空间限域封装策略构筑高稳定镍基催化剂及其在苯酚加氢中应用

doi:10.1016/S1872-2067(26)65220-5

催化学报 ›› 2026, Vol. 91: 351-364.DOI: 10.1016/S1872-2067(26)65220-5

空间限域封装策略构筑高稳定镍基催化剂及其在苯酚加氢中应用

钱茂辰^a^,^b, 刘稳^a^,^*(), 张新宝^a, 朱向学^a, 李秀杰^a^,^*()

^a 中国科学院大连化学物理研究所, 能源催化转化全国重点实验室, 辽宁大连 116023
^b 中国科学院大学, 北京 100049

收稿日期:2026-03-20 接受日期:2026-05-25 出版日期:2026-12-18 发布日期:2026-10-13
通讯作者: ^*电子信箱: liuwen@dicp.ac.cn (刘稳),
xiujieli@dicp.ac.cn (李秀杰).
基金资助:
国家重点研发计划(2023YFA1507604);国家自然科学基金(2230219);大连市领军人才团队项目(2024RG005);辽宁省科技计划(2024JH2/102600001);大连市芳香化合物工程研究中心;辽宁省重点实验室

Highly stable encapsulated Ni catalyst for phenol hydrogenation: Synthesis and mechanistic insight

Maochen Qian^a^,^b, Wen Liu^a^,^*(), Xinbao Zhang^a, Xiangxue Zhu^a, Xiujie Li^a^,^*()

^a State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^b University of Chinese Academy of Sciences, Beijing 100049, China

Received:2026-03-20 Accepted:2026-05-25 Online:2026-12-18 Published:2026-10-13
Supported by:
National Key Research and Development Program of China(2023YFA1507604);National Natural Science Foundation of China(2230219);Dalian High-Level Innovation Talents’ Team(2024RG005);Science and Technology Projects of Liaoning Province(2024JH2/102600001);Dalian Engineering Research Center for Key Aromatic Compounds;Key Laboratory of Liaoning Province

摘要/Abstract

摘要：

环己醇是合成己内酰胺、己二酸及塑料、纤维等大宗化学品的关键中间体, 其主流合成工艺路线包括环己烷氧化和苯酚加氢, 其中苯酚加氢路线因反应条件温和、原子经济性高而备受青睐. 随着生物质资源利用技术不断发展, 以苯酚为代表的木质素衍生酚类化合物通过催化加氢制备高附加值化学品与液体燃料成为研究热点. 在众多加氢催化体系中, 负载型镍基催化剂凭借成本低廉、加氢活性优异等特点在连续流反应中展现出良好的应用潜力. 目前传统镍基催化剂面临高温下易发生烧结团聚的挑战, 导致催化剂的快速、不可逆失活. 因此, 如何设计兼具高活性与高稳定性的非贵金属加氢催化剂, 是该领域亟待突破的核心问题.
针对上述挑战, 本文开发了一种无螯合剂参与的原位水热合成策略, 成功制备了封装型Ni@silicalite-1催化剂, 实现了高负载量下镍物种的高度分散, 并在固定床反应器中系统考察了其苯酚加氢制环己醇的催化性能. 具体而言, 在不添加螯合剂的条件下, 通过原位水热晶化法将镍物种限域于沸石晶体内, 获得封装型Ni@silicalite-1催化剂. 在连续流反应条件下, 传统浸渍型Ni/silicalite-1催化剂在运行12 h内即发生显著失活; 相比之下, Ni@silicalite-1展现出优异的加氢稳定性, 连续运行100 h后, 苯酚转化率高于95%(155 °C, 2.0 MPa, WHSV=1.0 h^-1), 环己醇选择性高于95%. 本文采用X-射线吸收光谱、原位漫反射红外傅里叶变换光谱以及高角环形暗场扫描透射电镜等多种表征手段, 对催化剂进行了精细结构解析, 发现Ni@silicalite-1中镍物种以~2.34 nm的纳米颗粒存在, 通过Ni-O-Si键的形成, 与沸石载体产生强金属-载体相互作用. 这一独特的金属-载体界面通过空间限域与化学键合的双重约束有效抑制了镍颗粒的高温烧结, 同时凭借封装效应降低了积碳前驱体的表面富集, 从而协同保障了催化剂在苛刻反应条件下的长周期稳定性. 采用X-射线衍射和透射电镜等技术动态追踪了分子筛晶化过程中镍物种的演化轨迹. 结果表明, 随着晶化进行与分子筛骨架的形成, 镍物种由片状硅酸镍前驱体逐渐分散转化为镍纳米颗粒. 其中, 模板剂空间分布是驱动镍物种原位再分散与Ni-O-Si化学键形成的关键因素.
综上, 本文成功采用原位水热法制备了兼具抗烧结与抗积碳性能的金属@沸石催化剂, 深入揭示了镍物种在沸石晶化过程中的原位分散演变机制. 上述金属-载体界面的设计思路为构建高稳非贵金属@沸石封装催化剂提供了重要的方法参考与理论依据.

关键词: 加氢反应, 苯酚, 环己醇, 镍基催化剂, 原位合成

Abstract:

Hydrogenation of biomass-derived phenol to cyclohexanol represents a sustainable pathway for cyclohexanol production. Although supported Ni catalysts exhibit potential for fixed-bed applications, traditional systems suffer from rapid deactivation. Herein, we demonstrate a highly stable encapsulated Ni@silicalite-1 catalyst synthesized via chelator-free hydrothermal route. Compared to conventional impregnated Ni/silicalite-1 counterparts, Ni@silicalite-1 maintains exceptional operational stability beyond 100 h with sustained phenol conversion exceeding 90% and cyclohexanol selectivity over 95% under continuous-flow conditions. Characterization results including X-ray absorption spectroscopy, in-situ diffuse reflectance infrared Fourier transform spectroscopy and high angle annular dark field scanning transmission electron microscopy reveal that ultrafine Ni nanoparticles (~2.34 nm) anchored via Ni-O-Si interfacial bonds constitute the active sites, conferring dual resistance to thermal sintering and carbon deposition under reaction conditions. Mechanistic studies tracking silicalite-1 crystallization demonstrate that amorphous nickel silicate precursors gradually transform into spatially confined Ni nanoparticles driven by the organic template. This work establishes a universal paradigm for constructing sintering-resistant metal-zeolite catalysts through nanoscale engineering of metal-support interfaces.

Key words: Hydrogenation, Phenol, Cyclohexanol, Nickel-based catalyst, In-situ synthesis

钱茂辰, 刘稳, 张新宝, 朱向学, 李秀杰. 空间限域封装策略构筑高稳定镍基催化剂及其在苯酚加氢中应用[J]. 催化学报, 2026, 91: 351-364.

Maochen Qian, Wen Liu, Xinbao Zhang, Xiangxue Zhu, Xiujie Li. Highly stable encapsulated Ni catalyst for phenol hydrogenation: Synthesis and mechanistic insight[J]. Chinese Journal of Catalysis, 2026, 91: 351-364.

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图/表 8

Fig. 1. General properties of different samples. (A) XRD patterns. (B) H2-TPR profiles. (C) Ni 2p3/2 XPS spectra. (D) UV-Raman spectra. (E) UV-vis spectra. Fourier transform of K3-weighted EXAFS spectra at R space (F) and Wavelet transforms (G,H) from experimental data.

Fig. 2. HAADF-STEM images and TEM-EDS mappings of NiO@S-1 (A), Ni@S-1-500C-R (B), NiO/S-1 (C), and Ni/S-1-500C-R (D).

Fig. 3. Catalytic performance of Ni@S-1 and Ni/S-1 in phenol hydrogenation: Phenol conversion and selectivity for cyclohexanol (A) and distribution of by-products (B) and long-term durability tests (C) of Ni@S-1. Reaction conditions: 155 °C, 2.0 MPa, WHSV: 3.0 h-1 or 1.0 h-1.

Fig. 4. Catalytic hydrogenation performance of Ni@S-1 for phenol and its derived compounds. a Reaction conditions: substrate (0.25 g), catalyst (0.05 g), isopropanol (5 mL), 150 °C, 1 MPa H2, 3 h. b Reaction conditions: substrate (0.15 g), catalyst (0.05 g), isopropanol (5 mL), 180 °C, 2 MPa H2, 5 h. c Reaction conditions: substrate (0.15 g), catalyst (0.05 g), isopropanol (5 mL), 150 °C, 2 MPa H2, 4 h. d Reaction conditions: substrate (0.15 g), catalyst (0.05 g), isopropanol (5 mL), 180 °C, 2 MPa H2, 7 h. e Reaction conditions: substrate (0.15 g), catalyst (0.05 g), isopropanol (5 mL), 220 °C, 1 MPa H2, 8 h.

Fig. 5. In-situ DRIFTS of cyclohexanol desorption during programmed temperature desorption experiments (A,B) and corresponding contour plots (C, D) within the characteristic cyclohexanol vibrational bands for Ni@S-1 and Ni/S-1. (E,F) Evolution of the cyclohexanone absorption region for Ni/S-1 before and after reaction.

Fig. 6. (A,B) HAADF-STEM observation of the spent Ni@S-1 and Ni/S-1 catalysts and their corresponding element maps. (C) UV-Raman spectra comparing the carbon deposits on the spent catalysts. (D) GC-MS spectrum of catalyst leachate after reaction. (E,F) TG and DTG curves of the spent catalysts.

Fig. 7. XRD patterns (A), H2-TPR profiles (B), IR spectra in the hydroxyl vibration region (C), and UV-Raman spectra (D) of NiO@S-1 after different crystallization time. (E) Possible nickel dispersion mechanism during in-situ zeolite synthesis, HAADF-STEM images and the corresponding element mapping and catalytic performance of Ni@S-1 after different crystallization time.

Fig. 8. TG-MS profiles (A,B) and in-situ DRIFT spectra in hydroxyl region (C,D) and C-H vibration region (E,F) of the as-synthesized S-1 and NiO@S-1.

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空间限域封装策略构筑高稳定镍基催化剂及其在苯酚加氢中应用

Highly stable encapsulated Ni catalyst for phenol hydrogenation: Synthesis and mechanistic insight

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