Cu/CeO2上可见光辅助热催化合成NH3: H2O存在下NO通过CO还原的途径

doi:10.1016/S1872-2067(23)64439-0

催化学报 ›› 2023, Vol. 49: 168-179.DOI: 10.1016/S1872-2067(23)64439-0

Cu/CeO₂上可见光辅助热催化合成NH₃: H₂O存在下NO通过CO还原的途径

宋昕杰^a^,^b, 范世鹏^a^,^c, 蔡泽华^a^,^c, 杨洲^a^,^c, 陈旬^a, 付贤智^a^,^*(), 戴文新^a^,^b^,^*()

^a福州大学光催化能源与环境国家重点实验室光催化研究所, 福建福州 350002
^b清源创新实验室, 福建泉州 362801
^c生态材料高等技术重点实验室(福州大学), 福建福州 350002

收稿日期:2023-03-15 接受日期:2023-04-04 出版日期:2023-06-18 发布日期:2023-06-05
通讯作者: ^*电子信箱: daiwenxin@fzu.edu.cn (戴文新),xzfu@fzu.edu.cn (付贤智).
基金资助:
国家自然科学基金(21872030);国家自然科学基金(22272025);清源创新实验室重点项目(00121001);福建省科技重点计划项目(2021YZ037005)

NH₃ synthesis via visible-light-assisted thermocatalytic NO reduction by CO in the presence of H₂O over Cu/CeO₂

Xinjie Song^a^,^b, Shipeng Fan^a^,^c, Zehua Cai^a^,^c, Zhou Yang^a^,^c, Xun Chen^a, Xianzhi Fu^a^,^*(), Wenxin Dai^a^,^b^,^*()

^aResearch Institute of Photocatalysis, State Key Laboratory of Photocatalysis on Energy and Environment, Fuzhou University, Fuzhou 350002, Fujian, China
^bQingyuan Innovation Laboratory, Quanzhou 362801, Fujian, China
^cKey Laboratory of Eco-materials Advanced Technology (Fuzhou University), Fujian Province University, Fuzhou 350002, Fujian, China

Received:2023-03-15 Accepted:2023-04-04 Online:2023-06-18 Published:2023-06-05
Contact: ^*E-mail: daiwenxin@fzu.edu.cn (W. Dai), xzfu@fzu.edu.cn (X. Fu).
Supported by:
National Natural Science Foundation of China(21872030);National Natural Science Foundation of China(22272025);Key Program of Qingyuan Innovation Laboratory(00121001);Science & Technology Key Plan Project of Fujian Province(2021YZ037005)

摘要/Abstract

摘要：

NH₃不仅是关键的工业化学原料, 而且是未来可再生能源的无碳燃料和可运输的载体. 目前, 工业合成NH₃仍然以传统的Haber-Bosch反应为主, 需要300‒500 °C的高温和20‒30 MPa的压力. 为克服这些缺点, 研究者设计了NO-CO-H₂O反应体系. 在该反应中, 通过有毒气体CO在H₂O存在的条件下将NO还原成NH₃, 这是一种近乎理想的生产NH₃的方法. 目前, 已经报道了Pt/Al₂O₃在NO-CO-H₂O反应中具有较高的NH₃选择性, 但反应温度(400 °C)仍然较高, 不利于实际应用. 因此, 在低温条件下引入光照, 通过光辅助热催化NO-CO-H₂O反应来获得NH₃产品, 是一种极具发展潜力的方法.

研究人员通过密度泛函理论(DFT)研究发现, Cu在NO还原反应中具有很高的活性和NH₃选择性, 且Cu在水煤气(CO+H₂O)变换反应中具有较高的活性. CeO₂具有丰富氧空位同时能充当碳酸盐的储存位点, 还可以起到稳定分散铜的作用. 因此, 本文将具有局域表面等离子体共振(LSPR)效应的金属Cu负载在具有氧空位的棒状CeO₂上形成Cu/CeO₂纳米复合材料, 并研究了其催化NO-CO-H₂O反应性能. 结果表明, Cu/CeO₂不仅在100‒270 °C下表现出较好的CO和NO去除效率, 且可以选择性地催化还原NO为NH₃. 其中, 5% Cu/CeO₂表现出最优催化活性, 210 °C时NO转化率为94.4%和NH₃选择性为66.5%. 在相同温度下, 可见光可以进一步提高NO转化率(97.7%)和NH₃选择性(69.1%). 通过对NO-CO-H₂O反应进行分步活性测试, 发现该反应的主要过程由水煤气变化反应生成活性H*及其进一步与NO发生选择性催化还原反应两部分组成. 准原位电子顺磁共振、原位漫反射傅立叶变换红外光谱和密度泛函理论计算表明, 在Cu/CeO₂上NO-CO-H₂O的反应机理是CO首先与H₂O反应形成HCO₃*中间物, 然后分解成CO₂和活性H*, 最后NO与活性H*反应产生NH₃. 而可见光诱导Cu的LSPR效应能有效地将催化剂的光吸收范围拓宽至可见光, 同时其产生的热电子能有效提高催化剂表面电子密度, 从而促进了HCO₃*分解为CO₂和活性H*; 另外, 在CeO₂上再生了氧空位(H₂O的活化点), 进而增加了NH₃产量. 综上, 本文提供了一种在温和条件下合成NH₃的可行性方法, 能为合成NH₃工艺提供一种新途径.

关键词: NO-CO-H₂O反应, NH₃合成, 局域表面等离子体共振, 氧空位, Cu/CeO₂

Abstract:

A photothermal catalytic system comprising Cu/CeO₂ was applied to the reaction between NO, CO and H₂O for the production of NH₃ under visible-light irradiation. High NO conversion (94.4%) and NH₃ selectivity (66.5%) were achieved over Cu/CeO₂ in the presence of H₂O at 210 °C. Visible light further improved the conversion of NO (97.7%) and selectivity for NH₃ (69.1%). The quasi-situ EPR and in-situ DRIFTS results indicated that CO initially reacts with H₂O to form an HCO₃^* intermediate, which then decomposes into CO₂ and activated H*. Finally, NO reacts with activated H* to produce NH₃. The localized surface plasmon resonance effect of Cu nanoparticles induced by visible light promotes the decomposition of HCO₃^* to CO₂ and H*, while regenerating oxygen vacancies (OVs, H₂O activation sites) at the CeO₂sites, resulting in enhanced NH₃ production. This study offers a convenient approach for NH₃ production under mild conditions.

Key words: NO-CO-H₂O reaction, NH₃ production, Localized surface plasmon resonance, Oxygen vacancies, Cu/CeO₂

宋昕杰, 范世鹏, 蔡泽华, 杨洲, 陈旬, 付贤智, 戴文新. Cu/CeO₂上可见光辅助热催化合成NH₃: H₂O存在下NO通过CO还原的途径[J]. 催化学报, 2023, 49: 168-179.

Xinjie Song, Shipeng Fan, Zehua Cai, Zhou Yang, Xun Chen, Xianzhi Fu, Wenxin Dai. NH₃ synthesis via visible-light-assisted thermocatalytic NO reduction by CO in the presence of H₂O over Cu/CeO₂[J]. Chinese Journal of Catalysis, 2023, 49: 168-179.

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图/表 12

Fig. 1. (a) XRD patterns of CeO2 and Cu/CeO2. (b) H2-TPR profiles of CeO2, CuOx/CeO2, and CuO. (c) Dispersion of metal Cu over Cu/CeO2. (d) DRS spectra of CeO2 and Cu/CeO2.

Fig. 2. HRTEM images (a,b) and elemental mapping (c) of Cu/CeO2.

Fig. 3. CO conversion (a), NO conversion (b), yield of NH3 (c), and NH3 selectivity (d) at various reaction temperatures over Cu/CeO2 in the dark or under visible light irradiation.

Fig. 4. (a) CO conversion in the CO-H2O reaction. (b) Yield of NH3 in the NO-H2 reaction. (c) Yield of H2 in the NO-CO-H2O reaction. (d) Yield of H2 in the CO-H2O reaction over Cu/CeO2 in the dark or under visible light irradiation.

Fig. 5. Quasi-situ EPR spectra of the Cu/CeO2 sample obtained with each treatment condition in the experimental sequence.

Fig. 6. High-resolution XPS O 1s (a), Ce 3d (b), Cu 2p (c) spectra, and Cu LMM Auger electron spectra (d) of Cu/CeO2 samples obtained before and after the reaction in the presence or absence of light. (Fresh): after N2 pretreatment for 2 h at 300 °C, (In Dark): after reacting at 210 °C in the dark, (In Light) means after reacting at 210 °C under visible irradiation.

Table 1 Relative contents of O and Ce elements in Cu/CeO2 before and after the reaction in the presence or absence of light.

Sample	Treatment	O_ad/O_total (at%)	Ce³⁺/Ce_total (at%)
	Fresh	25.3	29.5
Cu/CeO₂	In dark	23.4	27.7
	In light	27.4	30.3

Fig. 7. In-situ DRIFTS of Cu/CeO2 confirming H2O+CO (a) and NO adsorption (b) during the visible light reaction process.

Fig. 8. Adsorption models: (a) CO-OVs; (b) OC-OVs; (c) H2O-OVs; (d) H2O-Cu. The pristine bond lengths of CO and H2O are 1.128 and 0.960 ?, respectively. H2O is more likely to be adsorbed onto the OVs.

Fig. 9. Adsorption models: (a) NO-Cu; (b) NO-OVs. The pristine bond length of NO is 1.151 ?. (c) Differences in the charge distribution of Cu/CeO2 with adsorbed NO; the blue and yellow represent charge loss and accumulation, respectively. Δq < 0 implies electron donation from Cu to NO.

Fig. 10. (a) Transient photocurrent responses. (b) Electrochemical impedance spectroscopy results. (c) PL spectra of CeO2 and Cu/CeO2.

Fig. 11. Proposed NO-CO-H2O reaction process over Cu/CeO2.

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Cu/CeO₂上可见光辅助热催化合成NH₃: H₂O存在下NO通过CO还原的途径

NH₃ synthesis via visible-light-assisted thermocatalytic NO reduction by CO in the presence of H₂O over Cu/CeO₂

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