), 5Fe1Pt BR (b)和5Fe1Pt AR (c)的高自旋Fe 2p XPS谱图, 5Fe1Pt BR和5Fe1Pt AR的Pt 4f XPS谱图(d), 5Fe0Pt与5Fe1Pt AR的N 1s XPS谱图(e)

Figure 2. Full XPS pattern of 5Fe1Pt AR, and 5Fe0Pt, g-C3N4 (a), XPS pattern of high-spin Fe 2p for 5Fe1Pt BR (b) and 5Fe1Pt AR (c), Pt 4f for 5Fe1Pt BR and 5Fe1Pt AR (d), N 1s for 5Fe0Pt and 5Fe1Pt AR (e)

图3. 5Fe1Pt BR的HRTEM图(a)和扫描透射电子显微镜-能量色散X射线谱(STEM-EDS)元素分布图(b)

Figure 3. HRTEM of 5Fe1Pt BR (a) and STEM-EDS elemental mapping of 5Fe1Pt BR (b)

图4. 5Fe1Pt AR催化剂单个铁氧化物颗粒上的EDS线分析. EDS分析位置(a), 线扫图谱(b)

Figure 4. The position of the EDS line scan (a) and EDS line scan profile (b) of FeOx particle on 5Fe1Pt AR

图5. 5Fe1Pt AR的N2吸附-脱附等温线(a)和DFT脱附孔径分布增量图(b)

Figure 5. N2 absorption-desorption isotherm (a) and DFT desorption pore size distribution plot (b) of 5Fe1Pt AR

图6. 5Fe1Pt、5Fe0Pt、0Fe1Pt和0.5Fe1Pt的甲烷/一氧化碳产生速率(a)与光热-热表观活化能对比(b)

Figure 6. CH4 and CO evolution rates over 5Fe1Pt, 5Fe0Pt, 0Fe1Pt, and 0.5Fe1Pt (a), and apparent photothermal-thermal activation energy contrast (b)

图7. 5Fe1Pt、5Fe0Pt和0.5Fe1Pt不同光强下的热平衡温度

Figure 7. Thermal equilibrium temperatures for 5Fe1Pt, 5Fe0Pt and 0.5Fe1Pt at different power levels

图8. 各组样品的DRS (a)和荧光(b)谱图

Figure 8. The DRS spectra (a) and photoluminescence (PL) spectra (b) of samples

图9. 5Fe1Pt AR、5Fe0Pt和g-C3N4的光电流分析结果

Figure 9. Photocurrent of 5Fe1Pt, 5Fe0Pt and g-C3N4

图10. 5Fe1Pt AR在H2氛围中的红外吸收(a), 向CO2处理后的5Fe1Pt AR通入CO2/H2 (V/V, 1/1)原料气后的原位DRIFTS变化(b, c), 向CO2处理后的5Fe1Pt AR通入H2的原位DRIFTS变化(d), 不同气体条件吸收变化总谱(e)

Figure 10. IR spectra of 5Fe1Pt AR under H2 (a). Operando DRIFTS for 5Fe1Pt AR following exposure to CO2/H2 (V/V, 1/1) feed gas after pretreatment with pure CO2 (b, c), following exposure to H2 after pretreatment with pure CO2 (d), and absorption changes under different reaction conditions (e)

图11. 可能的光热CO2还原机理示意图

Figure 11. Illustration of possible mechanism of photothermal CO2 reduction

参考文献 41

[1]	Gao, W.; Liang, S.; Wang, R.; Jiang, Q.; Zhang, Y.; Zheng, Q.; Xie, B.; Toe, C. Y.; Zhu, X.; Wang, J.; Huang, L.; Gao, Y.; Wang, Z.; Jo, C.; Wang, Q.; Wang, L.; Liu, Y.; Louis, B.; Scott, J.; Roger, A.-C.; Amal, R.; He, H.; Park, S.-E. Chem. Soc. Rev. 2020, 49, 8584. doi: 10.1039/D0CS00025F
[2]	Ghoussoub, M.; Xia, M.; Duchesne, P. N.; Segal, D.; Ozin, G. Energy Environ. Sci. 2019, 12, 1122. doi: 10.1039/C8EE02790K
[3]	Yin, S.; Sun, L.; Zhou, Y.; Li, X.; Li, J.; Song, X.; Huo, P.; Wang, H.; Yan, Y. Chem. Eng. J. 2021, 406, 126776. doi: 10.1016/j.cej.2020.126776
[4]	Zhang, X.; Deng, B.; Fan, H.; Huang, W.; Zhang, Y. Acta Chim. Sinica. 2020, 78, 1120. (in Chinese) doi: 10.6023/A20060230
	(张旭寒, 邓博文, 范海东, 黄文辉, 张彦威, 化学学报, 2020, 78, 1120.) doi: 10.6023/A20060230
[5]	Hoch, L. B.; O’Brien, P. G.; Jelle, A.; Sandhel, A.; Perovic, D. D.; Mims, C. A.; Ozin, G. A. ACS Nano 2016, 10, 9017. doi: 10.1021/acsnano.6b05416
[6]	Wang, L.; Dong, Y.; Yan, T.; Hu, Z.; Jelle, A. A.; Meira, D. M.; Duchesne, P. N.; Loh, J. Y. Y.; Qiu, C.; Storey, E. E.; Xu, Y.; Sun, W.; Ghoussoub, M.; Kherani, N. P.; Helmy, A. S.; Ozin, G. A. Nat. Commun. 2020, 11, 2432. doi: 10.1038/s41467-020-16336-z pmid: 32415078
[7]	Hoch, L. B.; O’Brien, P. G.; Jelle, A.; Sandhel, A.; Perovic, D. D.; Mims, C. A.; Ozin, G. A. ACS Nano 2016, 10, 9017. doi: 10.1021/acsnano.6b05416
[8]	Li, Y. F.; Lu, W.; Chen, K.; Duchesne, P.; Jelle, A.; Xia, M.; Wood, T. E.; Ulmer, U.; Ozin, G. A. J. Am. Chem. Soc. 2019, 141, 14991. doi: 10.1021/jacs.9b08030
[9]	Jia, J.; Wang, H.; Lu, Z.; O’Brien, P. G.; Ghoussoub, M.; Duchesne, P.; Zheng, Z.; Li, P.; Qiao, Q.; Wang, L.; Gu, A.; Jelle, A. A.; Dong, Y.; Wang, Q.; Ghuman, K. K.; Wood, T.; Qian, C.; Shao, Y.; Qiu, C.; Ye, M.; Zhu, Y.; Lu, Z. H.; Zhang, P.; Helmy, A. S.; Singh, C. V.; Kherani, N. P.; Perovic, D. D.; Ozin, G. A. Adv. Sci. 2017, 4, 1700252. doi: 10.1002/advs.v4.10
[10]	Li, C.; Chen, F.; Ye, L.; Li, W.; Yu, H.; Zhao, T. Acta Chim. Sinica 2020, 78, 1448. (in Chinese) doi: 10.6023/A20070322
	(李宸, 陈凤华, 叶丽, 李伟, 于晗, 赵彤, 化学学报, 2020, 78, 1448.) doi: 10.6023/A20070322
[11]	Wang, X.; Maeda, K.; Thomas, A.; Takanabe, K.; Xin, G.; Carlsson, J. M.; Domen, K.; Antonietti, M. A. Nat. Mater. 2009, 8, 76. doi: 10.1038/nmat2317
[12]	Ong, W. J.; Tan, L. L.; Ng, Y. H.; Yong, S. T.; Chai, S. P. Chem. Rev. 2016, 116, 7159. doi: 10.1021/acs.chemrev.6b00075
[13]	Huang, Z. F.; Song, J.; Pan, L.; Wang, Z.; Zhang, X.; Zou, J. J.; Mi, W.; Zhang, X.; Wang, L. Nano Energy 2015, 12, 646. doi: 10.1016/j.nanoen.2015.01.043
[14]	Chen, P.; Lei, B.; Dong, X.; Wang, H.; Sheng, J.; Cui, W.; Li, J.; Sun, Y.; Wang, Z.; Dong, F. ACS Nano 2020, 14, 15841. doi: 10.1021/acsnano.0c07083
[15]	Chen, S.; Hu, Y.; Meng, S.; Fu, X. Appl. Catal., B 2014, 150-151, 564. doi: 10.1016/j.apcatb.2013.12.053
[16]	Grosvenor, A. P.; Kobe, B. A.; Biesinger, M. C.; McIntyre, N. S. Surf. Interface Anal. 2004, 36, 1564. doi: 10.1002/(ISSN)1096-9918
[17]	Palmer, J. W.; Swartz Jr, W. E.; King, D.; Stanko, J. A. Fla. Sci. 1993, 56, 123.
[18]	Romeo, M.; Majerus, J.; Legare, P.; Castellani, N. J.; Leroy, D. B. Surf. Sci. 1990, 238, 163. doi: 10.1016/0039-6028(90)90073-H
[19]	Liu, H. Y.; Chiou, W. A.; Fröhlich, G.; Sachtler, W. M. H. Top. Catal. 2000, 10, 49. doi: 10.1023/A:1019103815248
[20]	Sun, M. H.; Huang, S. Z.; Chen, L. H.; Li, Y.; Yang, X. Y.; Yuan, Z. Y.; Su, B. L. Chem. Soc. Rev. 2016, 45, 3479. doi: 10.1039/C6CS00135A
[21]	He, S.; Li, W.; Wang, X.; Ma, Q.; Li, M.; Xu, W.; Wang, X.; Zhao, C. Appl. Surf. Sci. 2020, 506, 144948. doi: 10.1016/j.apsusc.2019.144948
[22]	Kong, T.; Stolze, K.; Timmons, E. I.; Tao, J.; Ni, D.; Guo, S.; Yang, Z.; Prozorov, R.; Cava, R. J. Adv. Mater. 2019, 31, 1.
[23]	Wang, L.; Ghoussoub, M.; Wang, H.; Shao, Y.; Sun, W.; Tountas, A. A.; Wood, T. E.; Li, H.; Loh, J. Y. Y.; Dong, Y.; Xia, M.; Li, Y.; Wang, S.; Jia, J.; Qiu, C.; Qian, C.; Kherani, N. P.; He, L.; Zhang, X.; Ozin, G. A. Joule 2018, 2, 1369. doi: 10.1016/j.joule.2018.03.007
[24]	Zhu, Z.; Lu, Z.; Wang, D.; Tang, X.; Yan, Y.; Shi, W.; Wang, Y.; Gao, N.; Yao, X.; Dong, H. Appl. Catal., B 2016, 182, 115.
[25]	Xu, Y.; Schoonen, M. A. A. Am. Mineral. 2000,543.
[26]	Wu, H. Z.; Liu, L. M.; Zhao, S. J. Phys. Chem. Chem. Phys. 2014, 16, 3299. doi: 10.1039/c3cp54333a
[27]	Moniz, S. J. A.; Shevlin, S. A.; Martin, D. J.; Guo, Z. X.; Tang, J. Energy Environ. Sci. 2015, 8, 731. doi: 10.1039/C4EE03271C
[28]	Arndt, B.; Creutzburg, M.; Grånäs, E.; Volkov, S.; Krausert, K.; Vlad, A.; Noei, H.; Stierle, A. J. Phys. Chem. C 2019, 123, 26662. doi: 10.1021/acs.jpcc.9b07160
[29]	Mirabella, F.; Zaki, E.; Ivars-Barcelo, F.; Schauermann, S.; Shaikhutdinov, S.; Freund, H. J. J. Phys. Chem. C 2018, 122, 27433. doi: 10.1021/acs.jpcc.8b08240
[30]	Graciani, J.; Mudiyanselage, K.; Xu, F.; Baber, A. E.; Evans, J.; Senanayake, S. D.; Stacchiola, D. J.; Liu, P.; Hrbek, J.; Fernández Sanz, J.; Rodriguez, J. A. Science 2014, 345, 546. doi: 10.1126/science.1253057 pmid: 25082699
[31]	Hakim, A.; Marliza, T. S.; Abu Tahari, N. M.; Wan Isahak, R. W. N.; Yusop, R. M.; Mohamed Hisham, W. M.; Yarmo, A. M. Ind. Eng. Chem. Res. 2016, 55, 7888. doi: 10.1021/acs.iecr.5b04091
[32]	Gracia, F. J.; Bollmann, L.; Wolf, E. E.; Miller, J. T.; Kropf, A. J. J. Catal. 2003, 220, 382. doi: 10.1016/S0021-9517(03)00296-3
[33]	Benziger, J. B.; Larson, L. R. J. Catal. 1982, 77, 550. doi: 10.1016/0021-9517(82)90195-6
[34]	Li, X.; Lin, J.; Li, L.; Huang, Y.; Pan, X.; Collins, S. E.; Ren, Y.; Su, Y.; Kang, L.; Liu, X.; Zhou, Y.; Wang, H.; Wang, A.; Qiao, B.; Wang, X.; Zhang, T. Angew. Chem. Int. Ed. 2020, 59, 2.
[35]	Panayotov, D. A.; Yates, J. T. J. Phys. Chem. C 2007, 111, 2959. doi: 10.1021/jp066686k
[36]	Skomurski, F. N.; Kerisit, S.; Rosso, K. M. Geochim. Cosmochim. Acta 2010, 74, 4234. doi: 10.1016/j.gca.2010.04.063
[37]	Parkinson, G. S.; Mulakaluri, N.; Losovyj, Y.; Jacobson, P.; Pentcheva, R.; Diebold, U. Phys. Rev. B: Condens. Matter Mater. Phys. 2010, 82, 125413. doi: 10.1103/PhysRevB.82.125413
[38]	Novotny, Z.; Mulakaluri, N.; Edes, Z.; Schmid, M.; Pentcheva, R.; Diebold, U.; Parkinson, G. S. Phys. Rev. B: Condens. Matter Mater. Phys. 2013, 87, 195410. doi: 10.1103/PhysRevB.87.195410
[39]	Kurahashi, M.; Sun, X.; Yamauchi, Y. Phys. Rev. B: Condens. Matter Mater. Phys. 2010, 81, 193402. doi: 10.1103/PhysRevB.81.193402
[40]	Baltrusaitis, J.; Jensen, J. H.; Grassian, V. H. J. Phys. Chem. B 2006, 110, 12005. doi: 10.1021/jp057437j
[41]	Gálvez, M. E.; Loutzenhiser, P. G.; Hischier, I.; Steinfeld, A. Energy Fuels 2008, 22, 3544. doi: 10.1021/ef800230b

Pt_0.01Fe_0.05-g-C₃N₄催化剂高效光热催化二氧化碳还原

High-performance Pt_0.01Fe_0.05-g-C₃N₄ Catalyst for Photothermal Catalytic CO₂ Reduction

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