基于热解ZIF-8的氮掺杂碳电化学氧还原合成过氧化氢催化剂

doi:10.6023/A22010030

摘要/Abstract

氧气的两电子还原反应(2e-ORR)是绿色、安全的H₂O₂合成路线. 本工作以Zn²⁺和2-甲基咪唑合成的沸石型咪唑酸框架-8 (ZIF-8)为前驱体, 通过高温热解炭化, 利用ZIF-8中的锌在高温下的可挥发性, 制备了非金属氮掺杂石墨化多孔碳材料(p-ZIF), 系统考察了ZIF-8热解炭化温度(900、950和1000 ℃)对催化剂结构和2e-ORR催化性能的影响. p-ZIF不仅保留了ZIF-8规整的菱形十二面体形貌, 而且氮含量高, 拥有高的比表面积和多级孔结构. 在酸性条件下的2e-ORR反应中, 三个p-ZIF催化剂均显示了较低的过电位和较低的Tafel斜率, 而且稳定性良好. 其中在H₂O₂选择性最高的p-ZIF-950催化剂上, 过电位为86 mV, H₂O₂选择性最高可达89.2%. 在6 h恒电位反应中, p-ZIF-950催化剂能够以87 mmol•g_cat^-1•h^-1的恒定速率产生H₂O₂. 根据多种表征结果, 推测p-ZIF催化剂的孔径尺寸和石墨N含量是影响其2e-ORR催化性能的主要因素.

关键词: 过氧化氢, ZIF-8, 热解, 电催化, 氧还原反应

Electrochemical production of H₂O₂ from O₂ via the two-electron reduction reaction (2e-ORR) is a green and safe process that is being heavily investigated. Zeolitic imidazolate frameworks (ZIF) as a subclass of metal-organic frameworks (MOFs) have attracted enormous scientific interests due to their high porosity, excellent mechanical stability, tunable surface properties, and exceptional chemical and thermal stabilities. Herein, a series of pyrolyzed ZIF catalysts (p-ZIF) were synthesized by treating 2-methylimidazole zinc salt (ZIF-8) at high temperatures (900, 950 and 1000 ℃). During pyrolysis, zinc was vaporized, leaving the metal-free nitrogen-doped porous graphitic carbon materials. The effects of the pyrolysis temperature on the structure and catalytic performance of the p-ZIF catalysts in 2e-ORR were systematically studied. In 2e-ORR in an acidic electrolyte, the p-ZIF catalysts displayed low overpotential, low Tafel slope, and negligible activity loss after 3000 cycles of accelerated durability testing (ADT). In particular, the p-ZIF-950 catalyst possessed the highest H₂O₂ partial current of 0.185 mA at 0 V vs. RHE, followed by the p-ZIF-900 (0.146 mA) and p-ZIF-1000 (0.135 mA) catalysts. The H₂O₂ selectivity over the p-ZIF-950 catalyst was also constantly higher than those over the other two p-ZIF catalysts across the potential range investigated and maximized at 89.2%. Highly efficient and durable H₂O₂ production was demonstrated on the p-ZIF-950 catalyst by the linear accumulation of H₂O₂ to 522 mmol•g_cat^-1 within 6 h, translating to an H₂O₂ production rate of 87 mmol•g_cat^-1•h^-1. The morphology, composition, carbon defect, texture, and surface chemical state were characterized by techniques such as transmission electron microscopy (TEM), elemental analysis, Raman spectroscopy, N₂ physisorption, and X-ray photoelectron spectroscopy (XPS). The p-ZIF catalysts not only nicely carried over the regular rhombic dodecahedral morphology of ZIF-8, but also possessed abundant amount of nitrogen, high specific surface area, and hierarchical pore structure. According to the characterization results, the specific surface area and carbon defect are unlikely the key factors that determine the catalytic performance, while the evolutions of the average pore size and surface content of graphitic N mimicked those of the H₂O₂ partial current and selectivity on the p-ZIF catalysts. In light of the literature works, the large pore size is proposed to facilitate the in-diffusion of O₂ and out-diffusion of H₂O₂, while the graphitic N is able to enhance the activation of O₂ and desorption of H₂O₂, both of which are beneficial to the kinetics of the 2e-ORR reaction.

Key words: hydrogen peroxide, ZIF-8, pyrolysis, electrocatalysis, oxygen reduction reaction

引用此文

王丹, 封波, 张晓昕, 刘亚楠, 裴燕, 乔明华, 宗保宁. 基于热解ZIF-8的氮掺杂碳电化学氧还原合成过氧化氢催化剂[J]. 化学学报, 2022, 80(6): 772-780.

Dan Wang, Bo Feng, Xiaoxin Zhang, Yanan Liu, Yan Pei, Minghua Qiao, Baoning Zong. Nitrogen-doped Carbon Pyrolyzed from ZIF-8 for Electrocatalytic Oxygen Reduction to Hydrogen Peroxide[J]. Acta Chimica Sinica, 2022, 80(6): 772-780.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 12

图1. p-ZIF催化剂在O2饱和的0.1 mol•L-1 HClO4电解液中采用旋转环盘电极(RRDE)测得的ORR结果. (a) 线性扫描伏安曲线; (b) H2O2选择性; (c) 电子转移数

Figure 1. RRDE ORR results of the p-ZIF catalysts in the O2-saturated 0.1 mol•L-1 HClO4 electrolyte. (a) Linear sweep voltammograms (LSV), (b) H2O2 selectivity and (c) electron transfer number Reaction conditions: 40 µg of catalyst, scan rate of 10 mV•s-1, and rotation speed of 1600 r•min-1. The Pt ring was potentiostated at 1.2 V vs. RHE for H2O2 detection

图2. p-ZIF催化剂在O2饱和的0.1 mol•L-1 HClO4电解液中的Tafel斜率

Figure 2. Tafel slopes of the p-ZIF catalysts in the O2-saturated 0.1 mol•L-1 HClO4 electrolyte Reaction conditions: scan rate of 10 mV•s-1 and rotation speed of 1600 r•min-1

图3. p-ZIF催化剂在O2饱和的0.1 mol•L-1 HClO4中的加速耐久性测试结果. (a) p-ZIF-900, (b) p-ZIF-950, (c) p-ZIF-1000

Figure 3. Stability performance under accelerated durability testing (ADT) conditions in the O2-saturated 0.1 mol•L-1 HClO4 electrolyte. (a) p-ZIF-900, (b) p-ZIF-950, and (c) p-ZIF-1000 Reaction conditions: 40 µg of catalyst and scan rate of 200 mV•s-1

图4. p-ZIF-950催化剂在恒电位下的电流和H2O2生成量随时间的变化

Figure 4. The current (left) and the photometrically determined amount of H2O2 normalized by the mass of the p-ZIF-950 catalyst (right) as a function of the reaction time Reaction conditions: catalyst loading of 200 μg•cmgeo-2, rotation speed of the working electrode of 1600 r•min-1, and the working voltage of 0.1 V vs. RHE. The 0.1 mol•L-1 HClO4 electrolyte was continuously bubbled with O2

Catalyst	Bulk composition^a(w)/%				S_BET^b/ (m²•g^-1)	V_pore^b/ (cm³•g^-1)	d_pore^b/ nm
Catalyst	C	H	O	N	S_BET^b/ (m²•g^-1)	V_pore^b/ (cm³•g^-1)	d_pore^b/ nm
p-ZIF-900	62.10	3.71	23.12	11.05	870(610)	0.61(0.32)	5.6
p-ZIF-950	73.11	3.89	14.42	8.56	913(636)	0.85(0.34)	9.9
p-ZIF-1000	83.22	4.96	6.85	4.94	1190(761)	0.83(0.41)	5.1

表1. p-ZIF催化剂的体相元素组成和织构性质

Table 1. The bulk compositions and textural properties of the p-ZIF catalysts

图5. p-ZIF催化剂的XRD谱

Figure 5. XRD patterns of the p-ZIF catalysts

图6. 催化剂的TEM照片和EDS元素分布. (a), (d) p-ZIF-900; (b), (e) p-ZIF-950; (c), (f) p-ZIF-1000

Figure 6. TEM images and EDS mapping of the C, N, and O elements on the p-ZIF catalysts. (a), (d) p-ZIF-900; (b), (e) p-ZIF-950; (c), (f) p-ZIF-1000

图7. p-ZIF催化剂的拉曼谱

Figure 7. Raman spectra of the p-ZIF catalysts

图8. p-ZIF催化剂的(a) N2吸脱附等温线和(b)孔径分布曲线

Figure 8. (a) N2 adsorption-desorption isotherms and (b) pore size distributions of the p-ZIF catalysts

图9. p-ZIF-900, p-ZIF-950和p-ZIF-1000催化剂的(a) C 1s和(b) N 1s谱

Figure 9. (a) C 1s and (b) N 1s spectra of the p-ZIF-900, p-ZIF-950, and p-ZIF-1000 catalysts

Catalyst	Surface N/at%	Fraction in surface N				Surface graphitic N/at%
Catalyst	Surface N/at%	Pyridinic N	Pyrrolic N	Graphitic N	Oxidic N	Surface graphitic N/at%
p-ZIF-900	12.0	0.645	0.203	0.119	0.033	1.43
p-ZIF-950	8.5	0.562	0.113	0.263	0.062	2.23
p-ZIF-1000	4.7	0.414	0.255	0.294	0.037	1.38

表2. p-ZIF催化剂经XPS拟合得到的表面总氮量和表面各氮物种所占的分数

Table 2. Total surface content of nitrogen and the relative fraction of various surface nitrogen species on the p-ZIF catalysts determined by XPS

图10. (a) p-ZIF-900, (c) p-ZIF-950, (e) p-ZIF-1000催化剂在非法拉第范围内在N2饱和的0.1 mol•L-1 HClO4中不同扫描速率(5, 10, 15, 20, 25 mV•s-1)下的CV谱. (b), (d), (f)为相应的电流密度随扫描速率的变化曲线

Figure 10. Cyclic voltammograms in the non-Faradic potential region at varying scan rates of 5, 10, 15, 20, and 25 mV•s-1 in the N2-saturated 0.1 mol•L-1 HClO4 electrolyte for the (a) p-ZIF-900, (c) p-ZIF-950, and (e) p-ZIF-1000 catalysts. (b), (d), and (f) are the corresponding plots of average current density vs. scan rate

参考文献 57

[1]	Li, H. B.; Zheng, B.; Pan, Z. Y.; Zong, B. N.; Qiao, M. H. Front. Chem. Sci. Eng. 2018, 12, 124. doi: 10.1007/s11705-017-1676-5
[2]	Siahrostami, S.; Verdaguer-Casadevall, A.; Karamad, M.; Deiana, D.; Malacrida, P.; Wickman, B.; Escudero-Escribano, M.; Paoli, E. A.; Frydendal, R.; Hansen, T. W.; Chorkendorff, I.; Stephens, I. E. L.; Rossmeisl, J. Nat. Mater. 2013, 12, 1137. doi: 10.1038/nmat3795 pmid: 24240242
[3]	Campos-Martin, J. M.; Blanco-Brieva, G.; Fierro, J. L. G. Angew. Chem. Int. Ed. 2006, 45, 6962. doi: 10.1002/anie.200503779
[4]	Yang, S.; Verdaguer-Casadevall, A.; Arnarson, L.; Silvioli, L.; Colic, V.; Frydendal, R.; Rossmeisl, J.; Chorkendorff, I.; Stephens, I. E. L. ACS Catal. 2018, 8, 4064. doi: 10.1021/acscatal.8b00217
[5]	Freakley, S. J.; He, Q.; Harrhy, J. H.; Lu, L.; Crole, D. A.; Morgan, D. J.; Ntainjua, E. N.; Edwards, J. K.; Carley, A. F.; Borisevich, A. Y.; Kiely, C. J.; Hutchings, G. J. Science 2016, 351, 965. doi: 10.1126/science.aad5705 pmid: 26917769
[6]	Sun, Y. Y.; Li, S.; Jovanov, Z. P.; Bernsmeier, D.; Wang, H.; Paul, B.; Wang, X.; Kühl, S.; Strasser, P. ChemSusChem 2018, 11, 3388. doi: 10.1002/cssc.201801583
[7]	Xia, C.; Xia, Y.; Zhu, P.; Fan, L.; Wang, H. T. Science 2019, 366, 226. doi: 10.1126/science.aay1844
[8]	Zhang, J.; Zhang, H.; Cheng, M. J.; Lu, Q. Small 2020, 16, 1902845. doi: 10.1002/smll.201902845
[9]	Yang, S.; Kim, J.; Tak, Y. J.; Soon, A.; Lee, H. Angew. Chem. Int. Ed. 2016, 55, 2058. doi: 10.1002/anie.201509241
[10]	Wang, Y. L.; Li, S. S.; Yang, X. H.; Xu, G. Y.; Zhu, Z. C.; Chen, P.; Li, S. Q. J. Mater. Chem. A 2019, 7, 21329. doi: 10.1039/C9TA04788C
[11]	Zhao, H. Y.; Shen, X. Q.; Chen, Y.; Zhang, S. N.; Gao, P.; Zhen, X. J.; Li, X. H.; Zhao, G. H. Chem. Commun. 2019, 55, 6173. doi: 10.1039/C9CC02580D
[12]	Sa, Y. J.; Kim, J. H.; Joo, S. H. Angew. Chem. Int. Ed. 2019, 58, 1100. doi: 10.1002/anie.201812435
[13]	Zhou, W.; Meng, X.; Gao, J.; Alshawabkeh, A. N. Chemosphere 2019, 225, 588. doi: S0045-6535(19)30478-3 pmid: 30903840
[14]	Tian, X.; Zhao, X.; Su, Y. Q.; Wang, L.; Wang, H.; Dang, D.; Chi, B.; Liu, H.; Hensen, E. J. M.; Lou, X. W.; Xia, B. Y. Science 2019, 366, 850. doi: 10.1126/science.aaw7493
[15]	Gong, K.; Du, F.; Xia, Z.; Durstock, M.; Dai, L. Science 2009, 323, 760. doi: 10.1126/science.1168049
[16]	Sun, Y. Y.; Sinev, I.; Ju, W.; Bergmann, A.; Dresp, S.; Kühl, S.; Spöri, C.; Schmies, H.; Wang, H.; Bernsmeier, D.; Paul, B.; Schmack, R.; Kraehnert, R.; Roldan Cuenya, B.; Strasser, P. ACS Catal. 2018, 8, 2844. doi: 10.1021/acscatal.7b03464
[17]	Jiang, Y.; Ni, P.; Chen, C.; Lu, Y.; Yang, P.; Kong, B.; Fisher, A.; Wang, X. Adv. Energy Mater. 2018, 8, 1801909. doi: 10.1002/aenm.201801909
[18]	Melchionna, M.; Fornasiero, P.; Prato, M. Adv. Mater. 2019, 31, 1802920. doi: 10.1002/adma.201802920
[19]	Lu, X. Q.; Cao, S. F.; Wei, X. F.; Li, S. R.; Wei, S. X. Acta Chim. Sinica 2020, 78, 1001. (in Chinese) doi: 10.6023/A20060223
	(鲁效庆, 曹守福, 魏晓飞, 李邵仁, 魏淑贤, 化学学报, 2020, 78, 1001.) doi: 10.6023/A20060223
[20]	Jia, N.; Yang, T.; Shi, S.; Chen, X.; An, Z.; Chen, Y.; Yin, S.; Chen, P. ACS Sustainable Chem. Eng. 2020, 8, 2883. doi: 10.1021/acssuschemeng.9b07047
[21]	Pizzutilo, E.; Kasian, O.; Choi, C. H.; Cherevko, S.; Hutchings, G. J.; Mayrhofer, K. J. J.; Freakley, S. J. Chem. Phys. Lett. 2017, 683, 436. doi: 10.1016/j.cplett.2017.01.071
[22]	He, D. Q.; Zhong, L. J.; Gan, S. Y.; Xie, J. X.; Wang, W.; Liu, Z. B.; Guo, W.; Yang, X.; Niu, L. Electrochim. Acta 2021, 371, 137721. doi: 10.1016/j.electacta.2021.137721
[23]	Xi, J.; Yang, S.; Silvioli, L.; Cao, S.; Liu, P.; Chen, Q.; Zhao, Y.; Sun, H.; Hansen, J. N.; Haraldsted, J. B.; Kibsgaard, J.; Rossmeisl, J.; Bals, S.; Wang, S.; Chorkendorff, I. J. Catal. 2021, 393, 313. doi: 10.1016/j.jcat.2020.11.020
[24]	Shen, R. G.; Chen, W. X.; Peng, Q.; Lu, S. Q.; Zheng, L. R.; Cao, X.; Wang, Y.; Zhu, W.; Zhang, J. T.; Zhuang, Z. B.; Chen, C.; Wang, D. G.; Li, Y. D. Chem 2019, 5, 2099. doi: 10.1016/j.chempr.2019.04.024
[25]	Gao, J. J.; Yang, H. B.; Huang, X.; Hung, S. F.; Cai, W. Z.; Jia, C. M.; Miao, S.; Chen, H. M.; Yang, X. F.; Huang, Y. Q.; Zhang, T.; Liu, B. Chem 2020, 6, 658. doi: 10.1016/j.chempr.2019.12.008
[26]	Jiang, K.; Back, S.; Akey, A. J.; Xia, C.; Hu, Y.F.; Liang, W. T.; Schaak, D.; Stavitski, E.; Norskov, J. K.; Siahrostami, S.; Wang, H. T. Nat. Commun. 2019, 10, 3997. doi: 10.1038/s41467-019-11992-2 pmid: 31488826
[27]	Sun, Y.; Silvioli, L.; Sahraie, N. R.; Ju, W.; Li, J.; Zitolo, A.; Li, S.; Bagger, A.; Arnarson, L.; Wang, X.; Moeller, T.; Bernsmeier, D.; Rossmeisl, J.; Jaouen, F.; Strasser, P. J. Am. Chem. Soc. 2019, 141, 12372. doi: 10.1021/jacs.9b05576
[28]	Perazzolo, V.; Durante, C.; Pilot, R.; Paduano, A.; Zheng, J.; Rizzi, G. A.; Martucci, A.; Granozzi, G.; Gennaro, A. Carbon 2015, 95, 949. doi: 10.1016/j.carbon.2015.09.002
[29]	Hasché, F.; Oezaslan, M.; Strasser, P.; Fellinger, T. J. Energy Chem. 2016, 25, 251. doi: 10.1016/j.jechem.2016.01.024
[30]	Xia, Y.; Zhao, X. H.; Xia, C.; Wu, Z. Y.; Zhu, P.; Kim, J. Y.; Bai, X. W.; Gao, G. H.; Hu, Y. F.; Zhong, J.; Liu, Y. Y.; Wang, H.T. Nat. Commun. 2021, 12, 4225. doi: 10.1038/s41467-021-24329-9
[31]	Chen, S. Y.; Luo, T.; Chen, K. J.; Lin, Y. Y.; Fu, J. W.; Liu, K.; Cai, C.; Wang, Q. Y.; Li, H. J. W.; Li, X. Q.; Hu, J. H.; Li, H. M.; Zhu, M. S.; Liu, M. Angew. Chem. Int. Ed. 2021, 60, 16607. doi: 10.1002/anie.202104480
[32]	Xu, Z. H.; Shen, L. M.; Wu, Q.; Sun, T.; Xu, Y. Y.; Li, D. Q.; Du, L. Y.; Yang, L. J.; Wang, X. Z.; Hu, Z. Acta Chim. Sinica 2015, 73, 793. (in Chinese)
	(许智慧, 沈丽明, 吴强, 孙涛, 徐宇洋, 黎聃勤, 杜玲玉, 杨立军, 王喜章, 胡征, 化学学报, 2015, 73, 793.) doi: 10.6023/A15050354
[33]	Qin, M. C.; Fan, S. Y.; Wang, L.; Gan, G. Q.; Wang, X. Y.; Cheng, J.; Hao, Z. P.; Li, X. Y. J. Colloid Interface Sci. 2020, 562, 540. doi: 10.1016/j.jcis.2019.11.080
[34]	Chen, S. C.; Chen, Z. H.; Siahrostami, S.; Higgins, D.; Nordlund, D.; Sokaras, D.; Kim, T. R.; Liu, Y. Z.; Yan, X. Z.; Nilsson, E.; Sinclair, R.; Nørskov, J. K.; Jaramillo, T. F.; Bao, Z. N. J. Am. Chem. Soc. 2018, 140, 7851. doi: 10.1021/jacs.8b02798
[35]	Han, G. F.; Li, F.; Zou, W.; Karamad, M.; Jeon, J. P.; Kim, S. W.; Kim, S. J.; Bu, Y. F.; Fu, Z. P.; Lu, Y. L.; Siahrostami, S.; Baek, J. B. Nat. Commun. 2020, 11, 7293.
[36]	Zhao, K.; Su, Y.; Quan, X.; Liu, Y. M.; Chen, S.; Yu, H. T. J. Catal. 2018, 357, 118. doi: 10.1016/j.jcat.2017.11.008
[37]	Dong, K.; Liang, J.; Wang, Y. Y.; Xu, Z. Q.; Liu, Q.; Luo, Y. L.; Li, T. S.; Li, L.; Shi, X. F.; Asiri, A. M.; Li, Q.; Ma, D. M.; Sun, X. P. Angew. Chem. Int. Ed. 2021, 60, 10583. doi: 10.1002/anie.202101880
[38]	Fellinger, T.; Hasché, F.; Strasser, P.; Antonietti, M. J. Am. Chem. Soc. 2012, 134, 4072. doi: 10.1021/ja300038p
[39]	Zhou, Y.; Chen, G.; Zhang, J. J. J. Mater. Chem. A 2020, 8, 20849. doi: 10.1039/D0TA07900F
[40]	Zhang, L. J.; Su, Z. X.; Jiang, F. L.; Yang, L. L.; Qian, J. J.; Zhou, Y. F.; Li, W. M.; Hong, M. C. Nanoscale 2014, 6, 6590. doi: 10.1039/C4NR00348A
[41]	Guo, W. J.; Yu, J.; Dai, Z.; Hou, W. Z. Acta Chim. Sinica 2019, 77, 1203. (in Chinese) doi: 10.6023/A19080316
	(郭文娟, 于洁, 代昭, 侯伟钊, 化学学报, 2019, 77, 1203.) doi: 10.6023/A19080316
[42]	Liu, Y.; Quan, X.; Fan, X.; Wang, H.; Chen, S. Angew. Chem. Int. Ed. 2015, 54, 6837. doi: 10.1002/anie.201502396
[43]	Sun, Y. H.; Qi, Y. X.; Shen, Y.; Jing, C. J.; Chen, X. X.; Wang, X. X. Acta Chim. Sinica 2020, 78, 147. (in Chinese) doi: 10.6023/A19090338
	(孙延慧, 齐有啸, 申优, 井翠洁, 陈笑笑, 王新星, 化学学报, 2020, 78, 147.) doi: 10.6023/A19090338
[44]	Kaneti, Y. V.; Dutta, S.; Hossain, M. S. A.; Shiddiky, M. J. A.; Tung, K. L.; Shieh, F. K.; Tsung, C. K.; Wu, K. C. W.; Yamauchi, Y. Adv. Mater. 2017, 29, 1700213. doi: 10.1002/adma.201700213
[45]	Stanczyk, K.; Dziembaj, R.; Piwowarska, Z.; Witkowski, S. Carbon 1995, 33, 1383. doi: 10.1016/0008-6223(95)00084-Q
[46]	Amali, A. J.; Sun, J. K.; Xu, Q. Chem. Commun. 2014, 50, 1519. doi: 10.1039/C3CC48112C
[47]	Wei, S. J.; Li, A.; Liu, J. C.; Chen, W. X.; Gong, Y.; Zhang, Q. H.; Cheong, W. C.; Wang, Y.; Zheng, L. R.; Xiao, H.; Chen, C.; Wang, D. S.; Peng, Q.; Gu, L.; Han, X. D.; Li, J.; Li, Y. D. Nat. Nanotechnol. 2018, 13, 856. doi: 10.1038/s41565-018-0197-9
[48]	Lu, Z.; Chen, G.; Siahrostami, S.; Chen, Z.; Liu, K.; Xie, J.; Liao, L.; Wu, T.; Lin, D.; Liu, Y.; Jaramillo, T. F.; Nørskov, J. K.; Cui, Y. Nat. Catal. 2018, 1, 156. doi: 10.1038/s41929-017-0017-x
[49]	Perazzolo, V.; Daniel, G.; Brandiele, R.; Picelli, L.; Rizzi, G. A.; Isse, A. A.; Durante, C. Chem. Eur. J. 2021, 27, 1002. doi: 10.1002/chem.202003355
[50]	Zhang, P.; Sun, F.; Xiang, Z. H.; Shen, Z. G.; Yun, J.; Cao, D. P. Energy Environ. Sci. 2014, 7, 442. doi: 10.1039/C3EE42799D
[51]	Gu, D. G.; Wang, F. F.; Yan, K.; Ma, R. G.; Wang, J. C. ACS Sustainable Chem. Eng. 2018, 6, 1951. doi: 10.1021/acssuschemeng.7b03370
[52]	Li, L. Q.; Tang, C.; Zheng, Y.; Xia, B. Q.; Zhou, X. L.; Xu, H. L.; Qiao, S. Z. Adv. Energy Mater. 2020, 10, 2000789. doi: 10.1002/aenm.202000789
[53]	Chen, S. C.; Chen, Z. H.; Siahrostami, S.; Kim, T. R.; Nordlund, D.; Sokaras, D.; Nowak, S.; To, J. W. F.; Higgins, D.; Sinclair, R.; Nørskov, J. K.; Jaramillo, T. F.; Bao, Z. N. ACS Sustainable Chem. Eng. 2018, 6, 311. doi: 10.1021/acssuschemeng.7b02517
[54]	Park, J.; Nabae, Y.; Hayakawa, T.; Kakimoto, M. ACS Catal. 2014, 4, 3749. doi: 10.1021/cs5008206
[55]	Iglesias, D.; Giuliani, A.; Melchionna, M.; Marchesan, S.; Criado, A.; Nasi, L.; Bevilacqua, M.; Tavagnacco, C.; Vizza, F.; Prato, M.; Fornasiero, P. Chem 2018, 4, 106. doi: 10.1016/j.chempr.2017.10.013
[56]	Zhang, J. Y.; Zhang, G.; Jin, S. Y.; Zhou, Y. J.; Ji, Q. H.; Lan, H. C.; Liu, H. J.; Qu, J. H. Carbon 2020, 163, 154. doi: 10.1016/j.carbon.2020.02.084
[57]	Contreras, E.; Dominguez, D.; Tiznado, H.; Guerrero-Sanchez, J.; Takeuchi, N.; Alonso-Nunez, G.; Contreras, O. E.; Oropeza- Guzman, M. T.; Romo-Herrera, J. M. Nanoscale 2019, 11, 2829. doi: 10.1039/c8nr08384c pmid: 30676594