白钨矿型碱金属高铼酸盐负载的钴基催化剂用于高效合成氨

doi:10.1016/S1872-2067(26)64983-2

催化学报 ›› 2026, Vol. 83: 432-443.DOI: 10.1016/S1872-2067(26)64983-2

• 论文 • 上一篇

白钨矿型碱金属高铼酸盐负载的钴基催化剂用于高效合成氨

彭渲北^a^,^b^,¹, 安梦琪^b^,¹, 毛瑞绍^b^,¹, 周岩良^a^,^b^,^*(), 陈名^b, 黄东雅^b, 苏凯琳^b, 章世勇^b, 倪军^b^,^*(), 王秀云^a^,^b^,^*(), 江莉龙^a^,^b

^a清源创新实验室, 福建泉州 362801
^b福州大学化肥催化剂国家工程研究中心, 福建福州 350002

收稿日期:2025-07-02 接受日期:2025-08-15 出版日期:2026-04-18 发布日期:2026-03-04
通讯作者: * 电子信箱: zhouyl@fzu.edu.cn (周岩良), nj@fzu.edu.cn (倪军), xywangfzu@163.com (王秀云).
作者简介:¹共同第一作者.
基金资助:
国家重点研发计划(2022YFA1604101);国家自然科学基金(22222801);国家自然科学基金(22221005);国家自然科学基金(92361303);国家自然科学基金(92461312);国家自然科学基金(22478075);国家自然科学基金(22472028);上海市科学技术委员会重点研发计划(21DZ1209002);中国博士后科学基金(2025T180317)

Scheelite-type alkali metal perrhenates supported Co-based catalysts for highly efficient ammonia synthesis

Xuanbei Peng^a^,^b^,¹, Mengqi An^b^,¹, Ruishao Mao^b^,¹, Yanliang Zhou^a^,^b^,^*(), Ming Chen^b, Dongya Huang^b, Kailin Su^b, Shiyong Zhang^b, Jun Ni^b^,^*(), Xiuyun Wang^a^,^b^,^*(), Lilong Jiang^a^,^b

^aQingyuan Innovation Laboratory, Quanzhou 362801, Fujian, China
^bNational Engineering Research Center of Chemical Fertilizer Catalyst, Fuzhou University, Fuzhou 350002, Fujian, China

Received:2025-07-02 Accepted:2025-08-15 Online:2026-04-18 Published:2026-03-04
Contact: * E-mail: zhouyl@fzu.edu.cn (Y. Zhou), nj@fzu.edu.cn (J. Ni), xywangfzu@163.com (X. Wang).
About author:¹Contributed equally to this work.
Supported by:
National Key Research and Development Program(2022YFA1604101);National Natural Science Foundation of China(22222801);National Natural Science Foundation of China(22221005);National Natural Science Foundation of China(92361303);National Natural Science Foundation of China(92461312);National Natural Science Foundation of China(22478075);National Natural Science Foundation of China(22472028);Key R&D plan of Shanghai Science and Technology Commission(21DZ1209002);China Postdoctoral Science Foundation(2025T180317)

摘要/Abstract

摘要：

氨是生产化肥的关键原料, 也是潜在的氢能源载体. 工业上主要采用Haber-Bosch工艺生产氨, 该工艺使用传统的铁(Fe)基催化剂, 需要苛刻的反应条件(400-500 °C和10-30 MPa). 与Fe基催化剂相比, 钌(Ru)基催化剂虽然在温和条件下表现出更优异的催化活性, 但在工业应用中存在Ru价格昂贵等成本问题. 非贵金属钴(Co)基催化剂在合成氨催化性能中表现出色. 然而, 除了活性金属的选择, 载体的类型对于催化剂合成氨性能也具有重要影响. 目前, 各种传统载体材料的研究在合成氨中都呈现出反应惰性, 对于具有高反应性的载体研究较少. 因此, 通过高反应性载体和活性金属Co相结合以研发高效的合成氨催化剂并探究其反应机制是本文的主要研究思路.
本文通过浸渍法合成了一系列具有高反应性碱金属高铼酸盐(AMReO₄, AM = K, Na或Cs)载体负载的Co基催化剂. AMReO₄载体包含了活性金属Re和助剂, 在合成氨反应中呈现出一定的催化活性. 其中, 在400 °C和1 MPa下, KReO₄呈现出最高的合成氨速率为3.58 mmol_NH3 g_cat⁻¹ h⁻¹. 当以KReO₄为载体负载不同含量的Co后, 催化剂的合成氨速率显著增加. 在相同反应条件下, Co含量为15 wt%的15Co/KReO₄催化剂的合成氨速率达到11.48 mmol_NH3 g_cat⁻¹ h⁻¹, 是KReO₄载体的3.2倍, 且15Co/KReO₄催化剂在持续反应100 h后没有明显的活性下降趋势, 表现出较好的热稳定性. 通过X-射线衍射, 透射电子显微镜和原位拉曼光谱测试结果表明, 在合成氨反应条件下KReO₄载体中Re与Co金属存在强相互作用, 并观察到少量CoRe纳米颗粒以合金形式存在. 氮气或氢气程序升温脱附实验结果表明, 高反应性KReO₄对N₂具有很强的亲和力, 并对于H₂的活化起主要作用. X-射线吸收光谱和准原位X-射线光电子能谱结果表明, Re与Co存在强电子相互作用, Co的引入有利于向Re金属捐赠电子. 此外, Co的存在也为N₂的吸附和活化提供了活性位点, 能够与Re协同促进N₂的活化. 氢气程序升温还原实验和WO₃变色实验结果表明Co物种的引入促进了H溢流效应, 使*H物种从Re位点迁移到Co位点或载体上, 然后通过级联催化氢和解离氮物种相结合进行高效合成氨. 这些研究表明, 通过的高反应性AMReO₄载体和活性金属Co的协同作用, 有效调节N₂和H₂在催化剂上竞争性吸附活化机制到非竞争性机制来实现温和条件下氨的高效合成.
综上, 本工作强调了采用集活性金属和助剂于一体的高反应性载体与非贵金属Co位点的协同作用, 以增强在温和条件下合成氨性能的重要性, 为设计和开发温和条件下新型高效的合成氨催化剂提供了新思路.

关键词: 合成氨, 反应性载体, 氢溢流, 氮气活化, 碱金属高铼酸盐

Abstract:

The development of highly efficient and stable non-precious metal catalysts under mild conditions is highly desirable for NH₃ synthesis. However, the competitive adsorption of N₂ and H₂ on the single site and strong NH₃ adsorption greatly hinder the catalytic efficiency of catalysts under mild conditions. Herein, we propose the use of responsive alkali metal perrhenates (AMReO₄, AM = K, Na, or Cs) supports with scheelite-type structure that contains active Re metal and promoters to disperse cobalt (Co) species, constructing highly efficient catalysts by regulating the competitive reactant adsorption-activation pattern to a non-competitive mechanism. Our studies demonstrate that Co/KReO₄ catalyst shows excellent catalytic performance for NH₃ synthesis. Co and Re sites synergistically to promote the activation of N₂ molecules, while the adsorption and activation of H₂ primarily occur on Re sites of KReO₄. The presence of Co species facilitates H-spillover that enables the migration of *H species from Re to Co sites, then cascade catalysis of hydrogen and dissociated nitrogen species to form NH₃. Accordingly, the NH₃ synthesis rate of Co/KReO₄ (11.48 mmol_NH3 g_cat^-1 h^-1) is 3.2-fold higher than that of KReO₄ (3.58 mmol_NH3 g_cat^-1 h^-1) at 400 °C and 1 MPa. This work emphasizes the significance of employing reactive supports containing promoters and active metals, in collaboration with non-precious Co sites, to enhance NH₃ synthesis performance under mild conditions.

Key words: Ammonia synthesis, Responsive support, Hydrogen spillover, N₂ activation, Alkali metal perrhenates

彭渲北, 安梦琪, 毛瑞绍, 周岩良, 陈名, 黄东雅, 苏凯琳, 章世勇, 倪军, 王秀云, 江莉龙. 白钨矿型碱金属高铼酸盐负载的钴基催化剂用于高效合成氨[J]. 催化学报, 2026, 83: 432-443.

Xuanbei Peng, Mengqi An, Ruishao Mao, Yanliang Zhou, Ming Chen, Dongya Huang, Kailin Su, Shiyong Zhang, Jun Ni, Xiuyun Wang, Lilong Jiang. Scheelite-type alkali metal perrhenates supported Co-based catalysts for highly efficient ammonia synthesis[J]. Chinese Journal of Catalysis, 2026, 83: 432-443.

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图/表 9

Fig. 1. Catalytic performance. (a) NH3 synthesis rate of Co/AMReO4 (AM = K, Na and Cs) catalysts at 400 °C and 1 MPa. (b) NH3 synthesis rate of xCo/KReO4 with varying Co contents at 400 °C and 1 MPa. (c) Dependence of NH3 synthesis rate on the reaction pressure at 400 °C over KReO4 and xCo/KReO4 catalysts. (d) Catalytic stability of 15Co/KReO4 catalyst at 400 °C and 1 MPa.

Fig. 2. XRD pattern (a) and enlarged view of 2θ = 37°?44° (b) of KReO4 sample. XRD patterns (c) and enlarged view of 2θ = 42°?44° (d) of xCo/KReO4 catalysts.

Fig. 3. (a) HR-TEM image. (b,c) Enlarged view of the corresponding area in (a). HAADF-STEM image (d) and EDX mapping (e-h) of Co, Re, K, and O elements of 15Co/KReO4.

Fig. 4. Kinetic analyses. (a) Arrhenius plot of KReO4 and 15Co/KReO4 catalysts at 1 MPa. Reaction orders of N2 (b), H2 (c), and NH3 (d) over the KReO4 and 15Co/KReO4 catalysts at 400 °C and 1 MPa.

Fig. 5. Co K-edge XANES (a) and k3-weighted EXAFS (b) spectra of the xCo/KReO4 catalysts, Co foil and CoO references. Wavelet transform (WT) for the Co K-edge EXAFS signal of the15Co/KReO4 (c) and 20Co/KReO4 (d) catalysts.

Fig. 6. H2-TPR profiles of KReO4 and 15Co/KReO4 catalysts.

Fig. 7. Quasi in situ XPS spectra of (a) Re 4f and (b) Co 2p of 15Co/KReO4 under different gas environments: fresh, 10% H2/Ar, N2, and 25%N2-75%H2. The average valence of (c) Re and (d) Co evolved from quasi in situ XPS spectra of 15Co/KReO4 under different gas environments.

Fig. 8. Re 4f XPS spectra (a) and H2-TPD-MS profiles (b) of KReO4 and 15Co/KReO4 catalysts.

Fig. 9. Schematic illustration of Co and Re sites synergistic catalysis for NH3 synthesis in Co/KReO4 catalyst.

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白钨矿型碱金属高铼酸盐负载的钴基催化剂用于高效合成氨

Scheelite-type alkali metal perrhenates supported Co-based catalysts for highly efficient ammonia synthesis

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