硼修饰缺电子镍催化无积碳甲烷干重整

doi:10.1016/S1872-2067(26)65077-2

催化学报 ›› 2026, Vol. 87: 353-362.DOI: 10.1016/S1872-2067(26)65077-2

硼修饰缺电子镍催化无积碳甲烷干重整

王阳^a^,¹, 贺雷^a^,¹, 唐帆^a, 李文翠^a, 何博文^b, 刘晰^b, 陈立桅^b, 王东琪^a, 申文杰^c^,^*(), 陆安慧^a^,^*()

^a 大连理工大学化工学院, 辽宁省低碳资源高值化利用重点实验室, 精细化工全国重点实验室, 辽宁大连 116024
^b 上海交通大学化学化工学院, 物质科学原位中心, 上海 200240
^c 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 116024

收稿日期:2025-11-27 接受日期:2026-01-23 出版日期:2026-08-18 发布日期:2026-06-24
通讯作者: ^*电子信箱: anhuilu@dlut.edu.cn (陆安慧),
shen98@dicp.ac.cn (申文杰).
作者简介:¹共同第一作者.
基金资助:
国家重点研发计划(2021YFA1501301);国家重点研发计划(2021YFA1500301);国家自然科学基金(22478053);国家自然科学基金(U1908203)

Electron-deficient nickel tailored by boron for coke-free methane dry reforming

Yang Wang^a^,¹, Lei He^a^,¹, Fan Tang^a, Wen-Cui Li^a, Bowen He^b, Xi Liu^b, Liwei Chen^b, Dongqi Wang^a, Wenjie Shen^c^,^*(), An-Hui Lu^a^,^*()

^a State Key Laboratory of Fine Chemicals, Liaoning Key Laboratory for Catalytic Conversion of Carbon Resources, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning, China
^b School of Chemistry and Chemical Engineering, In-situ Center for Physical Science, Shanghai Jiao Tong University, Shanghai 200240, China
^c State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116024, Liaoning, China

Received:2025-11-27 Accepted:2026-01-23 Online:2026-08-18 Published:2026-06-24
About author:¹Contributed equally to this work.
Supported by:
National Key R&D Program of China(2021YFA1501301);National Key R&D Program of China(2021YFA1500301);National Natural Science Foundation of China(22478053);National Natural Science Foundation of China(U1908203)

摘要/Abstract

摘要：

甲烷干重整(MDR)可将两种主要温室气体(CO₂与CH₄)转化为合成气(H₂/CO), 衔接费托路线合成燃料与化学品, 兼具环境效益和经济价值, 是实现“双碳”目标的关键能源化工路径之一. 镍基催化剂具有高MDR催化活性和低成本优势, 但较低的塔曼温度(691 °C)使得Ni物种极易在MDR高温反应过程中烧结失活. 同时, Ni颗粒表面(特别是台阶位)对甲烷C-H键活化能力强, 而对中间碳物种的移除(主要通过CO₂活化)动力学缓慢, 导致碳物种的不断累积. 因此, 设计一种Ni颗粒稳定固载, 且能够调控甲烷活化与碳消除动态平衡的镍基催化剂, 同步解决烧结和积碳两大失活难题, 是实现MDR高活性与高稳定性运行的关键挑战.

本文创新性地采用静电驱动自组装策略, 成功将带正电的含镍层状双氢氧化物(Ni-LDH)纳米片与带负电的氮化硼(BN)纳米片进行了定向组装, 所得具有夹心结构的复合二维材料经高温焙烧还原后制备得到复合催化剂Ni_BN. 球差校正电镜及X-射线衍射(XRD)实验结果表明, Ni_BN催化剂中Ni纳米颗粒为尺寸均一的近球形(约6 nm), 稳定分散于MgAlO_x混合氧化物, 且外层被氮化硼包裹. Ni_BN在750 °C MDR反应条件下实现了长期(超过350 h)稳定运行, 反应后催化剂中的Ni颗粒未发生明显聚集. 原位XRD跟踪也未发现Ni颗粒的聚集烧结, 证实MgAlO_x混合氧化物基底的化学锚定与外层氮化硼的物理分隔双重作用, 实现了Ni颗粒的稳定固载. 需要强调的是, 反应后Ni_BN催化剂的热重和拉曼结果均未检测到积碳. 相比之下, 由Ni-LDH衍生的对比催化剂在20 h即因严重积碳而无法继续反应. 电子能量损失谱与X-射线光电子能谱分析表明, Ni_BN催化剂中部分界面处的Ni物种通过Ni-O-B键合作用, 呈现缺电子态. 利用智能重量分析与质谱联用对MDR反应、甲烷裂解及CO歧化三种不同气氛下催化剂质量变化及尾气组成的跟踪, 对积碳和消碳过程进行解耦, 发现Ni_BN催化剂的特殊结构有效抑制了甲烷的深度裂解积碳, 并促进了CO₂消碳速率. 催化剂中Ni颗粒为稳定的近球形结构, 无台阶位, 避免了积碳成核和聚集. 理论计算进一步证实, Ni-O-B结构的存在能够抑制甲烷最后一个C-H键的断裂, 同时提升了CO₂活化消碳能力, 促进了积碳-消碳基元步骤的速率匹配, 从而实现了催化剂在MDR反应中的无积碳稳定运行.

综上, 本工作创制了一种高稳定MDR催化剂, 同步实现了镍基催化剂的抗烧结和抗积碳. 通过机理研究明晰了非金属硼的电子调控作用, 揭示了C-H键活化与碳消除步骤动态平衡的普适性策略, 为设计高温条件下C-H键活化与定向转化的高稳定催化剂提供了新的思路.

关键词: 缺电子, 镍, 硼, 甲烷干重整, 无积碳

Abstract:

Methane dry reforming (MDR) converts two major greenhouse gases (CO₂ and CH₄) into syngas (H₂/CO) for synthesizing fuels and chemicals, which provides a process both economically viable and environmentally friendly, aligning with the goal of carbon neutrality. Ni is the most efficient and economic non-noble active metal for MDR but often suffers from deactivation caused by sintering or coking due to the fast C-H activation but sluggish carbon removal. Herein, we report a rather stable Ni catalyst (Ni_BN) derived from electrostatic-driven self-assembled 2D composites, which offered a coke-free manner for a prolonged stability (over 350 h) under typical MDR conditions. This outperformed catalyst featured with homogeneously distributed spherical Ni nanoparticles (~6 nm) stabilized within mixed-oxide matrix. Partially electron-deficient Ni species are tailored by surrounded boron species through the Ni-O-B structure, which hindered the last C-H bond cleavage of methane and accelerated CO₂ reactivity, thus balancing elementary steps to enable a coke-free operation. It marks an important step forward for C-H bond manipulation and inspires material design in other applications.

Key words: Electron-deficient, Nickel, Boron, Methane dry reforming, Coke-free

王阳, 贺雷, 唐帆, 李文翠, 何博文, 刘晰, 陈立桅, 王东琪, 申文杰, 陆安慧. 硼修饰缺电子镍催化无积碳甲烷干重整[J]. 催化学报, 2026, 87: 353-362.

Yang Wang, Lei He, Fan Tang, Wen-Cui Li, Bowen He, Xi Liu, Liwei Chen, Dongqi Wang, Wenjie Shen, An-Hui Lu. Electron-deficient nickel tailored by boron for coke-free methane dry reforming[J]. Chinese Journal of Catalysis, 2026, 87: 353-362.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(26)65077-2

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图/表 5

Fig. 1. Structure of NiBN catalyst. (a) Schematic illustration of the synthesis process. (b) Large-scale TEM image. (c) High resolution TEM image of one typical Ni particle. (d) Particle size distribution. (e) ADF-STEM image and the corresponding EDX mapping, showing the distribution of B, N, O, Ni, Al, Mg, and overlayer of the above elements. (f) In-situ XRD measurements of NiBN catalyst in temperature programmed reduction.

Fig. 2. Electron state of Ni. ADF-STEM image (a) and corresponding STEM-EELS element mapping (b-e) of boron. (f) Integrated EELS from the selected areas and reference B EELS spectra. (g) XPS profiles of Ni 2p3/2 for NiBN and the Ni-ref catalysts.

Fig. 3. Catalytic performance of NiBN catalyst. (a) MDR stability test (GHSV = 30000 mL g?1 h?1, inserted the TEM image for the spent catalyst). (b) Anti-coking test under nearly pure CH4/CO2 mixture. (c) High pressure MDR test. (d) TG-MS results (solid lines, TG; dotted lines, mass spectra) of spent catalyst under various conditions. (e) Large area TEM image of the spent NiBN catalyst (20 h at 600 °C).

Fig. 4. Coke resistance investigation. (a) In-situ XRD results (the patterns were taken every half hour, CH4:CO2:N2 = 1:1:3, flow rate = 30 mL min?1). (b) Mass change and the corresponding mass spectra signals of the outlet gas (600 °C, flow rate = 100 mL min?1). (c) Mass change and the corresponding mass spectra signal change in alternated CH4 and CO2 atmosphere (CH4:Ar =1:4 or CO2:Ar = 1:4, 600 °C, flow rate = 100 mL min?1).

Fig. 5. (a) The free energy profile of C-H bond cleavage in methane at 873 K. (b) Carbon migration on Ni-BN and Ni(111) at 873 K. (c) MDR catalytic cycle based on experimental and DFT calculation.

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硼修饰缺电子镍催化无积碳甲烷干重整

Electron-deficient nickel tailored by boron for coke-free methane dry reforming

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