引发二氧化碳选择性加氢制甲烷的最小镍物种: 限域在MFI结构中的镍二聚体以及锰氧化物的增强作用

doi:10.1016/S1872-2067(26)65095-4

催化学报 ›› 2026, Vol. 87: 113-125.DOI: 10.1016/S1872-2067(26)65095-4

引发二氧化碳选择性加氢制甲烷的最小镍物种: 限域在MFI结构中的镍二聚体以及锰氧化物的增强作用

王森^a^,¹, 李诗颖^a^,¹, 耿蕊^a^,^b, 周博^c^,^*(), 王鹏飞^a, 秦张峰^a, 董梅^a, 王建国^a^,^b, 樊卫斌^a^,^*()

^a 中国科学院山西煤炭化学研究所, 煤炭高效低碳利用全国重点实验室, 山西太原030001, 中国
^b 中国科学院大学化学化工学院, 北京 100049, 中国
^c 化学与精细化工广东省实验室, 广东汕头 515031, 中国
^d 挪威奥斯陆大学化学系, 材料与纳米科学中心(SMN), 奥斯陆, 挪威

收稿日期:2025-12-03 接受日期:2026-01-13 出版日期:2026-08-18 发布日期:2026-06-24
通讯作者: ^*电子信箱: zhoubo@ccelab.com.cn (周博),
fanwb@sxicc.ac.cn (樊卫斌).
作者简介:¹共同第一作者.
基金资助:
国家重点研发计划(2023YFB4103102);国家自然科学基金(21991090);国家自然科学基金(21991092);国家自然科学基金(22322208);国家自然科学基金(22272195);国家自然科学基金(U22A20431);国家自然科学基金(22402071);山西省基础研究计划(202203021224009);山西省基础研究计划(202403021212302);中国科学院山西煤炭化学研究所所创新项目(SCJC-DT-2023-06);中国科学院青年创新促进会项目(2021172)

The smallest Ni species triggering selective hydrogenation of CO₂ to methane: Ni dimer embedded in MFI and enhancement of MnO_x

Sen Wang^a^,¹, Shiying Li^a^,¹, Rui Geng^a^,^b, Bo Zhou^c^,^*(), Pengfei Wang^a, Zhangfeng Qin^a, Mei Dong^a, Jianguo Wang^a^,^b, Unni Olsbye^d, Weibin Fan^a^,^*()

^a State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, Shanxi, China
^b University of the Chinese Academy of Sciences, Beijing 100049, China
^c Chemistry and Chemical Engineering Guangdong Laboratory, Shantou 515031, Guangdong, China
^d Department of Chemistry, Centre for Materials and Nanoscience (SMN), University of Oslo, P.O. Box 1033, Blindern, NO-0315 Oslo, Norway

Received:2025-12-03 Accepted:2026-01-13 Online:2026-08-18 Published:2026-06-24
About author:¹Contributed equally to this work.
Supported by:
National Key R&D Program of China(2023YFB4103102);National Natural Science Foundation of China(21991090);National Natural Science Foundation of China(21991092);National Natural Science Foundation of China(22322208);National Natural Science Foundation of China(22272195);National Natural Science Foundation of China(U22A20431);National Natural Science Foundation of China(22402071);Fundamental Research Program of Shanxi Province(202203021224009);Fundamental Research Program of Shanxi Province(202403021212302);Innovation foundation of Institute of Coal Chemistry, Chinese Academy of Sciences(SCJC-DT-2023-06);Youth Innovation Promotion Association of Chinese Academy of Sciences (CAS)(2021172)

摘要/Abstract

摘要：

将二氧化碳(CO₂)转化为高附加值的燃料和化学品, 是实现碳资源循环利用的有效策略. CO₂可以通过催化加氢反应转化为多种化学产品, 如甲烷(CH₄)、一氧化碳(CO)、甲醇、低碳烯烃和芳烃等. 在这几种反应途径中, CO₂甲烷化反应具有更高的反应速率和目标产物选择性, 且能耗低于合成甲醇和C₂₊烃化合物. 此外, 相对温和的反应条件易于工业化放大, 也为缓解当前的天然气危机提供了一条潜在途径. Ni基催化剂被广泛用于CO₂加氢制CH₄反应中, 但传统报道的Ni基催化剂往往需要极高的Ni负载量(5%‒50%)才能有效促进CO₂的活化以及CH₄的生成. 过多Ni的使用, 不仅导致催化剂制备成本提高, 同时也降低了催化剂稳定性. 降低Ni负载量虽然可以显著提高活性位点的分散度, 有利于暴露更多的活性位点, 但在CO₂加氢过程中主要生成的产物是CO而非CH₄, 这是因为在较低Ni负载量情况下, NiO与载体相互作用过强, 抑制NiO还原为金属Ni, 导致催化剂的加氢性能下降.

因此, 提高Ni的原子利用效率、降低催化剂制备成本, 并且探明最小的活性Ni物种的结构以及在反应过程中的结构-性能关联, 对于设计和研制新型高性能Ni基催化剂至关重要. 本文制备了一系列Ni-MnO_x@MFI催化剂, 其中Ni氧化物和锰氧化物物种高度分散在全硅沸石孔道中. 通过原位X-射线衍射、高分辨球差电镜、积分差分相位衬度-扫描透射电镜、X-射线吸收近边结构/X-射线吸收精细结构、动力学实验、密度泛函理论(DFT)计算和从头计算分子动力模拟等方法, 研究了最小活性Ni物种的结构以及不同结构的Ni位点对H₂解离和CO*中间体加氢生成CH₄的催化活性的影响. 结果表明, Ni二聚体(Ni₂)是CO₂甲烷化的最小活性Ni团簇, CH₄形成活性随Ni₂含量的增加而线性增加. 引入锰氧化物(MnO_x)不仅有助于Ni氧化物还原为Ni₂位点, 而且还能增强H₂解离和CO*中间体吸附及加氢能力, 因为MnO_x增加了Ni位点的电子密度. 因此, 在400 °C、12000 mL·g^-1·h^-1和0.5 MPa条件下, Ni-MnO_x@MFI仅具有约0.86%的Ni负载量, 就实现了约76%的CO₂转化率、约98%的CH₄选择性和~455 mol•mol_Ni^-1•h^-1的CH₄时空产率, 超过了在类似条件下已报道的Ni基催化剂的性能. 原位漫反射红外光谱(DRIFTS)、D₂标记原位DRIFTS、质子转移反应飞行时间质谱以及DFT计算结果表明, 加入Mn助剂并没有改变中间体的生成方式, 但是促进了加氢反应, 产生了更多的CH_x*中间体, 最终促进了CH₄的生成. 进一步利用DFT计算考察了在单原子Ni₁, Ni二聚体以及Ni纳米颗粒上CO₂加氢的反应动力学. 通过计算不同基元反应本征活化能以及相应的反应速率常数, 证实了单原子Ni位点表现出了最低的CO₂加氢制CH₄活性, 因为其非常弱的加氢活性; 而相比于Ni纳米颗粒, Ni二聚体具有更低的加氢能垒, 因而具有更强的CH₄生成活性.

总之, 本文不仅阐明了对CO₂甲烷化反应具有活性的最小Ni团簇的结构, 还确定了结构不同的Ni物种的催化性能, 并实现了对催化剂中Ni物种结构的有效调控. 因此, 制备出了用于CO₂甲烷化的高效Ni基催化剂, 其Ni负载量可大幅降低至1%以下, 为进一步研发高性能CO₂加氢催化剂提供了理论指导.

关键词: 分子筛, 限域封装, Ni基催化剂, Ni二聚体, 二氧化碳加氢, 反应机理

Abstract:

Ni-based catalysts have shown significant potential in CO₂ methanation, but the high catalytic performance is usually obtained at quite high Ni loading, as small particles just transform CO₂ into CO via reverse water gas shift reaction. Thus, a scientifically and practically important work is clarification of the structure of the smallest active Ni species and the catalytic activity of structurally different Ni species. Here, MnO_x-modulated metallic nickel dimers (MnO_x-Ni₂) were embedded in silicalite-1 framework at a Ni loading of ~0.86%. It’s CO₂ conversion, CH₄ selectivity and CH₄ space time yield (STY) surprisingly reach ~76%, ~98% and ~450 mol·mol_Ni^-1·h^-1 at 400 °C, 0.5 MPa and 12000 mL·g^-1·h^-1. Such a catalytic performance can be well maintained at least within 200 h. In-situ spectroscopy, density functional theory (DFT) calculation and ab initio molecular dynamics simulation results confirm that Ni dimer (Ni₂) is the smallest Ni cluster triggering the CO₂ methanation and the CH₄ formation activity is linearly increased with the Ni₂ content. Introduction of MnO_x not only increases the number of Ni₂ species, but also improves its intrinsic activity in CO₂ methanation, as MnO_x enhances the electronic density of Ni species and facilitates NiO reduction to MnO_x-Ni₂ species. This species shows higher H₂ dissociation activity than single atom Ni (Ni₁), pure Ni₂ and large Ni nanoparticles (NPs). In addition, it exhibits much stronger CO adsorption and lower energy barrier of CO* intermediate hydrogenation to CH₄. In-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), isotope-labeled in-situ DRIFTS, on line mass spectroscopy (MS), Proton transfer reaction time of flight PTR TOF-MS and DFT calculation results reveal that CO₂ hydrogenation to methane on MnO_x-Ni₂@MFI mainly follows the HCOO* and CO* intermediates route.

Key words: Zeolite, Confined encapsulation, Ni-based catalyst, Nickel dimers, CO₂ hydrogenation, Reaction mechanism

王森, 李诗颖, 耿蕊, 周博, 王鹏飞, 秦张峰, 董梅, 王建国, 樊卫斌. 引发二氧化碳选择性加氢制甲烷的最小镍物种: 限域在MFI结构中的镍二聚体以及锰氧化物的增强作用[J]. 催化学报, 2026, 87: 113-125.

Sen Wang, Shiying Li, Rui Geng, Bo Zhou, Pengfei Wang, Zhangfeng Qin, Mei Dong, Jianguo Wang, Unni Olsbye, Weibin Fan. The smallest Ni species triggering selective hydrogenation of CO₂ to methane: Ni dimer embedded in MFI and enhancement of MnO_x[J]. Chinese Journal of Catalysis, 2026, 87: 113-125.

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图/表 5

Fig. 1. Catalytic performance of (x)Ni@MFI and (x)Ni-MnOx(y)@MFI in CO2 methanation. (a,b) Catalytic results of (0.9)Ni@MFI, (0.9)Ni-MnOx(y)@MFI and MnOx@MFI for CO2 hydrogenation to methane. (A) (0.9)Ni@MFI; (B) (0.9)Ni-MnOx(18.0)@MFI; (C) (0.9)Ni-MnOx(9.0)@MFI; (D) (0.9)Ni-MnOx(4.5)@MFI; (E) (0.9)Ni-MnOx(2.0)@MFI; (F) (0.9)Ni-MnOx(1.1)@MFI; (G) MnOx@MFI. Reaction conditions: 400 °C, 1 atm, 12000 mL·g-1·h-1, and H2/CO2 molar ratio of 4/1. (c) The CH4 STYs obtained on (0.9)Ni-MnOx(2.0)@MFI and reported typical Ni-based catalysts. (1) Ni3Fe2/ZrO2 (1 atm); (2) Ni-MCM-41 (1 atm); (3) Ni/a-TiO2-NH3 (1 atm); (4) Ni-sepiolite (1 atm); (5) Ni-La2O3/Na-Beta (1 atm); (6) Ni@NaX (0.5 MPa); (7) Ni/CeO2 (1 atm); (8) Ni/SiO2 (1 atm); (9) Ni-CeO2/Al2O3 (1 atm); (10) Ni@MGC (1 atm); (11) Ni/LaMgOx-ZSM-5 (1 atm); (12) Ni/SSZ-13 (1 atm); (13) NiMn/Al2O3 (1 atm); (14) Ni/CeO2 (1 atm); (15) LaNi1?xCoxO3 (1 atm); (16) Ni-CeO2/MCM-41 (1 atm); (17) Ni-CeO2-Y2O3 (1 atm); (18) LaNiOx (1 atm). (d) Catalytic stability test result of (0.9)Ni-MnOx(2.0)@MFI in CO2 hydrogenation to methane. Reaction conditions: 400 °C, 5 atm, 12000 mL·g-1·h-1 and H2/CO2 molar ratio of 4/1.

Fig. 2. Catalysts characterization of Ni-MnOx(x)@MFI catalyst. (a,b) In-situ XRD patterns of (0.9)Ni-MnOx(2.0)@MFI after reduction at 590 °C for 2 h in H2 atmosphere and further catalyzing CO2 hydrogenation at 400 °C for 6 h at 0.1 MPa and H2/CO2 molar ratio of 4/1. (c?e) TEM images of (0.9)Ni-MnOx(2.0)@MFI. High resolution aberration-corrected HAADF-STEM image (f) and corresponding color-enhanced contrast HAADF-STEM images (h,i) (the green-colored bright spots represent the highly dispersed NiOx and MnOx within silicalite-1 framework), and iDPC-STEM image (g) of (0.9)Ni-MnOx(2.0)@MFI. (j) STEM-EDX elemental mappings of Si, O, Ni and Mn in (0.9)Ni-MnOx(2.0)@MFI.

Fig. 3. Electronic structure and coordination state of Ni species. Ni-K edge XANES (a) and EXAFS (b) spectra of (0.9)Ni@MFI and (0.9)Ni-MnOx(2.0)@MFI after in-situ H2 reduction at 590 °C for 2 h, and reference samples of NiO and Ni foil. (c) The percentage of Ni species and the CN of Ni-Ni of reduced (x)Ni@MFI catalysts. (d) The dependence of CH4 formation rate (mol·h?1) derived from its space time yield on the Ni dimer amount of reduced (x)Ni@MFI catalysts. PDOS results for Ni, Mn, O and Si atoms of Ni-MnOx@MFI (e), and for Ni, O and Si atoms of Ni@MFI (f). (g) CDD result of Ni-MnOx@MFI. The accumulation and depletion charge regions are shown in yellow and cyan, respectively. Temperature and energy fluctuations (h) as well as the variation of Ni-Ni bonding distance of MnOx-Ni2 sites (i) in AIMD simulations at 873 K for a duration of ~10000 fs. (j) Radial distribution function (g(r)) and integrated g(r) for Ni-Ni bond of MnOx-Ni2 sites.

Fig. 4. Reaction mechanism of Ni@MFI and Ni-MnOx(x)@MFI catalysts in CO2 methanation. (a?c) Temperature-dependent in-situ DRIFTS of (0.9)Ni-MnOx(2.0)@MFI for CO2 hydrogenation. The arrow represents the increase in reaction temperature. Time-dependent in-situ DRIFTS of (0.9)Ni-MnOx(2.0)@MFI (d) and Ni@MFI (e) for CO2 hydrogenation at 180 °C. (f) Dependence of in-situ DRIFTS peak intensity of formate species on the reaction time at 180 °C on (0.9)Ni-MnOx(2.0)@MFI and (0.9)Ni@MFI. (g) On-line MS of the effluents during CO2 hydrogenation of (0.9)Ni-MnOx(2.0)@MFI. (h,i) Temperature-dependent in-situ PTR TOF-MS for CO2 hydrogenation on (0.9)Ni-MnOx(2.0)@MFI.

Fig. 5. DFT calculations and AIMD simulations. Reaction scheme for CO2 methanation (a) and free energy profiles of various elemental steps for CO2 hydrogenation to methane on Ni2 and MnOx-Ni2 sites (b). The free energy surface of CO* adsorption on Ni1 (c), Ni2 (d) and MnOx-Ni2 (e) sites obtained from metadynamics (MTD) calculations.

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引发二氧化碳选择性加氢制甲烷的最小镍物种: 限域在MFI结构中的镍二聚体以及锰氧化物的增强作用

The smallest Ni species triggering selective hydrogenation of CO₂ to methane: Ni dimer embedded in MFI and enhancement of MnO_x

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引发二氧化碳选择性加氢制甲烷的最小镍物种: 限域在MFI结构中的镍二聚体以及锰氧化物的增强作用

The smallest Ni species triggering selective hydrogenation of CO2 to methane: Ni dimer embedded in MFI and enhancement of MnOx

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The smallest Ni species triggering selective hydrogenation of CO₂ to methane: Ni dimer embedded in MFI and enhancement of MnO_x