Chelating-agent-free incorporation of isolated Ni single-atoms within BEA zeolite for enhanced biomass hydrogenation  

Ni单原子在BEA沸石中无螯合剂的原位封装提升生物质加氢性能

作　　者：Meng Liu Caixia Miao Yumeng Fo Wenxuan Wang Yao Ning Shengqi Chu Weiyu Song Ying Zhang Jian Liu Zhijie Wu Wenhao Luo 刘萌;苗彩霞;佛雨萌;王文璇;宁尧;储胜启;宋卫余;张瑛;刘健;吴志杰;罗文豪(中国石油大学(北京),重质油全国重点实验室和CNPC催化重点实验室,北京102249;内蒙古大学化学化工学院,内蒙古自治区稀土催化重点实验室,内蒙古呼和浩特010021;中国石油大学(北京)新能源与材料学院,北京102249;中国科学院高能物理研究所多科学中心,北京100049)

机构地区：[1]State Key Laboratory of Heavy Oil Processing and Key Laboratory of Catalysis of CNPC,China University of Petroleum-Beijing,Beijing 102249,China [2]Inner Mongolia Key Laboratory of Rare Earth Catalysis,College of Chemistry and Chemical Engineering,Inner Mongolia University,Hohhot 010021,Inner Mongolia,China [3]Department of Materials Science and Engineering,China University of Petroleum-Beijing,Beijing 102249,China [4]Beijing Synchrotron Radiation Facility,Institute of High Energy Physics,Chinese Academy of Sciences,Beijing 100049,China

出　　处：《Chinese Journal of Catalysis》2025年第4期308-318,共11页催化学报(英文)

基　　金：国家重点研发发展计划(2022YFB3805602);中国石油天然气集团有限公司创新基金(2021DQ02-0702);国家自然科学基金(22078316,22479082);内蒙古大学基金(10000-23112101/081);内蒙古青年科技英才基金(NJYT24019);中央引导地方科技发展专项资金(2024ZY0116).

摘　　要：Precisely tailoring metal single-atoms within zeolite scattfolds and understanding the origin of the unique behavior of such atomically dispersed catalysts are pivotal and challenge in chemistry and catalysis.Herein,we have successfully fabricated Ni single-atoms within BEA zeolite(Ni1@Beta)through a facile in situ two-step hydrothermal strategy,notably without using any chelating agent for stabilizing Ni species.With the aid of advanced characterization techniques,such as aberration-corrected high-angle annular dark-field scanning transmission electron microscopy,X-ray absorption spectroscopy,etc.,and combined with density functional theory calculations,the nature and micro-environment of isolated Ni species,which are incorporated within 6-membered rings and stabilized by four skeletal oxygens of Beta zeolite,have been identified.The as-obtained Ni1@Beta exhibits a superior performance in terms of activity(with a turnover frequency value up to 114.1 h^(–1))and stability(for 5 consecutive runs)in the selective hydrogenation of furfural,surpassing those of Ni nanoparticle analogues and previously reported Ni-based heterogeneous catalysts.This study provides an efficient strategy for the fabrication of non-noble metal single-atoms within zeolites,which could be of great help for the design of metal-zeolite combinations in the chemoselective reactions involved in biomass conversion and beyond.沸石基双功能催化剂在能源化工领域涉氢反应中应用广泛,特别是沸石微孔内封装金属催化剂在生物质增值转化与石油炼制等关键反应中展现优异的反应性能.金属纳米颗粒(1–2 nm)的封装可能会堵塞沸石的微孔(<2 nm),导致催化活性降低.相比之下,将原子级分散的孤立金属原子锚定在沸石孔道中,既可实现金属原子的最大利用率,又能最小化对沸石孔道体积的占比,从而赋予催化剂独特的反应性能.近年来,贵金属单原子在沸石微孔内的成功封装已有报道,但多数方法需依赖螯合剂来稳定贵金属前体.然而螯合剂的引入可能会干扰沸石的自组装过程.因此,开发无需螯合剂、可普适性构筑沸石封装非贵金属单原子催化剂的合成方法,仍是该领域亟待突破的挑战.本文采用一种简易的原位两步水热合成法,首次在不使用任何螯合剂稳定镍金属前体的情况下,成功将镍单原子限域在BEA沸石孔道中(Ni1@Beta).该原位两步水热法首先在较低温度(100℃)下通过成核过程生成晶核,随后添加镍金属前体并在高温(140℃)下完成晶化.通过球差校正透射电子显微镜、X射线吸收光谱和密度泛函理论计算分析了Ni1@Beta催化剂的基本结构;进而利用氢气程序升温还原、X射线光电子能谱和CO吸附红外光谱等表征技术研究了Ni在BEA沸石中的存在状态.表征结果表明,Ni物种以Ni^(2+)的形式被锚定在BEA沸石的六元环内,并由四个骨架氧原子所稳定,与沸石骨架之间具有强相互作用.得益于BEA沸石独特的限域环境与镍单原子的最大原子利用率,所得Ni1@Beta催化剂在糠醛选择性加氢制糠醇反应中呈现较好的催化性能,转换频率值高达114.1 h^(–1),显著高于镍纳米颗粒催化剂以及已报道的镍基多相催化剂.此外,Ni1@Beta催化剂具有良好的稳定性,连续五次循环后,糠醛转化率和糠醇选择性未发现明显下降.综上所述,本�

关 键 词：NICKEL Single-atoms Zeolites Catalytic hydrogenation Biomass conversion 

分 类 号：O643.36[理学—物理化学]