耦合氨氧化和水还原反应实现电化学共合成硝酸盐和氢气

doi:10.1016/S1872-2067(23)64561-9

催化学报 ›› 2023, Vol. 55: 216-226.DOI: 10.1016/S1872-2067(23)64561-9

耦合氨氧化和水还原反应实现电化学共合成硝酸盐和氢气

朱可涵^a, 蒋海凤^a^,^b^,^*(), 陈高锋^a^,^*(), 吴昊^c, 丁良鑫^a, 王海辉^b^,^*()

^a华南理工大学化学与化工学院, 广东广州 510640
^b清华大学化工系, 膜材料与工程北京重点实验室, 北京 100084
^c华南理工大学物理与光电子学院, 广东广州 510641

收稿日期:2023-10-07 接受日期:2023-11-02 出版日期:2023-12-18 发布日期:2023-12-07
通讯作者: *电子信箱: jhfeng1006@mail.tsinghua.edu.cn (蒋海凤), chengf@scut.edu.cn (陈高锋), cehhwang@tsinghua.edu.cn (王海辉).
基金资助:
国家重点研发计划(2022YFB4002602);国家自然科学基金(22022503);国家自然科学基金(22138005);新基石科学基金会探索者奖;中国博士后科学基金(2023TQ0185);清华大学水木清华学者计划.

Simultaneous electrosynthesis of nitrate and hydrogen by integrating ammonia oxidation and water reduction

Kehan Zhu^a, Haifeng Jiang^a^,^b^,^*(), Gao-Feng Chen^a^,^*(), Hao Wu^c, Liang-Xin Ding^a, Haihui Wang^b^,^*()

^aSchool of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, Guangdong, China
^bBeijing Key Laboratory for Membrane Materials and Engineering, Department of Chemical Engineering, Tsinghua University, Beijing 100084, China
^cSchool of Physics and Optoelectronics, South China University of Technology, Guangzhou 510641, Guangdong, China

Received:2023-10-07 Accepted:2023-11-02 Online:2023-12-18 Published:2023-12-07
Contact: *E-mail: jhfeng1006@mail.tsinghua.edu.cn (H. Jiang), chengf@scut.edu.cn (G. Chen), cehhwang@tsinghua.edu.cn (H. Wang).
Supported by:
National Key R&D Program of China(2022YFB4002602);Natural Science Foundation of China(22022503);Natural Science Foundation of China(22138005);New Cornerstone Science Foundation through the XPLORER PRIZE;China Postdoctoral Science Foundation(2023TQ0185);Shuimu Tsinghua Scholar Program from Tsinghua University.

摘要/Abstract

摘要：

硝酸(HNO₃)是一种重要的含氮化学品, 在肥料、火药及炸药等制造领域有广泛的应用, 全球年产量高达5000万公吨. 传统的硝酸生产主要通过Ostwald工艺, 该工艺需要高温(600‒800 °C)和高压(4‒10 bar)条件, 并使用贵金属催化剂(如Pt-Rh合金网), 先通过逐步催化氧化Haber-Bosch法制得氨, 再进一步生成硝酸和水. 该方法能耗高, 对化石燃料依赖性强, 且会排放温室气体CO₂. 因此, 探索在温和条件下高效、环保和可持续地制备硝酸方法具有重要意义.

本文设计了一种新型的电化学氨氧化和水还原反应耦合体系, 可同时电化学合成硝酸盐和氢气. 通过电化学氧化方法原位实现了Cu原子和O原子的可控重组, 在不同条件下合成出以Cu₂O为主的Cu-OX-PBS催化剂和以CuO为主的Cu-OX-KOH纳米片阵列催化剂. 对比两种催化剂催化氨氧化反应性能发现, CuO是将氨转化为NO₃^-的主要活性位点. 在使用Cu-OX-KOH催化剂进行氨氧化反应时, 通过调控氨氧化电位策略可实现八电子转移过程中氨到NO₃^-的转化. Cu-OX-KOH纳米片阵列催化剂在1.5 V vs. RHE下合成NO_x^-的法拉第效率高达98.7%, 并且最高产率达到121.0 ± 5.4 μmol h^‒1 cm^‒2 (2.1 V vs. RHE); 同时, 在阴极端连续产生H₂时具有97.7%的法拉第效率(1.8 V vs. RHE), 从而实现了硝酸盐和氢气的同时高效合成. 此外, 在经108 h稳定性测试后, 该反应体系可收集到0.2 mol L^-1 NO_x^-产物, 且反应后催化剂形貌未发生改变, 表明CuO纳米片阵列催化剂具有较高的稳定性和实际应用潜力. 通过监测反应体系中NH₃, NO₂^-, NO₃^-三种物质随时间的变化情况, 考察了氨氧化电合成NO₃^-的反应过程. 结果表明, NO₂^-是氨氧化到NO₃^-反应过程中的重要中间体, 并且随着反应进行, NO₂^-最终转化为NO₃^-. 为进一步分析反应机理, 利用原位红外技术检测重要中间体*NH₂, *NH, *NO和NO₂等的形成, 并通过密度泛函理论验证了在CuO催化作用下氨氧化到NO₃^-是一个逐级脱氢加氧的过程, 进而推测出氨氧化到NO₃^-的八电子反应路径并分析了实验过程中NO₂^-中间体生成的可能原因.

综上所述, 本文将氨氧化与电解水巧妙地耦合电化学共合成硝酸盐和氢气, 为在温和条件下利用可再生能源实现氨与水共活化及高效转化提供了新思路, 并为现场原位生成硝酸和氢气提供了参考.

关键词: 氨氧化, CuO纳米片阵列, 硝酸电合成, 水还原, 产氢

Abstract:

Electrosynthesis of nitrate powered by renewable energy sources under mild conditions is an attractive alternative to the Oswald process for avoiding consuming large amounts of fossil fuels and eliminating associated greenhouse gas emissions. Here, we present an energy-saving and environmentally friendly strategy for efficient electrosynthesis of nitrate from ammonia oxidation by integrating hydrogen production from water reduction. We design a superior stable CuO nanosheet array catalyst and realize a total NO_x^- Faradaic efficiency of 98.7% via ammonia oxidation reaction (AOR) in an aqueous electrolyte. Hydrogen generation with a high Faradaic efficiency of 97.7% at the cathodic side is a concomitant AOR process. 0.2 mol L^-1 NO_x^- can be produced after a long-term stability testing for 108 h, suggesting a potential practical application in decentralized nitrate and green hydrogen production.

Key words: Ammonia oxidation, CuO nanosheet array, Nitrate electrosynthesis, Water reduction, Hydrogen production

朱可涵, 蒋海凤, 陈高锋, 吴昊, 丁良鑫, 王海辉. 耦合氨氧化和水还原反应实现电化学共合成硝酸盐和氢气[J]. 催化学报, 2023, 55: 216-226.

Kehan Zhu, Haifeng Jiang, Gao-Feng Chen, Hao Wu, Liang-Xin Ding, Haihui Wang. Simultaneous electrosynthesis of nitrate and hydrogen by integrating ammonia oxidation and water reduction[J]. Chinese Journal of Catalysis, 2023, 55: 216-226.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(23)64561-9

https://www.cjcatal.com/CN/Y2023/V55/I12/216

图/表 6

Fig. 1. (a) Schematics illustrating the industrial nitric acid synthesis by the Ostwald process. (b) Electrochemical technology for nitrate production at the anodic part with assisted green hydrogen production at the cathodic part.

Fig. 2. Physical characterization of synthesis CuO nanosheet covered vertical Cu nanorod arrays substrate (Cu-OX-KOH). SEM images at two scale bars of 5 μm (a) and 500 nm (b). (c) SAED pattern. TEM image (d) and corresponding HR-TEM image (e). (f) STEM and corresponding elemental mapping images.

Fig. 3. Comparison with electrocatalytic AOR performance and identification of active sites. (a) XRD patterns of Cu-NA, Cu-OX-PBS, and Cu-OX-KOH. (b) High-resolution Cu 2p XPS spectrum. (c) Comparison NO2- and NO3- yield rate for AOR process by employing Cu-OX-KOH and Cu-OX-PBS at 1.7, 1.8 and 1.9 V vs. RHE in 137 ppm NH3/0.1 mol L?1 KOH electrolyte. (d) Total Faradaic efficiency yielding NO2- and NO3- at three potentials.

Fig. 4. Electrochemical ammonia oxidation activities. (a) LSV curves of Cu-OX-KOH recorded in three electrolytes at a scan rate of 5 mV s-1. (b) NOx- yield rate and total Faradaic efficiency in 137 ppm NH3/0.1 mol L-1 KOH at various applied potentials. (c) The corresponding NH3 conversion at different applied potentials. (d) Time-dependent initial NH3 and NOx- yield change profiles at 1.8 V vs. RHE when using 137 pm NH3/0.1 mol L-1 KOH as reactant. (e) The cyclic stability of Cu-OX-KOH at 1.8 V vs. RHE. (f) Hydrogen yield and Faradaic efficiency at cathodic side during AOR process at 1.8 V vs. RHE. (g) Long-term stability of Cu-OX-KOH for large-scale production of nitric acid in 70 mL 200 ppm NH3/0.1 mol L-1 KOH working at 1.8 V vs. RHE. (h) Cu 2p XPS spectrum before and after long-term stability testing.

Fig. 5. Electrochemical in-situ FTIR spectra of the AOR on the Cu-OX-KOH electrode at 2.1 V vs. RHE under 200 ppm/0.1 mol L?1 KOH.

Fig. 6. DFT calculations for AOR processes. (a) DFT-calculated bonding energy of NH3 on Cu2O (111), CuO (111), CuO (002) and Cu (111) facet, respectively. (b) Gibbs free energy profiles of NH3 oxidation to NO3? reaction on CuO (002) surface of Cu-OX-KOH with an applied potential of U = 2.1 V vs. RHE. (c) Schematic diagram of pathways for the electrochemical oxidation of NH3 to NO3- and the corresponding transition state (TS) barriers.

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耦合氨氧化和水还原反应实现电化学共合成硝酸盐和氢气

Simultaneous electrosynthesis of nitrate and hydrogen by integrating ammonia oxidation and water reduction

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