Fe2O3/TiO2催化剂高效催化NO加氢制NH3

doi:10.1016/S1872-2067(24)60251-2

催化学报 ›› 2025, Vol. 71: 330-339.DOI: 10.1016/S1872-2067(24)60251-2

Fe₂O₃/TiO₂催化剂高效催化NO加氢制NH₃

李彦琴^a^,^b, 汪文龙^a^,^*(), 田俊奇^c, 崔丹^b, 袁军^c, 方彬^a^,^e, 尹年良^a, 李泽龙^c^,^*(), 于锋^b^,^d^,^*()

^a东莞理工学院材料科学与工程学院, 广东东莞 523808
^b石河子大学化学化工学院新疆兵团化工绿色加工重点实验室, 新疆石河子 832003
^c兰州大学化学化工学院甘肃省高级催化重点实验室, 甘肃兰州 730000
^d石河子大学兵团工业技术研究院碳中和与环境催化技术实验室, 新疆石河子 832003
^e中国科学技术大学化学与材料科学学院, 安徽合肥 230026

收稿日期:2024-11-27 接受日期:2025-01-03 出版日期:2025-04-18 发布日期:2025-04-13
通讯作者: * 电子信箱: wangwl@dgut.edu.cn (汪文龙), lizl@lzu.edu.cn (李泽龙), yufeng05@mail.ipc.ac.cn (于锋).
基金资助:
新疆科技计划(2023TSYCCX0118);国家自然科学基金(21972018)

Highly efficient hydrogenation of NO to NH₃ via a Fe₂O₃/TiO₂ catalyst

Yanqin Li^a^,^b, Wenlong Wang^a^,^*(), Junqi Tian^c, Dan Cui^b, Jun Yuan^c, Bin Fang^a^,^e, Nianliang Yin^a, Zelong Li^c^,^*(), Feng Yu^b^,^d^,^*()

^aSchool of Materials Science and Engineering, Dongguan University of Technology, Dongguan 523808, Guangdong, China
^bKey Laboratory for Green Processing of Chemical Engineering of Xinjiang Bingtuan, School of Chemistry and Chemical Engineering, Shihezi University, Shihezi 832003, Xinjiang, China
^cKey Laboratory of Advanced Catalysis, Gansu Province, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, Gansu, China
^dCarbon Neutralization and Environmental Catalytic Technology Laboratory, Bingtuan Industrial Technology Research Institute, Shihezi University, Shihezi 832003, Xinjiang, China
^eSchool of Chemistry and Materials Science, University of Science and Technology of China, Hefei 230026, Anhui, China

Received:2024-11-27 Accepted:2025-01-03 Online:2025-04-18 Published:2025-04-13
Contact: * E-mail: wangwl@dgut.edu.cn (W. Wang), lizl@lzu.edu.cn (Z. Li), yufeng05@mail.ipc.ac.cn (F. Yu).
Supported by:
Xinjiang Science and Technology Program(2023TSYCCX0118);National Natural Science Foundation of China(21972018)

摘要/Abstract

摘要：

氮氧化物(NO_x)作为大气的主要污染物, 不仅危害生物体的健康, 还会破坏生态环境系统. 为了缓解环境污染, 目前已开发了多种NO消除技术, 其中选择性催化还原NO(NH₃-SCR)因其脱硝效率高、过程相对简单、清洁而成为最成熟、最可靠的脱硝技术之一. 然而, NO本身作为一种含氮分子, 是一种更具活性和经济可行性的氮资源, 相较于直接通过NH₃-SCR技术将其转化为N₂排放，若能利用绿色氢能(H₂)将其催化转化为NH₃，既可实现污染物治理，又能完成高附加值含氮化学品的可持续合成. 因此, 设计一种既能高效去除NO又能实现其加氢合成NH₃催化剂对缓解环境污染和能源危机至关重要.
本文结合水热和浸渍法制备了一种新型Fe₂O₃/TiO₂-MOF催化剂, 并用于催化NO加氢制NH₃. 该催化剂在450 °C, 0.1 MPa和38000 mL g^-1 h^-1的气体空速条件下, 具有99%的NO转化率和95%的NH₃选择性. 此外, 该催化剂还表现出优异的稳定性和耐水、耐硫性能. 通过H₂程序升温还原、NO程序升温脱附和原位红外光谱结果表明, Fe₂O₃/TiO₂-MOF的优异活性归因于Fe₂O₃和TiO₂之间的强相互作用, 这有助于在反应条件下产生用于NO吸附和活化的Fe²⁺活性位点. 密度泛函理论计算表明, 在Fe₂O₃/TiO₂-MOF表面上的NO活化后, 在氮末端发生氢化, 从而进一步加氢生成NH₃. 此外, 探索了NO加氢生成NH₃的反应途径, 证实了该过程的热力学可行性.
综上, 本文采用金属有机框架(MIL-125)衍生的MOF作为载体, 合成了Fe₂O₃/TiO₂-MOF催化剂并高效催化NO选择性转化NH₃, 此反应的关键是Fe₂O₃和TiO₂-MOF之间的相互作用, 在反应条件下产生用于NO吸附和活化的Fe²⁺. 本文为合理设计NO加氢合成NH₃催化剂提供了新思路.

关键词: 氮氧化物, 合成氨, NO加氢, 选择性催化还原, 脱硝

Abstract:

Nitrogen oxides (NO_x) present in flue gas are economically renewable N1 resources. Unlike traditional selective catalytic reduction processes that convert NO into N₂, redirecting NO towards the synthesis of value-added NH₃ offers significant practical benefits. In this study, a Ti-based metal-organic framework (Ti-MOF), specifically MIL-125, was utilized as a support for Fe, which was subsequently calcined at 400 °C to produce a Fe₂O₃/TiO₂-MOF catalyst. The resulting catalyst demonstrated exceptional performance, achieving 99% NO conversion and 95% NH₃ selectivity under optimal conditions of 450 °C, 0.1 MPa, and a gas hourly space velocity of 38000 mL g^-1 h⁻¹. Additionally, the catalyst exhibited excellent stability and resistance to water and sulfur. The high efficiency of Fe₂O₃/TiO₂-MOF is attributed to the abundance of Fe²⁺ sites at the reaction temperature, which enhances NO adsorption and activation. Furthermore, density functional theory calculations suggest that NO undergoes hydrogenation at the N-terminus on the Fe₂O₃/TiO₂-MOF surface, leading directly to NH₃ synthesis rather than dissociation followed by hydrogenation. This catalyst presents a novel approach for converting NO_x into high-value chemical products.

Key words: Nitrogen oxides, Synthetic ammonia, NO hydrogenation, Selective catalytic reduction, Denitration

李彦琴, 汪文龙, 田俊奇, 崔丹, 袁军, 方彬, 尹年良, 李泽龙, 于锋. Fe₂O₃/TiO₂催化剂高效催化NO加氢制NH₃[J]. 催化学报, 2025, 71: 330-339.

Yanqin Li, Wenlong Wang, Junqi Tian, Dan Cui, Jun Yuan, Bin Fang, Nianliang Yin, Zelong Li, Feng Yu. Highly efficient hydrogenation of NO to NH₃ via a Fe₂O₃/TiO₂ catalyst[J]. Chinese Journal of Catalysis, 2025, 71: 330-339.

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Fig. 1. Catalytic performance of the catalyst. (a) NO conversion. (b) NH3 selectivity of the TiO2-HC, TiO2-MOF, Fe2O3, Fe2O3/TiO2-HC, and Fe2O3/TiO2-MOF catalysts. Stability test (c) and resistance to H2O and SO2 (d) of the Fe2O3/TiO2-MOF catalysts. Reaction conditions: [NO] = 350 ppm, [H2] = 2000 ppm, balance N2, total flow rate: 100 mL min?1, GHSV: 38000 mL g-1 h?1, catalyst: 0.2 g.

Fig. 2. Structural characterization of the catalysts. (a) XRD patterns of the Ti-MOF (MIL-125), TiO2-HC, TiO2-MOF, Fe2O3/TiO2-HC, and Fe2O3/TiO2-MOF catalysts. (b,c) Raman spectra of catalysts at 532 and 325 nm laser. XPS spectra of the Fe 2p (d), O 1s (e), Ti 2p (f). (g) EPR spectra of the TiO2-HC, TiO2-MOF, Fe2O3/TiO2-HC, and Fe2O3/TiO2-MOF catalysts. (h) H2-TPR profiles of the TiO2-HC, TiO2-MOF, Fe2O3, Fe2O3/TiO2-HC, and Fe2O3/TiO2-MOF catalysts. (i) Schematic description of the Fe2O3/TiO2 catalyst model.

Fig. 3. NO desorption, NH3 desorption, and characterization of surface species. NO-TPD (a) and NH3-TPD (b) curves of the TiO2-HC, TiO2-MOF, Fe2O3, Fe2O3/TiO2-HC, and Fe2O3/TiO2-MOF catalysts after treatment with H2 at 450 °C. In situ DRIFTS spectra of the Fe2O3/TiO2-MOF catalyst: (c) adsorption spectra of NO on the catalyst at different temperatures; (d) Co-adsorption spectra of NO-H2 gas at different temperatures.

Fig. 4. DFT calculations. (a,b) Partial density of states (PDOS) of NO and NH3 adsorbed at the surface of Fe2O3/TiO2. (c,d) Corresponding charge differential density. The pink area represents the accumulation of electrons; the blue area represents the loss of electrons. (e) Energy potential and molecular configuration changes during the (I) *NO → *N + *O dissociation, (II) *NO + H → *NOH hydrogenation, and (II) *HNO → *NO + *H processes. The initial state (IS), transition state (TS), and final state (FS) are shown. The units of the values in the images are in Angstrom (?).

Fig. 5. Reaction path calculation. Possible pathway of NO hydrogenation to NH3 using the Fe2O3/TiO2 catalyst.

参考文献

[1]	X. Wang, H. Ma, B. Li, Y. Wang, S. Zhang, W. Li, S. Li, Chem. Eng. J., 2022, 435, 134892.
[2]	W. Hu, J. He, X. Liu, H. Yu, X. Jia, T. Yan, L. Han, D. Zhang, Environ. Sci. Technol., 2022, 56, 5170-5178.
[3]	L. E. Gevers, L. R. Enakonda, A. Shahid, S. Ould-Chikh, C. I. Silva, P. P. Paalanen, A. Aguilar-Tapia, J.-L. Hazemann, M. N. Hedhili, F. Wen, J. Ruiz-Martinez, Nat. commun., 2022, 13, 2960.
[4]	F. Yu, Chem. Ind. Eng. Prog., 2023, 42, 6136.
[5]	S. Li, X. Chen, F. Wang, Z. Xie, Z. Hao, L. Liu, B. Shen, J. Hazard. Mater., 2022, 431, 128622.
[6]	Y. Zhang, J. Chen, Z. Liu, Catal. Today, 2022, 402, 115-121.
[7]	X. Yi, J. Wang, Y. Liu, Y. Chen, J. Chen, Catal. Sci. Technol., 2022, 12, 4169-4180.
[8]	Z. Fan, J.-W. Shi, C. Gao, G. Gao, B. Wang, C. Niu, ACS Appl. Mater. Interfaces, 2017, 9, 16117-16127.
[9]	L. Li, P. Li, W. Tan, K. Ma, W. Zou, C. Tang, L. Dong, Chin. J. Catal., 2020, 41, 364-373.
[10]	Q. Lin, J. Liu, S. Liu, S. Xu, C. Lin, X. Feng, Y. Wang, H. Xu, Y. Chen, Dalton Trans., 2018, 47, 15038-15048.
[11]	R. Li, X. Jiang, J. Lin, Z. Zhang, Q. Huang, G. Fu, Y. Zhu, J. Jiang, Chem. Eng. J., 2022, 441, 136021.
[12]	S. Liu, B. Wang, Z. Guo, B. Wang, Z. Zhang, M. Xiao, C.-T. Chang, W. Peng, H. Xin, X. Sun, S. Shuai, Appl. Therm. Eng., 2022, 205, 117994.
[13]	F. Yu, Int. J. Hydrogen Energy, 2024, 61, 1043-1046.
[14]	R. Schlögl, Angew. Chem. Int. Ed., 2003, 42, 2004-2008.
[15]	A. Klerke, C. H. Christensen, J. K. Nørskov, T. Vegge, J. Mater. Chem., 2008, 18, 2304-2310.
[16]	H. Su, L. Chen, Y. Chen, R. Si, Y. Wu, X. Wu, Z. Geng, W. Zhang, J. Zeng, Angew. Chem. Int. Ed., 2020, 59, 20411-20416.
[17]	L. Wang, M. Xia, H. Wang, K. Huang, C. Qian, C. T. Maravelias, G. A. Ozin, Joule, 2018, 2, 1055-1074.
[18]	G. Qing, R. Ghazfar, S. T. Jackowski, F. Habibzadeh, M. M. Ashtiani, C.-P. Chen, M. R. Smith III, T. W. Hamann, Chem. Rev., 2020, 120, 5437-5516.
[19]	W. Guo, K. Zhang, Z. Liang, R. Zou, Q. Xu, Chem. Soc. Rev., 2019, 48, 5658-5716.
[20]	S. Smidstrup, T. Markussen, P. Vancraeyveld, J. Wellendorff, J. Schneider, T. Gunst, B. Verstichel, D. Stradi, P. A. Khomyakov, U. G. Vej-Hansen, M.-E. Lee, S. T. Chill, F. Rasmussen, G. Penazzi, F. Corsetti, A. Ojanperae, K. Jensen, M. L. N. Palsgaard, U. Martinez, A. Blom, M. Brandbyge, K. Stokbro, J. Phys. Condens. Mater., 2020, 32, 015901.
[21]	Y. Li, J. Tian, Z. Liu, Z. Liu, D. Dong, F. Wang, W. Wang, M. Liu, J. Dan, Y. Li, F. Yu, B. Dai, Y. Yu, Green Energy Environ., 2023, 8, 1102-1116.
[22]	C. H. Lee, E. B. Nam, M. E. Lee, S. U. Lee, Nano Energy, 2019, 63, 103863.
[23]	J. Qiu, D. Dai, L. Zhang, M. Li, J. Xu, J. Yao, Microporous Mesoporous Mater., 2021, 319, 111043.
[24]	J. Cao, W. Liu, K. Kang, L. Chen, X. Qiao, X. Yao, Appl. Catal. A, 2021, 623, 118285.
[25]	L. Qi, Z. Sun, Q. Tang, J. Wang, T. Huang, C. Sun, F. Gao, C. Tang, L. Dong, J. Hazard. Mater., 2020, 396, 122459.
[26]	Z. Bao, W. Ding, Q. Li, Int. J. hydrogen Energy, 2012, 37, 951-955.
[27]	K. Zhao, Z. Li, T. Yan, Z. Gao, Q. He, Q. Wang, W. Liu, J. Zhang, X. Zhao, L. Liu, C. Liu, J. Environ. Chem. Eng., 2023, 11, 109757.
[28]	X. Yao, L. Chen, J. Cao, Y. Chen, M. Tian, F. Yang, J. Sun, C. Tang, L. Dong, Chem. Eng. J., 2019, 369, 46-56.
[29]	Z. Liu, S. Zhang, J. Li, L. Ma, Appl. Catal. B, 2014, 144, 90-95.
[30]	Y. Peng, K. Li, J. Li, Appl. Catal. B, 2013, 140-141, 483-492.
[31]	G. Berlier, G. Spoto, P. Fisicaro, S. Bordiga, A. Zecchina, E. Giamello, C. Lamberti, Microchem. J., 2002, 71, 101-116.
[32]	Y. Wang, C. Ge, L. Zhan, C. Li, W. Qiao, L. Ling, Ind. Eng. Chem. Res., 2012, 51, 11667-11673.
[33]	G. Spoto, A. Zecchina, G. Berlier, S. Bordiga, M. Clerici, L. Basini, J. Mol. Catal. A, 2000, 158, 107-114.
[34]	S. Yuen, J. Kubsh, J. Dumesic, N. Topsoee, H. Topsoee, Y. Chen, J. Phys. Chem., 1982, 86, 3022-3032.
[35]	M. Zhu, J.-K. Lai, U. Tumuluri, Z. Wu, I. E. Wachs, J. Am. Chem. Soc., 2017, 139, 15624-15627.
[36]	C. He, H. Yang, M. Xi, L. Fu, J. Huo, C. Zhao, Environ. Res., 2022, 212, 113479.
[37]	B. Huang, B. Chen, G. Zhu, J. Peng, P. Zhang, Y. Qian, N. Li, ChemPhysChem, 2022, 23, e202100785.
[38]	J. Yang, H. Qi, A. Li, X. Liu, X. Yang, S. Zhang, Q. Zhao, Q. Jiang, Y. Su, L. Zhang, J.-F. Li, Z.-Q. Tian, W. Liu, A. Wang, T. Zhang, J. Am. Chem. Soc., 2022, 144, 12062-12071.

Fe₂O₃/TiO₂催化剂高效催化NO加氢制NH₃

Highly efficient hydrogenation of NO to NH₃ via a Fe₂O₃/TiO₂ catalyst

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