调控Pt/Cu-SSZ-13界面相互作用优化氨选择性催化氧化性能

doi:10.1016/S1872-2067(26)64958-3

催化学报 ›› 2026, Vol. 83: 376-387.DOI: 10.1016/S1872-2067(26)64958-3

调控Pt/Cu-SSZ-13界面相互作用优化氨选择性催化氧化性能

李佳幸^,¹, 彭悦^,¹, 李一凡, 隆云鹏, William Orbell, 高传, 朱晓, 袁兴, 陈琳, 李俊华^*()

清华大学环境学院, 北京 100084

收稿日期:2025-09-10 接受日期:2025-11-12 出版日期:2026-04-18 发布日期:2026-03-04
通讯作者: * 电子信箱: lijunhua@tsinghua.edu.cn (李俊华).
作者简介:¹共同第一作者.
基金资助:
国家自然科学基金(22406102);国家自然科学基金(22276104);国家自然科学基金(T2341002);中国博士后科学基金(2024M751726);中国博士后科学基金会博士后资助计划(GZB20240348);清华大学“水木学者”计划(2023SM224)

Modulation of Pt-Cu interaction in Pt/Cu-SSZ-13 for selective catalytic oxidation of ammonia

Jiaxing Li^,¹, Yue Peng^,¹, Yifan Li, Yunpeng Long, William Orbell, Chuan Gao, Xiao Zhu, Xing Yuan, Lin Chen, Junhua Li^*()

School of Environment, Tsinghua University, Beijing 100084, China

Received:2025-09-10 Accepted:2025-11-12 Online:2026-04-18 Published:2026-03-04
Contact: * E-mail: lijunhua@tsinghua.edu.cn (J. Li).
About author:¹Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22406102);National Natural Science Foundation of China(22276104);National Natural Science Foundation of China(T2341002);China Postdoctoral Science Foundation(2024M751726);Postdoctoral Fellowship Program of CPSF(GZB20240348);Shui Mu Tsinghua Scholar(2023SM224)

摘要/Abstract

摘要：

随着全球能源结构向零碳化转型, 氨(NH₃)作为一种高能量密度的无碳燃料及氢能载体, 其应用前景广阔. 然而, 利用过程中NH₃的逃逸会造成严重的氮污染, 开发高效的NH₃选择性催化氧化(NH₃-SCO)催化剂是解决该问题的关键. 传统的Pt基催化剂虽然低温活性优异, 但受限于Pt位点过强的本征氧化能力及对中间产物不适宜的吸附强度, 极易驱动关键中间物种(-NH_x)深度氧化生成N₂O或NO_x, 难以克服“活性-选择性”的博弈难题. 利用Cu-SSZ-13分子筛优异的选择性催化还原(SCR)氧化还原特性构建Pt/Cu双功能催化剂是突破该瓶颈的有效途径. 然而, 如何从微观层面精准调控Pt与Cu物种间的电子状态及空间分布, 阐明双位点间的中间体传递机制与动力学匹配规律, 仍是催化领域亟待解决的核心科学问题.
本文通过控制合成策略, 对比了物理混合(PM)与高能机械研磨(GR)两种方法, 构建了具有差异化界面耦合模式的Pt/Cu-SSZ-13催化剂, 旨在探究Pt-Cu相互作用对SCO反应路径的调控机制. 多尺度结构表征(X-射线衍射, 高分辨透射电镜, 扩展X-射线吸收精细结构)与电子态分析(X-射线光电子能谱, X-射线吸收近边结构, CO-漫反射红外光谱(DRIFTS))结果表明, 简便的物理混合策略(Pt/Cu-CHA-PM)成功构建了适度的Pt-Cu相互作用, 使得Pt纳米颗粒维持在优化的电子状态(粒径~11.8 nm), 同时完整保留了分子筛骨架中高活性的孤立Z₂Cu位点(其中Z代表分子筛骨架上的负电荷位点); 相反, 剧烈研磨诱导了强烈的Pt-Cu合金化效应及Pt位点过高的电子云密度, 抑制了O₂的解离活化. 催化性能测试显示, Pt/Cu-CHA-PM表现出较好的低温活性(T₉₀ = 180 °C)和宽温区高N₂选择性(280‒300 °C, > 90%), 160 °C时转换频率达0.00402 s^‒1, 是GR样品的4.6倍. 动力学分析、¹⁸O同位素示踪及原位光谱学(原位DRIFTS和紫外-可见光漫反射光谱)研究揭示了构效关系: PM样品中适度的电子相互作用优化了Pt表面的O₂吸附能与NH₃脱氢能垒, 倾向于生成易于转化的^*NO_x中间物种, 而非发生寄生性的N-N偶联生成N₂O; 生成的NO_x随后迅速迁移至邻近的Z₂Cu位点, 通过“快速内部SCR(i-SCR)”机制与吸附的NH₃反应高效转化为N₂. 此外, 在苛刻的水热老化条件(750 °C, 10 h)下, 该催化剂表现出独特的活性位点动态重构机制: 一方面, 分子筛骨架中热力学不稳定的ZCuOH位点通过脱羟基作用转化为SCR活性更高且更稳定的孤立Z₂Cu位点; 另一方面, Pt纳米颗粒的受控烧结(Ostwald熟化)使其尺寸与电子态向“火山型”曲线的顶点演变. 这种双位点的协同演化机制有效维持了高效的i-SCR反应路径, 赋予了催化剂优异的抗老化性能.
综上, 本研究阐明了通过物理限域调控双金属位点电子相互作用与空间距离的重要性, 揭示了双功能催化剂中氧化-还原半反应的动力学匹配机制, 为理性设计下一代高性能、高稳定性的氨逃逸控制催化剂提供了普适性的理论指导与合成策略.

关键词: Cu-SSZ-13, 内部选择性催化还原机理, 氨选择性催化氧化, 氮气选择性增加, 抗水热老化

Abstract:

Modulating the potent oxidative nature of Pt sites is the central strategy for optimizing the selective catalytic oxidation of NH₃ (NH₃-SCO). The primary challenge is to suppress byproduct formation (N₂O, NO_x) while preserving the intrinsic activity for N₂ production, a balance governed by the metal-support interaction. Herein, a facile physical-mixing strategy is demonstrated to engineer a Pt/Cu-SSZ-13 catalyst that simultaneously establishes a moderate Pt-Cu interaction while preserving the integrity of isolated Z₂Cu sites. This catalyst demonstrates superior performance, achieving 98% NH₃ conversion at 180 °C and over 90% N₂ selectivity (280‒300 °C), outperforming its counterpart prepared by intensive grinding. It also exhibits exceptional hydrothermal stability (750 °C, 10 h). Electronic structure and in-situ spectroscopy results reveal that the Pt-Cu electronic interaction tunes the reactivity of Pt sites to selectively catalyze the formation of *NO_x intermediates. Concurrently, the preserved Z₂Cu sites act as distinct active centers for NH₃ adsorption, which then readily reduce these intermediates to N₂.

Key words: Cu-SSZ-13, Internal-selective catalytic reduction mechanism, NH₃-selective catalytic oxidation, N₂ selectivity enhancement, Hydrothermal aging resistance

李佳幸, 彭悦, 李一凡, 隆云鹏, William Orbell, 高传, 朱晓, 袁兴, 陈琳, 李俊华. 调控Pt/Cu-SSZ-13界面相互作用优化氨选择性催化氧化性能[J]. 催化学报, 2026, 83: 376-387.

Jiaxing Li, Yue Peng, Yifan Li, Yunpeng Long, William Orbell, Chuan Gao, Xiao Zhu, Xing Yuan, Lin Chen, Junhua Li. Modulation of Pt-Cu interaction in Pt/Cu-SSZ-13 for selective catalytic oxidation of ammonia[J]. Chinese Journal of Catalysis, 2026, 83: 376-387.

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Fig. 1. (a) XRD patterns of Cu-SSZ-13, Pt/Cu-CHA-PM and Pt/Cu-CHA-GR catalyst. HR-TEM images of Pt/Cu-CHA-PM (b) and Pt/Cu-CHA-GR (c) catalysts obtained after different treatments. (d) Metal particle size distributions of the Pt/Cu-CHA-PM and Pt/Cu-CHA-GR. The histograms were obtained from the statistical analysis of over 150 particles for each catalyst. (e) EDX-mapping and line scan of selected area of Pt/Cu-CHA-PM.

Fig. 2. (a) XANES spectra at Pt L3-edge of Pt foil, PtO2, Pt/Cu-CHA-PM and Pt/Cu-CHA-GR. (b) In-situ DRIFTS of CO adsorption at 25 °C on Pt/Cu- CHA-PM and Pt/Cu-CHA-GR. (c) H2-TPR profiles for Cu-SSZ-13, Pt/Cu-CHA-GR and Pt/Cu-CHA-PM. (d) Fourier-transformed EXAFS k2-weighted χ(k) function spectra of Pt foil, PtO2, Pt/Cu-CHA-PM and Pt/Cu-CHA-GR. (e) WT k2-weighted EXAFS contour plots for Cu foil, CuO, Pt/Cu-CHA-PM and Pt/Cu-CHA-GR.

Fig. 3. (a) TOF of Pt/Cu-CHA-PM and Pt/Cu-CHA-GR at 160 °C. (b) N2 selectivity on Pt/Cu-CHA-PM, Pt/Cu-CHA-GR, Cu-SSZ-13 and Pt/Al2O3 in the NH3 SCO reaction. Reaction conditions: 500 ppm NH3, 2 vol% O2, balance with N2, WHSV = 60000 mL·gcat?1·h?1. (c) Reaction orders for NH3 and O2 of Pt/Cu-CHA-PM, Pt/Cu-CHA-GR and Cu-SSZ-13. (d) NH3 SCO performance as a function of NH3 conversion at 180 °C on different catalysts. (e) Concentrations of N2O, NOx and N2 selectivity at 300 °C of different catalysts.

Fig. 4. In-situ DRIFTS contour image during the reaction between the pulsed O2 with NH3 ad at 180 °C of Pt/Cu-CHA-PM (a) and Pt/Cu-CHA-GR (b). Evolution of the UV-vis spectra of Pt/Cu-CHA-PM (c) and Pt/Cu-CHA-GR (d) during successive feed of NH3+O2 at 180 °C. Comparison of time-dependent peak intensities between the LMCT band at 265 nm in DRUVS of Pt/Cu-CHA-PM (e) and Pt/Cu-CHA-GR (f) during the reduction (in NH3) and reoxidation (in NH3 + O2) half-cycles. NH3 atmosphere: 500 ppm NH3; NH3 + O2 atmosphere: 500 ppm NH3, 2 vol% O2. All feedings had a total flow rate of 100 mL·min?1 and were balanced with Ar. In-situ DRUVS spectra of Pt/Cu-CHA-PM (g) and Pt/Cu-CHA-GR (h) in different gas mixtures at 300 °C.

Fig. 5. Mass signals of O species during in-situ pulses of 16O16O/18O18O over the Pt/Cu-CHA-PM (a) and Pt/Cu-CHA-GR (b) catalyst. In-situ DRIFTS spectra during the reaction between the pulsed O2 with NH3 ad as a function of temperature over the Pt/Cu-CHA-PM (c) and Pt/Cu-CHA-GR (d) catalyst. (e) A schematic illustration of selective NH3-to-N2 oxidation over Pt/Cu-CHA-PM via the fast i-SCR mechanism.

Fig. 6. (a) NH3 conversion on Pt/Cu-CHA-PM, Pt/Cu-CHA-PM(aged), Pt/Cu-CHA-GR and Pt/Cu-CHA-GR(aged) in the NH3 SCO reaction. (b) Correlation between PtCu nanoparticle size and NH3 conversion rate at 180 °C. (c) N2 selectivity on Pt/Cu-CHA-PM, Pt/Cu-CHA-PM(aged), Pt/Cu-CHA-GR and Pt/Cu-CHA-GR(aged) in the NH3 SCO reaction. Reaction conditions: 500 ppm NH3, 2 vol% O2, balance with N2, WHSV = 60000 mL·gcat?1·h?1. (d) Product distribution of Pt/Cu-CHA-PM, Pt/Cu-CHA-PM(aged), Pt/Cu-CHA-GR and Pt/Cu-CHA-GR(aged). (e) The Cu sites proportion on Pt/Cu-CHA-PM, Pt/Cu-CHA-PM(aged), Pt/Cu-CHA-GR and Pt/Cu-CHA-GR(aged), obtained from normalized peak area results in in-situ DRIFTS. (f) In-situ DRIFTS contour image during the reaction between the pulsed O2 with NH3 ad at 180 °C of Pt/Cu-CHA-GR(aged).

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调控Pt/Cu-SSZ-13界面相互作用优化氨选择性催化氧化性能

Modulation of Pt-Cu interaction in Pt/Cu-SSZ-13 for selective catalytic oxidation of ammonia

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