基于Pt@TiO2催化剂光-热协同催化甲醇-水液相重整甲醇制氢

doi:10.1016/S1872-2067(21)63963-3

催化学报 ›› 2022, Vol. 43 ›› Issue (5): 1258-1266.DOI: 10.1016/S1872-2067(21)63963-3

基于Pt@TiO₂催化剂光-热协同催化甲醇-水液相重整甲醇制氢

李垒^a, 欧阳汶俊^a, 郑泽锋^a, 叶凯航^a, 郭禹希^a, 秦延林^a, 伍珍珍^b, 林展^a(), 王铁军^a(), 张山青^b()

^a广东工业大学广东省植物资源生物炼制重点实验室, 广东广州510006, 中国
^b格里菲斯大学环境与科学学院, 催化与清洁能源中心, 昆士兰, 澳大利亚

收稿日期:2021-09-19 接受日期:2021-10-22 出版日期:2022-05-18 发布日期:2022-03-23
通讯作者: 林展,王铁军,张山青
基金资助:
国家自然科学基金(21902034)

Synergetic photocatalytic and thermocatalytic reforming of methanol for hydrogen production based on Pt@TiO₂ catalyst

Lei Li^a, Wenjun Ouyang^a, Zefeng Zheng^a, Kaihang Ye^a, Yuxi Guo^a, Yanlin Qin^a, Zhenzhen Wu^b, Zhan Lin^a(), Tiejun Wang^a(), Shanqing Zhang^b()

^aGuangdong Provincial Key Laboratory of Plant Resources Biorefinery, Guangdong University of Technology, Guangzhou 510006, Guangdong, China
^bCentre for Catalysis and Clean Energy, School of Environment and Science, Gold Coast Campus, Griffith University, Queensland, Australia

Received:2021-09-19 Accepted:2021-10-22 Online:2022-05-18 Published:2022-03-23
Contact: Zhan Lin, Tiejun Wang, Shanqing Zhang
Supported by:
National Natural Science Foundation of China(21902034)

摘要/Abstract

摘要：

氢能以其高能量密度和零排放的特点成为新一代能源载体的理想选择. 作为一种潜在的二次能源, 氢气在商业燃料电池、发电、汽车、航空航天等领域引起了广泛关注. 甲醇-氢能源体系对于解决氢能应用中储存和输送的瓶颈问题具有重大意义. 传统甲醇-水重整制氢由于氢释放过程的吉布斯自由能很高(决速步$\Delta_{r} G_{m}^{\varnothing}$63.7 kJ·mol^‒1), 通常需要较高的温度(>200 ºC). 相比较而言, 常温光催化分解水制氢被认为是另一种很有前途的方法. 当甲醇作为牺牲剂时, 通过光生电子-空穴对与甲醇-水分子之间的氧化还原反应, 可在比单纯热催化过程低得多的温度下生成氢气, 但由于动力学的限制, 光催化制氢的能量转换效率仍然远远低于工业要求. 为了解决热催化制氢能垒高、能耗大以及光催化反应效率低的问题, 将光引入热重整催化过程, 改善热催化反应过程及热加速光催化反应相结合, 有望解决传统热催化或纯光催化制氢技术的有关问题.

本文利用经典催化剂体系Pt@TiO₂, 系统考察了其在光催化、热催化以及光辅助热催化条件下的甲醇-水体系液相重整制氢的效率, 并通过X射线衍射、扫描电子显微镜、透射电子显微镜、能量色散X射线光谱、拉曼光谱、光电流测试、X射线光电子能谱等对催化剂进行了系统的表征, 深入深究了催化剂的理化性质以及部分反应机理. 结果表明, 光的引入可以显著降低反应活化能并提升制氢效率, 光辅助条件下产氢速率明显优于单一的热催化和光催化下的产氢效率, 且大于两种单一催化条件下产氢速率之和. 其中, 0.05%Pt@TiO₂催化剂催化制氢效率达到5.66 μmol·H₂·g^‒1catalyst·s^‒1, 比单纯热催化和光催化条件下分别提高了约3倍和7倍. 同位素实验及活性中间体捕获实验结果表明, 光生空穴和羟基自由基增强了甲醇脱氢活性, 同时光辅助热催化条件下改善了水分子裂解的动力学过程. 光辅助的热催化液相甲醇重整制氢过程遵循了不同于传统热催化机理, 并由于光和热的协同作用而大大提升了制氢效率.

关键词: 水相重整, 光催化, 热催化, 协同效应, Pt@TiO₂催化剂, 甲醇, 氢气

Abstract:

In order to efficiently produce H₂, conventional methanol-water thermocatalytic (TC) reforming requires a very high temperature due to high Gibbs free energy, while the energy conversion efficiency of methanol-water photocatalytic (PC) reforming is far from satisfaction because of the kinetic limitation. To address these issues, herein, we incorporate PC and TC processes together in a specially designed reactor and realize simultaneous photocatalytic/thermocatalytic (PC-TC) reforming of methanol in an aqueous phase. Such a design facilitates the synergetic effect of the PC and TC process for H₂ production due to a lower energy barrier and faster reaction kinetics. The methanol-water reforming based on the optimized 0.05%Pt@TiO₂catalyst delivers an outstanding H₂ production rate in the PC-TC process (5.66 μmol H₂·g^‒1 catalyst·s^‒1), which is about 3 and 7 times than those of the TC process (1.89 μmol H₂·g^‒1 catalyst·s^‒1) and the PC process (0.80 μmol H₂·g^‒1 catalyst·s^‒1), respectively. Isotope tracer experiments, active intermediate trapping experiments, and theoretical calculations demonstrate that the photo-generated holes and hydroxyl radicals could enhance the methanol dehydrogenation, water molecule splitting, and water-gas shift reaction, while high temperature accelerates reaction kinetics. The proposed PC-TC reforming of methanol for hydrogen production can be a promising technology to solve the energy and environmental issue in the closed-loop hydrogen economy in the near future.

Key words: Aqueous-phase reforming, Photocatalysis, Thermocatalysis, Pt@TiO₂ catalyst, Methanol, Hydrogen

李垒, 欧阳汶俊, 郑泽锋, 叶凯航, 郭禹希, 秦延林, 伍珍珍, 林展, 王铁军, 张山青. 基于Pt@TiO₂催化剂光-热协同催化甲醇-水液相重整甲醇制氢[J]. 催化学报, 2022, 43(5): 1258-1266.

Lei Li, Wenjun Ouyang, Zefeng Zheng, Kaihang Ye, Yuxi Guo, Yanlin Qin, Zhenzhen Wu, Zhan Lin, Tiejun Wang, Shanqing Zhang. Synergetic photocatalytic and thermocatalytic reforming of methanol for hydrogen production based on Pt@TiO₂ catalyst[J]. Chinese Journal of Catalysis, 2022, 43(5): 1258-1266.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(21)63963-3

https://www.cjcatal.com/CN/Y2022/V43/I5/1258

图/表 8

Scheme 1. Schematic illustration of the hydrogen production process.

Fig. 1. Hydrogen production from MeOH/water over Pt@TiO2 catalysts. (a) Reaction rates of H2 over x%Pt@TiO2 (x = 0.05, 0.1, 0.2, 0.5) under PC, TC and PC-TC conditions; (b) ATOF of H2 over x%Pt@TiO2 (x = 0.05, 0.1, 0.2, 0.5) under PC, TC and PC-TC conditions. Reaction conditions: n(CH3OH):n(H2O)=1:3, 40 mL total volume of liquid, 50 mg catalysts, 190 °C; reaction for 1.25 h; 2.0 MPa N2.

Fig. 2. Morphology characterizations of x%Pt@TiO2. (a?d) TEM image of x%Pt@TiO2 (x = 0.05, 0.1, 0.2, 0.5); (e) HRTEM image of 0.05%Pt@TiO2; (f) PXRD patterns of the x%Pt@TiO2 (x = 0.05, 0.1, 0.2, 0.5) samples.

Fig. 3. The characterizations of x%Pt@TiO2 catalysts. (a) Raman spectra of x%Pt@TiO2 (x = 0.05, 0.1, 0.2); (b) EPR profiles of TiO2 and 0.05%Pt@TiO2; (c,d) High-resolution XPS spectra for O 2s and Ti 2p of 0.1%Pt@TiO2.

Fig. 4. The photo-related properties of x% Pt@TiO2. (a) Tauc plot for the band gap calculation of TiO2 and 0.1%Pt@TiO2; (b) Schematic illustration for the electronic structures of TiO2 and 0.1%Pt@TiO2; (c) VB XPS spectra of TiO2 and 0.1%Pt@TiO2; (d) Photocurrent of TiO2 and 0.05%Pt@TiO2.

Fig. 5. (a) TC and PC-TC H2 production rates over 0.5%Pt@TiO2 catalyst at various temperatures; (b) Arrhenius plot of TC and PC-TC performance over 0.5%Pt@TiO2 catalyst at various temperatures.

Fig. 6. Reaction rates values of H2 were obtained under PC (a), TC (b), PC-TC (c) catalytic conditions with hydroxyl radical and hole scavenger.

Scheme 2. Proposed reaction mechanisms of H2 production in the TC (up) and PC-TC (down) process.

参考文献

[1]	M. S. Dresselhaus, I. L. Thomas, Nature, 2001, 414, 332-337.
[2]	M. G. Schultz, T. Diehl, G. P. Brasseur, W. Zittel, Science, 2003, 302, 624-627.
[3]	J. A. Turner, Science, 2004, 305, 972-974.
[4]	A. Kubacka, M. Fernández-García, G. Colón, Chem. Rev., 2012, 112, 1555-1614.
[5]	Y. Tachibana, L. Vayssieres, J. R. Durrant, Nat. Photonics, 2012, 6, 511-518.
[6]	T. Hisatomi, J. Kubotaa, K. Domen, Chem. Soc. Rev., 2014, 43, 7520-7535.
[7]	D. Li, X. Li, J. Gong, Chem. Rev., 2016, 116, 11529-11653.
[8]	S. Sá, H. Silva, L. Brandao, J. M. Sousa, A. Mendes, Appl. Catal. B, 2010, 99, 43-57.
[9]	Y. Shen, Y. Zhan, S. Li, F. Ning, Y. Du, Y. Huang, T. He, X. Zhou, Chem. Sci., 2017, 8, 7498-7504.
[10]	J. Corredor, M. J. Rivero, C. M Rangel, F. Gloaguen, I. Ortiz, J. Chem. Technol. Biotechnol., 2019, 94, 3049-3063.
[11]	I. Coronado, M. Stekrova, L. G. Moreno, M. Reinikainen, P. Simell, R. Karinen, J. Lehtonen, Biomass Bioenergy, 2017, 106, 29-37.
[12]	D. Li, Y. Li, X. Liu, Y. Guo, C. Pao, J. L. Chen, Y. Hu, Y. Wang, ACS Catal. 2019, 9, 9671-9682.
[13]	L. Lin, W. Zhou, R. Gao, S. Yao, X. Zhang, W. Xu, S. Zheng, Z. Jiang, Q. Yu, Y. Li, C. Shi, X. Wen, D. Ma, Nature, 2017, 544, 80-83.
[14]	J. W. Shabaker, R. R. Davda, G. W. Huber, R. D. Cortright, J. A. Dumesic, J. Catal., 2003, 215, 344-352.
[15]	A. Fujishima, K. Honda, Nature, 1972, 238, 37-38.
[16]	I. Rossetti, ISRN Chem. Eng., 2012, 2012, 21.
[17]	C. Courtois, M. Eder, S. L. Kollmannsberger, M. Tschurl, C. A. Walenta, U. Heiz, ACS Catal., 2020, 10, 7747-7752.
[18]	K. A. Davis, S. Yoo, E. W. Shuler, B. D. Sherman, S. Lee, G. Leem, Nano Converg., 2021, 8, 1-19.
[19]	H. T. Huang, J. Y. Feng, S. Zhang, H. N. Zhang, X. Wang, T. Yu, C. C. Chen, Z. G. Yi, J. H. Ye, Z. S. Li, Z. G. Zou, Appl. Catal. B, 2020, 272, 118980
[20]	M. Yasuda, T. Matsumoto, T. Yamashita, Renew. Sust. Energy Rev., 2018, 81, 1627-1635.
[21]	J. Zhang, C. Peng, H. Wang, P. Hu, ACS Catal., 2017, 7, 2374-2380.
[22]	Y. Khani, P. Tahay, F. Bahadoran, N. Safari, S. Soltanali, A. Alavi, Appl. Catal. A, 2020, 594, 117456.
[23]	U. Caudillo-Flores, G. Agostini, C. Marini, A. Kubacka, M. Fernández-García, Appl. Catal. B, 2019, 256, 117790.
[24]	Z. Sun, S. Fang, Y. Lin, Y. Hang, Chem. Eng. J., 2019, 375, 121909.
[25]	V. Nair, M. J. Muñoz-Batista, M. Fernández-García, R. Luque, J. C. Colmenares, ChemSusChem, 2019, 12, 2098-2116.
[26]	C. Wang, S. Fang, S. Xie, Y. Zheng, Y. H. Hu, J. Mater. Chem. A, 2020, 8, 7390-7394.
[27]	D. Li, J. Sun, R. Ma, J. Wei, ES Energy Environ., 2020, 9, 82-88.
[28]	B. Han, W. Wei, M. Li, K. Sun, Y. H. Hu, Chem. Commun., 2019, 55, 7816-7819.
[29]	Z. Wang, H. Wang, X. Wang, X. Chen, Y. Yu, W. Dai, X. Fu, Chin. J. Catal., 2021, 42, 1538-1552
[30]	Y. Yang, Y. Li, M. Zeng, M. Mao, L. Lan, H. Liu, J. Chen, X. Zhao, Appl. Catal. B, 2018, 224, 751-760.
[31]	D. Li, Y. Huang, S. Li, C. Wang, Y. Li, X. Zhang, Y. Liu, Chin. J. Catal., 2020, 41, 154-160.
[32]	S. Luo, H. Lin, Q. Wang, X. Ren, D. Hernandez-Pinilla, T. Nagao, Y. Xie, G. Yang, S. Li, H. Song, M. Oshikiri, J. Ye, J. Am. Chem. Soc., 2021, 143, 12145-12153.
[33]	C. Xu, W. Huang, Z. Li, B. Deng, Y. Zhang, M. Ni, K. Cen, ACS Catal., 2018, 8, 6582-6593.
[34]	K. K. Mandari, B. S. Kwak, A. K. R. Police, M. Kang, Mater. Res. Bull., 2017, 95, 515-524.
[35]	A. Pandikumar, R. Ramaraj, J. Renew. Sustain. Energy, 2013, 5, 043101.
[36]	Y. Chen, S. Ji, W. Sun, Y. Lei, Q. Wang, A. Li, W. Chen, G. Zhou, Z. Zhang, Y. Wang, L. Zheng, Q. Zhang, L. Gu, X. Han, D. Wang, Y. Li, Angew. Chem. Int. Ed., 2020, 59, 1295-1301.
[37]	I. D. C. Silva, F. A. Sigoli, I. O. Mazali, J. Phys. Chem. C, 2017, 121, 12928-12935.
[38]	O. Bikondoa, C. L. Pang, R. Ithnin, C. A. Muryn, H. Onishi, G. Thornton, Nat. Mater., 2006, 5, 189-192.
[39]	L. Hu, Y. Li, W. Zheng, Y. Peng, S. C. E. Tsang, L. Y. S. Lee, K. Wong, J. Mater. Chem. A, 2020, 8, 22828-22839.
[40]	K. Majrik, Z. Pászti, L. Korecz, L. Trif, A. Domján, G. Bonura, C. Cannilla, F. Frusteri, A. Tompos, E. Tálas, Materials, 2018, 11, 1927.
[41]	H. Gao, J. Wang, M. Jia, F. Yang, R. S. Andriamitantsoa, X. Huang, W. Dong, G. Wang, Chem. Eng. J., 2019, 374, 684-693.
[42]	S. Mohajernia, P. Andryskova, G. Zoppellaro, S. Hejazi, S. Kment, R. Zboril, J. Schmidt, P. Schmuki, J. Mater. Chem. A, 2020, 8, 1432-1442.
[43]	O. Al-Madanat, Y. AlSalka, R. Dillert, D. W. Bahnemann, Catalysts, 2021, 11, 107.
[44]	C. Foo, Y. Li, K. Lebedev, T. Chen, S. Day, C. Tang, S. C. E. Tsang, Nat. Commun., 2021, 12, 661.
[45]	K. Zhang, L. Wang, J. K. Kim, M. Ma, G. Veerappan, C. Lee, K. Kong, H. Lee, J. H. Park, Energy Environ. Sci., 2016, 9, 499-503.
[46]	H. Park, T. Goto, S. Cho, H. Nishida, T. Sekino, ACS Omega, 2020, 5, 21753-21761.
[47]	H. Zhang, J. Cai, Y. Wang, M. Wu, M. Meng, Y. Tian, X. Li, J. Zhang, L. Zheng, Z. Jiang, J. Gong, Appl. Catal. B, 2018, 220, 126-136.
[48]	H.-J. Chen, Y.-L. Yang, X.-X. Zou, X.-L. Shi, Z.-G. Chen, J. Mater. Sci. Technol., 2022, 98, 143-150.
[49]	Y. X. Bi, Y. L. Yang, X.-L. Shi, L. Feng, X. J. Hou, X. H. Ye, L. Zhang, G. Q. Suo, S. Y. Lu, Z.-G. Chen, J. Mater. Sci. Technol., 2021, 83, 102-112.
[50]	J. Cai, A. Cao, Z. Wang, S. Lu, Z. Jiang, X. Dong, X. Li, S. Zang, J. Mater. Chem. A, 2021, 9, 13890-13897
[51]	Y. Nosaka, A. Nosaka, ACS Energy Lett., 2016, 1, 356-359.
[52]	J. T. Schneider, D. S. Firak, R. R. Ribeiroa, P. Peralta-Zamoraa, Phys. Chem. Chem. Phys., 2020, 22, 15723-15733.
[53]	L. Bobrova, D. Andreev, E. Ivanov, N. Mezentseva, M. Simonov, L. Makarshin, A. Gribovskii, V. Sadykov, Catalysts, 2017, 7, 310.
[54]	Y. Li, S. C. E. Tsang, Mater. Today Sustain., 2020, 9, 100032.
[55]	Y. Li, Y. Peng, L. Hu, J. Zheng, D. Prabhakaran, S. Wu, T. J. Puchtler, M. Li, K. Wong, R. A. Taylor, S. C. E. Tsang, Nat. Commun., 2019, 10, 4421.
[56]	D. Wang, T. Sheng, J. Chen, H. Wang, P. Hu, Nat. Catal., 2018, 1, 291-299.

基于Pt@TiO₂催化剂光-热协同催化甲醇-水液相重整甲醇制氢

Synergetic photocatalytic and thermocatalytic reforming of methanol for hydrogen production based on Pt@TiO₂ catalyst

RichHTML

PDF

Supporting Information

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

图/表 8

参考文献

相关文章 15

编辑推荐

Metrics

[1]	赵彬彬, 钟威, 陈峰, 王苹, 别传彪, 余火根. 高晶化g-C₃N₄光催化剂: 合成、结构调控和光催化产氢[J]. 催化学报, 2023, 52(9): 127-143.
[2]	唐小龙, 李锋, 李方, 江燕斌, 余长林. 单原子催化剂在光催化和电催化合成过氧化氢中的研究进展[J]. 催化学报, 2023, 52(9): 79-98.
[3]	蔡铭洁, 刘艳萍, 董珂欣, 陈晓波, 李世杰. 漂浮型Bi₂WO₆/C₃N₄/碳布S型异质结光催化材料用于高效净化水体环境[J]. 催化学报, 2023, 52(9): 239-251.
[4]	孙丽娟, 于晓慧, 唐丽永, 王伟康, 刘芹芹. 构建K₃PW₁₂O₄₀/CdS核壳S型异质结实现同步太阳能光催化分解水和选择性苯甲醇氧化反应[J]. 催化学报, 2023, 52(9): 164-175.
[5]	王思恺, 闵祥婷, 乔波涛, 颜宁, 张涛. 单原子催化: 追寻催化领域的“圣杯”[J]. 催化学报, 2023, 52(9): 1-13.
[6]	江梓聪, 程蓓, 张留洋, 张振翼, 别传彪. 氧化锌基梯型异质结光催化剂[J]. 催化学报, 2023, 52(9): 32-49.
[7]	刘博文, 蔡家杰, 张建军, 谭海燕, 程蓓, 许景三. MOF/CdS梯型光催化剂同时进行苯甲醇氧化和析氢反应及其机理研究[J]. 催化学报, 2023, 51(8): 204-215.
[8]	乔蔚, 于立策, 常进法, 杨甫林, 冯立纲. MoSe₂纳米片耦合Pt纳米颗粒用于高效双功能催化甲醇辅助水电解制氢[J]. 催化学报, 2023, 51(8): 113-123.
[9]	宋明明, 宋相海, 刘鑫, 周伟强, 霍鹏伟. ZnIn₂S₄/MOF-808微球结构S型异质结光催化剂的制备及其光还原CO₂性能研究[J]. 催化学报, 2023, 51(8): 180-192.
[10]	邵秀丽, 李可, 李静萍, 程强, 王国宏, 王楷. 揭示NiS@Ta₂O₅纳米纤维中梯型电荷转移路径及光催化CO₂转化性能[J]. 催化学报, 2023, 51(8): 193-203.
[11]	李嘉明, 李源, 王小田, 杨直雄, 张高科. TiO₂上原子分散的Fe位点促进光催化CO₂还原: 增强的催化活性、 DFT计算和机制洞察[J]. 催化学报, 2023, 51(8): 145-156.
[12]	程璐, 陈许宁, 胡培君, 曹宵鸣. 双氧水对于单核铜分子筛催化甲烷直接氧化制甲醇反应性能的利弊[J]. 催化学报, 2023, 51(8): 135-144.
[13]	阎菲, 张由子, 刘思碧, 邹睿卿, Jahan B Ghasemi, 李炫华. 供体-受体型卟啉基金属有机框架实现有效电荷分离高效光催化析氢[J]. 催化学报, 2023, 51(8): 124-134.
[14]	孙利娟, 王伟康, 路平, 刘芹芹, 王乐乐, 唐华. 纳米高熵合金实现光催化剂肖特基势垒的调控用于光催化制氢与苯甲醇氧化耦合反应[J]. 催化学报, 2023, 51(8): 90-100.
[15]	刘海峰, 黄祥, 陈加藏. 电子态调控促进氢气无损耗纯化中CO的光致富集和氧化[J]. 催化学报, 2023, 51(8): 49-54.