层状双金属氢氧化物的层间阴离子对衍生的Ni-Al2O3催化剂光热催化CO2甲烷化反应的影响

doi:10.3866/PKU.WHXB202309002

物理化学学报 >> 2025, Vol. 41 >> Issue (1): 100002.doi: 10.3866/PKU.WHXB202309002

所属专题：能源化学

层状双金属氢氧化物的层间阴离子对衍生的Ni-Al₂O₃催化剂光热催化CO₂甲烷化反应的影响

郭李娜¹, 李睿哲¹, 孙闯¹, 罗小利¹, 石义秋¹, 原弘¹^,*(), 欧阳述昕¹^,*(), 张铁锐²^,*()

¹ 华中师范大学化学学院, 教育部光能利用与减污降碳工程研究中心, 农药与化学生物学教育部重点实验室, 武汉 430079
² 中国科学院物理化学技术研究所, 光化学转化与功能材料重点实验室, 北京 100190

收稿日期:2023-09-01 修回日期:2023-10-06 录用日期:2023-10-19 发布日期:2023-12-20
通讯作者: Email: yuanhong@mail.ccnu.edu.cn (原弘)oysx@mail.ccnu.edu.cn (欧阳述昕)tierui@mail.ipc.ac.cn (张铁锐)
基金资助:
国家自然科学基金(21972052); 国家自然科学基金(22272061); 辐射化学与功能材料湖北省重点实验室开放基金(2021KF01)

Effect of Interlayer Anions in Layered Double Hydroxides on the Photothermocatalytic CO₂ Methanation of Derived Ni-Al₂O₃ Catalysts

Lina Guo¹, Ruizhe Li¹, Chuang Sun¹, Xiaoli Luo¹, Yiqiu Shi¹, Hong Yuan¹^,*(), Shuxin Ouyang¹^,*(), Tierui Zhang²^,*()

¹ Engineering Research Center of Photoenergy Utilization for Pollution Control and Carbon Reduction, Ministry of Education; Key Laboratory of Pesticide and Chemical Biology of Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, China
² Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, China

Received:2023-09-01 Revised:2023-10-06 Accepted:2023-10-19 Published:2023-12-20
Contact: Email: yuanhong@mail.ccnu.edu.cn (Hong Yuan)oysx@mail.ccnu.edu.cn (Shuxin Ouyang)tierui@mail.ipc.ac.cn (Tierui Zhang)
Supported by:
the National Natural Science Foundation of China(21972052); the National Natural Science Foundation of China(22272061); Foundation Project of Hubei Key Laboratory of Radiation Chemistry and Functional Materials(2021KF01)

1. 附件.pdf(1692KB)

摘要/Abstract

摘要：

太阳能驱动的二氧化碳(CO₂)甲烷化反应不仅有助于减少多余的碳排放，而且是生产燃料的重要途径。层状金属双氢氧化物(layered double hydroxides，LDH)可以在高温还原气(H₂/Ar)氛围中还原，转化为金属负载于氧化物(MO)的催化剂。这些催化剂在CO₂加氢反应中作为优秀的光热催化剂被广泛应用。然而，有关LDH的层间阴离子类型如何影响CO₂甲烷化活性的研究还相对有限。本文研究了包含不同层间阴离子的镍(Ni)铝(Al) LDH前驱体，通过在H₂/Ar气氛中还原处理，制备了一系列Ni负载在氧化铝(Al₂O₃)上的MO催化剂，这些催化剂被命名为NiAl-x-MO (其中x代表CO₃、NO₃、Cl和SO₄，分别代表碳酸根、硝酸根、氯离子和硫酸根等阴离子)。其中，NiAl-CO₃-MO催化剂表现出50.1%的CO₂转化率，99.9%的甲烷(CH₄)选择性以及94.4 mmol∙g⁻¹∙h⁻¹的CH₄产出速率。与之相比，NiAl-Cl-MO和NiAl-SO₄-MO催化剂的CO₂甲烷化活性极低。H₂程序升温脱附(temperature programmed desorption with H₂，H₂-TPD)实验和密度泛函理论计算(density functional theory，DFT)结果表明，低CO₂转化率是由于残留的氯(Cl)或硫(S)与金属Ni形成的强配位键阻碍了H₂的吸附和活化。因此，在设计LDH衍生的催化剂，特别是用于氢化反应的Ni基催化剂时，应优先考虑层间阴离子在LDH中的重要作用。

关键词: 光热催化, CO₂甲烷化, Ni-Al₂O₃催化剂, 层状金属双氢氧化物, 层间阴离子

Abstract:

The concentration of carbon dioxide (CO₂) in the atmosphere is progressively increasing due to industrial development, leading to environmental concerns such as the greenhouse effect. Consequently, it is crucial to decrease dependence on the fossil fuels and mitigate the CO₂ emissions. Photothermocatalysis technology facilitates the conversion of light energy into heat energy on the surface of catalysts, thereby driving chemical reactions. This catalytic approach effectively harnesses ample solar energy, consequently reducing non-renewable energy consumption. Solar-driven CO₂ methanation is an important route to simultaneously mitigate excessive carbon emissions and produce fuels. Layered double hydroxides (LDH) can be reduced at high temperature in a reductive atmosphere of a hydrogen/argon (H₂/Ar) mixture to prepare metal-loaded oxide (MO) catalysts, which are widely used in CO₂ hydrogenation reactions as excellent photothermal catalysts. However, there is limited study on how the interlayer anion type of LDH affects the activity of CO₂ methanation. Herein, a series of LDH precursors, intercalated with various anions, were synthesized using a co-precipitation method. The LDH precursors were reduced in a H₂/Ar atmosphere to acquire a group of nickel (Ni) loaded on alumina (Al₂O₃) catalysts, referred to as NiAl-x-MO (x = CO₃, NO₃, Cl, and SO₄, which represents carbonate, nitrate, chloride, and sulfate anions, respectively). Energy dispersive spectrometer (EDS) elemental mapping and X-ray photoelectron spectroscopy (XPS) results revealed the presence of nitrogen (N), chlorine (Cl), and sulfur (S) species on the surfaces of NiAl-NO₃-MO, NiAl-Cl-MO, and NiAl-SO₄-MO catalysts, respectively. Photothermocatalytic tests were conducted on the catalysts to assess the potential influence of the residual species on CO₂ methanation. Among them, the NiAl-CO₃-MO catalyst demonstrated a CO₂ conversion of 50.1%, methane (CH₄) selectivity of 99.9%, along with a CH₄ production rate of 94.4 mmol∙g⁻¹∙h⁻¹. The performance of the NiAl-NO₃-MO catalyst was found to be comparable to that of the NiAl-CO₃-MO catalyst. In contrast, the CO₂ methanation activity of the NiAl-Cl-MO and NiAl-SO₄-MO catalysts were negligible. CO₂ temperature programmed desorption (CO₂-TPD) analysis demonstrated that the presence of N, Cl, and S species had a negligible effect on the adsorption of CO₂. H₂ temperature programmed desorption (H₂-TPD) and density functional theory (DFT) results suggested that the strong coordination bond between residual Cl or S species and metallic Ni impeded the absorption and activation of H₂, which was responsible for the low CO₂ conversion. Hence, the significant role of the interlayer anion in LDH should be preferentially considered when designing LDH-derived catalysts, especially the Ni-based catalysts for hydrogenation reactions.

Key words: Photothermocatalysis, CO₂ methanation, Ni-Al₂O₃ catalyst, Layered double hydroxides, Interlayer anion

郭李娜, 李睿哲, 孙闯, 罗小利, 石义秋, 原弘, 欧阳述昕, 张铁锐. 层状双金属氢氧化物的层间阴离子对衍生的Ni-Al₂O₃催化剂光热催化CO₂甲烷化反应的影响[J]. 物理化学学报, 2025, 41(1), 100002. doi: 10.3866/PKU.WHXB202309002

Lina Guo, Ruizhe Li, Chuang Sun, Xiaoli Luo, Yiqiu Shi, Hong Yuan, Shuxin Ouyang, Tierui Zhang. Effect of Interlayer Anions in Layered Double Hydroxides on the Photothermocatalytic CO₂ Methanation of Derived Ni-Al₂O₃ Catalysts[J]. Acta Phys. -Chim. Sin. 2025, 41(1), 100002. doi: 10.3866/PKU.WHXB202309002

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB202309002

https://www.whxb.pku.edu.cn/CN/Y2025/V41/I1/100002

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层状双金属氢氧化物的层间阴离子对衍生的Ni-Al₂O₃催化剂光热催化CO₂甲烷化反应的影响

Effect of Interlayer Anions in Layered Double Hydroxides on the Photothermocatalytic CO₂ Methanation of Derived Ni-Al₂O₃ Catalysts

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