铂镍单原子合金催化剂在一氧化碳还原一氧化氮反应中协同效应的最大化

doi:10.1016/S1872-2067(26)65149-2

催化学报 ›› 2026, Vol. 88: 422-431.DOI: 10.1016/S1872-2067(26)65149-2

铂镍单原子合金催化剂在一氧化碳还原一氧化氮反应中协同效应的最大化

张盛鑫^a^,^b^,¹, 李安琦^a^,^b^,¹, 虞周楠^a^,^b, 李林^a, 刘晓艳^a, 刘伟^a^,^*(), 王爱琴^a^,^*(), 张涛^a^,^*()

^a 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 116023
^b 中国科学院大学, 北京 100049

收稿日期:2025-12-22 接受日期:2026-02-28 出版日期:2026-09-18 发布日期:2026-09-05
通讯作者: *电子信箱: aqwang@dicp.ac.cn (王爱琴),
weiliu@dicp.ac.cn (刘伟),
taozhang@dicp.ac.cn (张涛).
基金资助:
国家重点研发计划(2023YFA1506603);国家自然科学基金委单原子催化基础科学中心(22388102);国家自然科学基金(22132006)

Pt-Ni single atom alloy: Maximized synergistic effect for NO reduction with CO

Shengxin Zhang^a^,^b^,¹, Anqi Li^a^,^b^,¹, Zhounan Yu^a^,^b, Lin Li^a, Xiaoyan Liu^a, Wei Liu^a^,^*(), Aiqin Wang^a^,^*(), Tao Zhang^a^,^*()

^a State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^b University of Chinese Academy of Sciences, Beijing 100049, China

Received:2025-12-22 Accepted:2026-02-28 Online:2026-09-18 Published:2026-09-05
About author:First author contact:1 共同第一作者.
1 Contributed equally to this work.
Supported by:
The National Key R&D Program of China(2023YFA1506603);The National Natural Science Foundation of China Center for Single-Atom Catalysis(22388102);The National Natural Science Foundation of China(22132006)

摘要/Abstract

摘要：

CO+NO反应是汽车尾气净化中的核心反应, 也是铂族贵金属催化的典型模型反应. 如何通过催化剂的创新, 在维持优异催化活性和选择性的同时大幅降低贵金属用量, 是该反应实际应用过程中面临的长期挑战. 单原子催化剂由于其100%的贵金属原子利用率、孤立的活性位点以及可调控的配位环境, 为发展低成本贵金属催化剂提供了机遇. 但传统的单一金属单原子催化剂在反应过程中容易聚集烧结而导致失活. 与之相比, 单原子合金催化剂具有优异的热稳定性和两种不同金属元素之间的协同效应, 有望在CO+NO反应中实现高活性和高稳定性.
本文设计并制备了一种TiO₂纳米片负载的PtNi单原子合金催化剂, 其中孤立的单原子Pt均匀分散于Ni颗粒中. 高分辨电镜和多种光谱表征结果显示, 当Pt/Ni原子比为1/40时, 能够形成稳定的PtNi单原子合金结构; 并且由于Ni向Pt单原子发生显著的电子转移, 使得Pt单原子携带一定负电荷. 与对应的单金属Pt, Ni以及PtNi非均匀合金催化剂相比, 该PtNi₄₀/TiO₂单原子合金催化剂表现出显著提升的催化性能, 在250 °C即可实现NO的完全转化, 且N₂选择性达100%; 在长达100 h的连续运行中展现出优异的结构稳定性. 进一步研究发现, 催化剂的高活性与Pt单原子位点孤立度和富电子程度密切相关, 表明了单原子合金结构在该反应中的关键作用. 结合原位红外光谱实验与理论计算分析进一步揭示了反应机制, NO分子倾向于在Ni位点上发生吸附与解离, 而CO则优先吸附在富电子的Pt单原子位点. 与单金属Pt催化剂相比, NO与CO在PtNi单原子合金结构上反应能垒显著降低, 从理论上解释了该催化剂在提高反应活性和产物选择性方面的优异表现.
综上, 本工作开发的PtNi₄₀/TiO₂单原子合金催化剂, 通过构建富电子Pt单原子与Ni基底形成的单原子合金结构进而调节反应物吸附位点和降低反应能垒, 从而在CO还原NO反应中表现出卓越的催化性能. 本文为在相关催化体系中设计兼具高性能与低成本的贵金属催化剂, 提供了一种可行的结构设计策略.

关键词: 铂镍合金, 单原子合金, 一氧化氮还原, 带负电荷的单原子铂, 吸附位点

Abstract:

The reduction of NO with CO is a key reaction in emission control and heavily relies on the use of noble metal catalysts. Reducing the catalyst cost without compromising the activity and selectivity is still a challenge. In this work, we design a PtNi₄₀ single atom alloy (SAA) catalyst featuring Pt single atoms uniformly distributed in a Ni matrix supported on TiO₂ nanosheets. The PtNi₄₀/TiO₂ catalyst exhibits superior performance compared to its monometallic and random alloy counterparts, achieving complete NO conversion and 100% N₂ selectivity at 250 °C and outstanding stability over a 100-h run. High angle annular dark field scanning transmission electron microscopy imaging, X-ray absorption fine structure, in-situ diffuse reflectance infrared Fourier transform spectroscopy and X-ray photoelectron spectroscopy characterizations reveal a distinctive synergy between the two metals. Pt single atoms are negatively charged due to remarkable electron transfer from Ni to Pt, and NO dissociation occurs on Ni ensembles whereas CO is preferentially adsorbed on electron-rich Pt single atoms. The reaction of NO+CO proceeds over the Pt-Ni SAA structure with a much lower barrier compared to monometallic Pt catalyst, demonstrating the unrivalled capability of SAA for enhancing the activity and selectivity with much reduced use of noble metals.

Key words: PtNi alloy, Single atom alloy, NO reduction, Negatively charged Pt atoms, Adsorption sites

张盛鑫, 李安琦, 虞周楠, 李林, 刘晓艳, 刘伟, 王爱琴, 张涛. 铂镍单原子合金催化剂在一氧化碳还原一氧化氮反应中协同效应的最大化[J]. 催化学报, 2026, 88: 422-431.

Shengxin Zhang, Anqi Li, Zhounan Yu, Lin Li, Xiaoyan Liu, Wei Liu, Aiqin Wang, Tao Zhang. Pt-Ni single atom alloy: Maximized synergistic effect for NO reduction with CO[J]. Chinese Journal of Catalysis, 2026, 88: 422-431.

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图/表 6

Fig. 1. HAADF-STEM characterization of different catalysts. (a-d) images of Pt/TiO2 (a), PtNi1/TiO2 (b), PtNi4/TiO2 (c), and PtNi40/TiO2 and corresponding EDS mapping images (d) of Ti, Ni, O, Pt. (e) Average particle sizes.

Fig. 2. Identification of microstructure of PtNix/TiO2 catalysts with different Pt/Ni atomic ratios. XANES spectra (a) and Fourier transformed EXAFS (b) at Pt L3-edge. (c) In-situ DRIFTS for CO adsorption. (d) Pt 4f XPS for Pt/TiO2 and PtNi40/TiO2 catalysts.

Fig. 3. Catalytic performances of PtNix/TiO2 catalysts for CO-NO reaction. (a) NO conversion. (b) N2 selectivity. (c) The TOF at 250 °C as a function of Pt-Ni percentage. (d) The TOF at 250 °C as a function of wavenumber of linearly adsorbed CO on Pt. Reaction conditions: 100 mg catalyst; 0.2% CO; 0.2% NO; He balance; total flow rate 33.3 mL/min; GHSV of 20000 h-1.

Fig. 4. NO-TPD profiles over different catalysts. (a) Pt/TiO2; (b) Ni/TiO2; (c) PtNi4/TiO2; (d) PtNi40/TiO2.

Fig. 5. In-situ DRIFTS spectra on different catalysts. (a) NO adsorption. (b) NO+CO co-adsorption.

Fig. 6. Calculated mechanism of CO-SCR over Pt/TiO2 and PtNi40/TiO2.

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铂镍单原子合金催化剂在一氧化碳还原一氧化氮反应中协同效应的最大化

Pt-Ni single atom alloy: Maximized synergistic effect for NO reduction with CO

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