硫酸化氧化锆负载的Ru单原子催化甲烷直接转化制甲醇

doi:10.1016/S1872-2067(22)64191-3

催化学报 ›› 2023, Vol. 46: 64-71.DOI: 10.1016/S1872-2067(22)64191-3

硫酸化氧化锆负载的Ru单原子催化甲烷直接转化制甲醇

刘华^a^,^b, 康磊磊^a, 王华^a, 蒋齐可^c, 刘晓艳^a^,^*(), 王爱琴^a

^a中国科学院大连化学物理研究所, 中国科学院航天催化材料重点实验室, 辽宁大连 116023
^b中国科学院大学, 北京 100049
^c中国科学院大连清洁能源国家实验室, 辽宁大连 116023

收稿日期:2022-09-09 接受日期:2022-11-02 出版日期:2023-03-18 发布日期:2023-02-21
通讯作者: *电子信箱: xyliu2003@dicp.ac.cn (刘晓艳)
基金资助:
辽宁省兴辽英才计划项目(XLYC2007070);, 国家自然科学基金项目(22102180);, 中国科学院洁净能源创新研究院合作基金资助项目(DNL202002);, 中央高校基本科研业务费专项资金资助(20720220009)

Ru single-atom catalyst anchored on sulfated zirconia for direct methane conversion to methanol

Hua Liu^a^,^b, Leilei Kang^a, Hua Wang^a, Qike Jiang^c, Xiao Yan Liu^a^,^*(), Aiqin Wang^a

^aCAS Key Laboratory of Science and Technology on Applied Catalysis, iChEM, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^bUniversity of Chinese Academy of Sciences, Beijing 100049, China
^cDalian National Laboratory for Clean Energy, Chinese Academy of Sciences, Dalian 116023, Liaoning, China

Received:2022-09-09 Accepted:2022-11-02 Online:2023-03-18 Published:2023-02-21
Contact: *E-mail: xyliu2003@dicp.ac.cn (X. Liu)
Supported by:
Liaoning Revitalization Talents Program, China(XLYC2007070);The National Natural Science Foundation of China(22102180);Dalian National Laboratory Cooperation Fund, Chinese Academy of Sciences, China(DNL202002);The Fundamental Research Funds for the Central Universities(20720220009)

摘要/Abstract

摘要：

天然气作为一种低碳清洁能源, 其储量大、价格低、热值高, 被认为是最有前途的石油替代资源之一. 甲烷是天然气的主要成分, 直接转化为甲醇是有效利用甲烷的一种途径, 也是一个极具挑战性的课题. 一方面, 甲烷的C‒H键(439.3 kJ·mol^-1)强度非常高, 活化十分困难; 另一方面, 在反应条件下, 甲醇等产物比甲烷更容易被氧化, 从而导致目标产物的选择性不高. 因此, 设计高效催化剂是解决该难题的有效途径之一. 研究(J. Catal., 1993, 144. 238-253和Catal. Today, 2021, 365, 71-79)发现, 硫酸化的氧化锆(SZ)负载的贵金属(例如Pt等)等超强酸催化剂能够促进甲烷在脱氢芳构化反应中的活化.

受该工作启发, 本文通过模拟均相催化设计了固体超强酸负载的Ru单原子催化剂(SAC), 并在温和条件(70 ^oC)下将其用于甲烷直接转化制甲醇反应. 结果发现, 在Ru/SZ SAC上的含氧化合物(CH₃OH, CH₃OOH和HCOOH)收率(18.32 µmol, ≥ 80 h^-1)显著超过SZ(0.67 µmol)和Ru/ZrO₂ (0.29 µmol), 这表明在Ru/SZ SAC上形成了新的活性中心. 结合¹³CH₄同位素标记实验、吡啶吸附红外光谱(PY-IR)、电子顺磁共振(EPR)和X射线光电子能谱(XPS)等表征结果, 提出了Ru单原子和超强酸位点协同催化甲烷转化制甲醇的反应机理. 首先, 通过AC-HADDF-STEM证明了Ru/SZ SAC的成功制备; PY-IR谱和氨气程序升温脱附结果证明了在该体系中硫酸化处理有效增加了催化剂表面的强酸位点(包括B-酸和L-酸). EPR结果表明, 与ZrO₂和0.1Ru/ZrO₂相比, 在SZ和0.1Ru/SZ上产生更多^•OH. 进一步结合催化剂表面酸性变化情况和文献报道说明, 催化剂表面的强酸位点(包括B-酸和L-酸)可以促进H₂O₂有效分解成^•OH和^•OOH, 而^•OH在甲烷活化的过程中起着至关重要的作用, 这合理解释了0.1Ru/SZ比0.1Ru/ZrO₂催化性能更好的原因. 结合XPS结果推测, 硫酸根的强吸电子作用使与其相邻的Ru^δ⁺和Zr^γ⁺的价态都高于+4 (δ > 4, γ > 4). 综上提出了Ru^δ⁺和Zr^γ⁺协同催化甲烷C‒H键断裂的反应机理: CH₄和H₂O₂分别在Ru^δ⁺和Zr^γ⁺上形成Ru^δ⁺-CH₄和Zr^γ+-^•OH; 然后, Zr^γ⁺-^•OH提取相邻Ru^δ⁺-CH₄的氢原子并生成CH₃OH. Ru单原子与SZ的协同作用有效地促进了CH₄向C1含氧化合物的转化, 这为设计高效的多功能协同催化甲烷直接转化制甲醇反应的SACs开辟了新途径.

关键词: 单原子钌, 硫酸化氧化锆, 强酸位点, 直接CH₄转化, 协同催化

Abstract:

The direct CH₄ conversion (DMC) to methanol is a challenging topic. In this study, the Ru/SZ (sulfated zirconia) single-atom catalysts (SACs) were synthesized and utilized to the DMC to methanol under mild conditions (70 °C). The yield over the Ru/SZ SACs (18.32 µmol, TOF ≥ 80 h^-1) significantly exceeded the sum of the yields over the SZ (0.67 µmol) and Ru/ZrO₂ (0.29 µmol), indicating that a new active center was formed on the Ru/SZ SACs. Combined with the results of the ¹³CH₄ isotope labeling experiments and various characterizations including the pyridine adsorption infrared spectroscopy, electron paramagnetic resonance and X-ray photoelectron spectroscopy, an unprecedented synergy effect between the single-atom and the super acid sites was pictured: The strong acidity of the Ru/SZ SACs could effectively promote the decomposition of H₂O₂ into the ^•OH, and the Ru^δ⁺ (δ > 4) and the adjacent Zr^γ⁺-^•OH (γ > 4) could synergistically catalyze the CH₄ to methanol.

Key words: Ru single atom, Sulfated zirconia, Strong acid site, Direct methane conversion, Synergistic catalysis

刘华, 康磊磊, 王华, 蒋齐可, 刘晓艳, 王爱琴. 硫酸化氧化锆负载的Ru单原子催化甲烷直接转化制甲醇[J]. 催化学报, 2023, 46: 64-71.

Hua Liu, Leilei Kang, Hua Wang, Qike Jiang, Xiao Yan Liu, Aiqin Wang. Ru single-atom catalyst anchored on sulfated zirconia for direct methane conversion to methanol[J]. Chinese Journal of Catalysis, 2023, 46: 64-71.

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https://www.cjcatal.com/CN/Y2023/V46/I3/64

图/表 6

Fig. 1. (a) XRD patterns of the ZrO2, SZ and Ru/SZ catalysts. AC-HAADF-STEM images of the 0.05Ru/SZ (b), 0.1Ru/SZ (c) and 0.3Ru/SZ catalysts (d).

Fig. 2. (a) Catalytic performance of DMC on ZrO2, 0.1Ru/ZrO2, SZ and Ru/SZ catalysts. (b) The TOF of oxygenates on Ru/SZ catalysts for the DMC reaction.

Fig. 3. PY-IR spectra (a) and NH3-TPD results (b) of the ZrO2, 0.1Ru/ZrO2, SZ and 0.1Ru/SZ catalysts.

Fig. 4. EPR spectra of the DMC on the ZrO2, 0.1Ru/ZrO2, SZ and 0.1Ru/SZ catalysts.

Fig. 5. 13C NMR spectra of reaction products from the DMC.

Fig. 6. Reaction mechanism for the DMC over the Ru/SZ SACs.

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硫酸化氧化锆负载的Ru单原子催化甲烷直接转化制甲醇

Ru single-atom catalyst anchored on sulfated zirconia for direct methane conversion to methanol

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