分子筛硅醇巢锚定的配位不饱和Co位点高效催化丙烷脱氢

doi:10.1016/S1872-2067(25)64660-2

催化学报 ›› 2025, Vol. 72: 323-333.DOI: 10.1016/S1872-2067(25)64660-2

分子筛硅醇巢锚定的配位不饱和Co位点高效催化丙烷脱氢

郭丽雯^a, 石导^a, 章天骏^b, 马延航^c, 齐国栋^d^,^*(), 徐君^d, 孙启明^a^,^*()

^a苏州大学材料与化学化工学部, 江苏省先进负碳技术重点实验室, 化学科学国际合作创新中心, 江苏苏州 215123
^b河北大学化学与材料科学学院, 新型药物制剂与辅料全国重点实验室, 河北保定 071002
^c上海科技大学物质科学与技术学院, 上海市高分辨电子显微学重点实验室, 上海 201210
^d中国科学院武汉物理与数学研究所, 精密测量科学与技术创新研究院, 武汉磁共振中心, 波谱与原子分子物理国家重点实验室, 湖北武汉 430071

收稿日期:2024-11-25 接受日期:2025-02-25 出版日期:2025-05-18 发布日期:2025-05-20
通讯作者: *电子信箱: sunqiming@suda.edu.cn (孙启明),qgdong@wipm.ac.cn (齐国栋).
基金资助:
国家重点研发计划(2022YFA1506000);江苏特聘教授项目;姑苏创新创业领军人才计划(ZXL2022497)

Unsaturated cobalt single-atoms stabilized by silanol nests of zeolites for efficient propane dehydrogenation

Liwen Guo^a, Dao Shi^a, Tianjun Zhang^b, Yanhang Ma^c, Guodong Qi^d^,^*(), Jun Xu^d, Qiming Sun^a^,^*()

^aInnovation Center for Chemical Science, College of Chemistry, Chemical Engineering and Materials Science, Jiangsu Key Laboratory of Advanced Negative Carbon Technologies, Soochow University, Suzhou 215123, Jiangsu, China
^bState Key Laboratory of New Pharmaceutical Preparations and Excipients, College of Chemistry and Materials Science, Hebei University, Baoding 071002, Hebei, China
^cSchool of Physical Science and Technology & Shanghai Key Laboratory of High-resolution Electron Microscopy, ShanghaiTech University, Shanghai 201210, China
^dNational Center for Magnetic Resonance in Wuhan, State Key Laboratory Magnetic Resonance and Atomic Molecular Physics, Wuhan Institute of Physics and Mathematics, Innovation Academy for Precision Measurement Science and Technology, Chinese Academy of Sciences, Wuhan 430071, Huebi, China

Received:2024-11-25 Accepted:2025-02-25 Online:2025-05-18 Published:2025-05-20
Contact: *E-mail: sunqiming@suda.edu.cn (Q. Sun), qgdong@wipm.ac.cn (G. Qi).
Supported by:
National Key R&D Program of China(2022YFA1506000);Jiangsu Distinguished Professor program, and the Gusu Innovation;Entrepreneurship Leading Talents Program(ZXL2022497)

摘要/Abstract

摘要：

丙烯作为多种高价值化学品的重要前体, 是最重要的基础化工原料之一. 丙烷直接脱氢(PDH)反应作为一种具有广阔发展前景的丙烯生产途径, 已引起工业界与学术界的广泛关注. 然而, 目前工业上常用的负载型铬基和铂基PDH催化剂存在毒性强和成本高等问题. 因此, 开发新颖的合成策略, 制备低成本、环保且高效的PDH催化剂, 具有重要的研究价值.

沸石分子筛由于其规则的孔道结构、较大的比表面积和较好的热稳定性, 成为负载型金属催化剂理想的载体材料. 本文设计并合成了三种具有不同硅醇巢含量的Beta分子筛, 分别为脱铝介孔Beta分子筛(deAl-meso-Beta)、脱铝传统Beta分子筛(deAl-con-Beta)和纯硅Beta分子筛(Si-Beta), 并用作催化剂载体负载高分散的Co活性物种, 详细地研究了分子筛硅醇巢数量与丙烷脱氢催化性能之间的关系. PDH催化性能测试和多种表征分析结果表明, 在Co负载量相同时, 催化剂的丙烷脱氢活性随载体硅醇巢含量的增加而提升. 具体而言, 在550 °C, 4.5 h^-1的重时空速条件下, 活性最优的Co_0.3%/deAl-meso-Beta催化剂的丙烯生成速率可达到21.2 mmol_C3H6 g_cat^-1 h^-1, 并表现出出色的再生稳定性, 连续五轮PDH循环测试中未观察到明显失活. 此外, 红外光谱和魔角旋转核磁共振等结果表明, Beta分子筛的硅醇巢能够有效锚定Co物种, 并显著提高催化剂的稳定性. CO程序升温表面反应和X射线吸收光谱结果揭示, 由硅醇巢稳定的Co物种为具有独特不饱和三配位结构的Co₁O₃H_x位点, 该物种在PDH反应中具有高效催化活性. 同时, Co₁O₃H_x位点还展示了较好的抗积碳能力, 其积碳速率仅为3.3 × 10^-4 g_coke g_cat^-1 h^-1, 比Co纳米粒子的积碳速率低一个数量级.

综上所述, 本文通过对分子筛硅醇巢的调控, 成功构建了配位不饱和Co₁O₃H_x活性位点, 并在PDH反应中展现出较好的催化活性和稳定性. 本研究为开发高效、稳定且环境友好的非贵金属催化剂提供了新思路.

关键词: 丙烷脱氢, 配位不饱和Co, 单原子, 硅醇巢, 分子筛

Abstract:

Propane dehydrogenation (PDH) has emerged as a key on-purpose technology for the production of propylene, but it often depends on toxic chromium and expensive platinum catalysts, highlighting the need for environmentally friendly and cost-effective alternatives. In this study, we developed a facile impregnation method to fabricate unsaturated Co single-atoms with a tricoordinated Co₁O₃H_x structure by regulating silanol nests in purely siliceous Beta zeolites. Detailed PDH catalytic tests and characterizations revealed a positive correlation between the presence of silanol nests and enhanced catalytic activity. Additionally, the unsaturated Co single-atoms exhibited a carbon deposition rate more than an order of magnitude slower than that of Co nanoparticles. Notably, the optimized Co_0.3%/deAl-meso-Beta catalyst achieved a record-high propylene formation rate of 21.2 mmol_C3H6 g_cat^-1 h^-1, with an exceptional propylene selectivity of 99.1% at 550 °C. Moreover, the Co_0.3%/deAl-meso-Beta catalyst demonstrated excellent stability, with negligible deactivation after 5 consecutive regeneration cycles. This study emphasizes the pivotal role of silanol nests of zeolites in stabilizing and modulating the coordination environment of metallic active sites, providing valuable insights for the design of high-activity, high-stability, and low-cost PDH catalysts.

Key words: Propane dehydrogenation, Unsaturated cobalt, Single-atoms, Silanol nest, Zeolite

郭丽雯, 石导, 章天骏, 马延航, 齐国栋, 徐君, 孙启明. 分子筛硅醇巢锚定的配位不饱和Co位点高效催化丙烷脱氢[J]. 催化学报, 2025, 72: 323-333.

Liwen Guo, Dao Shi, Tianjun Zhang, Yanhang Ma, Guodong Qi, Jun Xu, Qiming Sun. Unsaturated cobalt single-atoms stabilized by silanol nests of zeolites for efficient propane dehydrogenation[J]. Chinese Journal of Catalysis, 2025, 72: 323-333.

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Fig. 1. (a) Schematic illustration of creating silanol nests by dealumination and single-sites Co trapped by silanol nests. (b) FT-IR spectra of pyridine adsorption on meso-Beta and deAl-meso-Beta. ATR-IR spectra (c) and FT-IR spectra (d) of hydroxyl group on the meso-Beta and deAl-meso-Beta. STEM image (e), aberration-corrected HAADF-STEM image (f) and EDX elemental mapping images (g) of Co0.3%/deAl-meso-Beta.

Fig. 2. Catalytic performance of Co0.3%/deAl-meso-Beta, Co0.3%/deAl-con-Beta, and Co0.3%/Si-Beta catalysts in propane dehydrogenation. Conversion of propane (a) and selectivity of propylene (b) over various catalysts. Reaction conditions: 0.33 g of catalyst, C3H8: N2 = 12.5: 37.5 mL min-1, WHSV = 4.5 h-1, 550 °C. Propane conversion and propylene selectivity over Co0.3%/deAl-meso-Beta at various temperature (525-600 °C) under 4.5 h-1 (c) and at 550 °C under various WHSVs (1.5-9.0 h-1) (d). (e) Arrhenius plots of various reaction temperatures of Co0.3%/deAl-meso-Beta and Co0.3%/deAl-con-Beta. (f) The comparison of the net propylene formation rate over Co0.3%/deAl-meso-Beta and previously reported state-of-the-art Co-based catalysts (see Table S4 for details). (g) Regeneration test of Co0.3%/deAl-meso-Beta. Regeneration condition: calcination in air at 600 °C for 1 h.

Fig. 3. (a) FT-IR spectra of hydroxyl group on the deAl-meso-Beta and Co0.3%/deAl-meso-Beta (I3500 and I3740 is the signal intensity at 3500 and 3740 cm-1). XANES spectra (b) and the Fourier transforms of k2-weighted Co K-edge EXAFS experimental data and fitting curves (dashed line) (c) for Co0.3%/deAl-meso-Beta, Co0.3%/Si-Beta and standards. (d) CO-TPSR curves of Co0.3%/deAl-meso-Beta.

Fig. 4. ATR-IR spectra (a) and FT-IR spectra (b) of deAl-meso-Beta before and after recrystallization. (c) Catalytic performance of recrystallization catalysts. 1H MAS NMR (d) and 1H-29Si CP MAS NMR (e) spectra of deAl-meso-Beta and Cox%/deAl-meso-Beta (x = 0.1-0.3). (f) Propane conversion of various Cox%/deAl-meso-Beta.

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分子筛硅醇巢锚定的配位不饱和Co位点高效催化丙烷脱氢

Unsaturated cobalt single-atoms stabilized by silanol nests of zeolites for efficient propane dehydrogenation

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