Al2O3孤岛与Ir@Pt/TiO2协同催化实现高活性耐硫甲烷氧化

doi:10.1016/S1872-2067(26)64951-0

催化学报 ›› 2026, Vol. 83: 400-410.DOI: 10.1016/S1872-2067(26)64951-0

Al₂O₃孤岛与Ir@Pt/TiO₂协同催化实现高活性耐硫甲烷氧化

武金玮, 陈俊妃, 张明康, 芮泽宝^*()

中山大学化学工程与技术学院, 广东省海洋生物质平台化学品及其功能化工程技术研究中心, 广东省南方海洋实验室(珠海), 广东珠海 519082

收稿日期:2025-08-11 接受日期:2025-10-27 出版日期:2026-04-18 发布日期:2026-03-04
通讯作者: * 电子信箱: ruizebao@mail.sysu.edu.cn (芮泽宝).
基金资助:
国家自然科学基金(22476222);广东省重点领域研发项目(2020B1111360004);广东省自然科学基金杰出青年基金(2022B1515020098)

Engineering isolated Al₂O₃ island enables adjacent TiO₂-supported Ir@Pt nanoparticles for efficient and sulfur-resistant lean methane oxidation

Jinwei Wu, Junfei Chen, Mingkang Zhang, Zebao Rui^*()

School of Chemical Engineering and Technology, Guangdong Engineering Technology Research Center for Platform Chemicals from Marine Biomass and their Functionalization, Southern Marine Science and Engineering Guangdong Laboratory (Zhuhai), Sun Yat-sen University, Zhuhai 519082, Guangdong, China

Received:2025-08-11 Accepted:2025-10-27 Online:2026-04-18 Published:2026-03-04
Contact: * E-mail: ruizebao@mail.sysu.edu.cn (Z. Rui).
Supported by:
National Natural Science Foundation of China(22476222);R&D projects in key areas of Guangdong Province(2020B1111360004);Natural Science Funds of Guangdong for Distinguished Young Scholar(2022B1515020098)

摘要/Abstract

摘要：

在天然气利用和煤矿开采过程中, 低浓度CH₄的释放会加剧温室效应. 在催化剂的作用下, 将CH₄氧化为温室效应低21倍的CO₂是缓解全球变暖的一种可行方法. 然而, 天然气田中存在的微量的SO₂会覆盖催化剂活性位点导致其快速失活. 当前提高CH₄氧化催化剂抗硫性能的常规策略是在催化剂本体中引入牺牲剂, 例如贵金属添加剂、可硫酸化载体. 尽管这些策略可以延缓硫中毒, 但由于载体硫酸盐的形成, 催化剂的失活速率仍较快. 此外, 牺牲剂的添加在某些情况下也会导致成本增加和活性降低. 因此, 如何在不损失催化剂反应活性、不增加成本的前提下提升催化剂的抗硫性能仍是一个挑战.
本工作创新性地提出了Al₂O₃孤岛策略, 在不牺牲活性且不增加成本的情况下保护了催化剂活性组分免受SO₂毒化失活. 首先, 考虑到IrO_x具有较高的C‒H活化能力、Pt-Ir协同对CH₄氧化活性的促进作用以及TiO₂载体具有较强的金属-载体相互作用, 设计了具有优异活性的Ir@Pt/TiO₂催化剂. 然后, 将Al₂O₃孤岛与Ir@Pt/TiO₂进行物理混合, 构建了兼具高活性和抗硫性能的Ir@Pt/TiAl催化剂. 得益于Ir@Pt纳米颗粒的核壳结构、Pt原子的电子修饰作用以及TiO₂载体的促分散作用, Ir@Pt纳米颗粒在TiO₂载体上实现了均匀分散, 在常规空速30000 mL g^-1 h^-1(T₉₀ = 325 °C)和极高空速600000 mL g^-1 h^-1(T₉₀ = 500 °C)下, 均表现出优异的CH₄氧化活性(TOF = 1.2 s^-1, 350 °C). 此外, H₂-程序升温还原和X射线光电子能谱结果表明, Al₂O₃孤岛的添加对Ir@Pt纳米颗粒与TiO₂载体的相互作用影响较小, 因此没有影响Ir@Pt纳米颗粒的高CH₄氧化活性. 在反应气体含硫条件下, 原位红外结果表明, Al₂O₃孤岛优先吸附SO₂生成了Al₂(SO₄)₃, 抑制了载体硫酸盐Ti(SO₄)₂的形成. 反应后的能量散射谱结果表明, 反应过程中设计的Al₂O₃孤岛结构稳定, 具有较高的SO₂吸附量, 显著提升了催化剂的抗硫性能. 基于上述实验结果, 可以得出催化剂抗硫机理: SO₂首先吸附在Ir@Pt纳米颗粒上, 然后在高温下迁移到邻近的Al₂O₃孤岛上形成了Al₂(SO₄)₃, 避免了载体硫酸盐Ti(SO₄)₂的形成, 从而保护了活性位点不受SO₂毒化失活. 通过结合Al₂O₃孤岛的SO₂吸附功能和Ir@Pt/TiO₂催化剂的高活性, 制备的Ir@Pt/TiAl同时表现出优异的抗硫能力和CH₄氧化活性, 在50 ppm SO₂和30000 mL g^-1 h^-1的反应条件下, 连续反应50 h没有明显失活.
综上, 本文提出了在不损失活性和增加成本的前提下提高催化剂抗硫性能的孤岛策略, 并阐明了Al₂O₃孤岛的抗硫作用机理, 为解决CH₄氧化催化剂SO₂毒化失活问题提供了新路径, 为高效抗硫催化体系的开发设计提供了参考.

关键词: 抗硫, 甲烷催化氧化, 孤岛, 金属-载体相互作用, 氧化铝

Abstract:

Sulfur-induced catalyst deactivation has been a challenge in the design of gaseous pollutants purified catalyst. As the mainstream strategy for anti-sulfur catalyst design, the incorporation of sacrificial components into the catalyst bulk still faces issues such as increased cost and rapid activity decline. Herein, the physical isolated island strategy is proposed to improve the sulfur resistance and cost-effectiveness of a lean methane oxidation catalyst at no cost of its high activity. The isolated Al₂O₃ island suppresses the formation of sulfates on adjacent Ir@Pt nanoparticles and avoids the sulfation of Ir@Pt/TiO₂. Meanwhile, the isolated Al₂O₃ island draws little effect on the chemical states of active sites. The sulfur adsorption function of isolated Al₂O₃ island and high activity of Ir@Pt/TiO₂ are synergistically combined, leading to both remarkably high CH₄ oxidation activity (TOF = 1.2 s^‒1 at 350 °C) and high sulfur resistance without observable activity loss during 50 h on-stream test under 50 ppm SO₂ and a space velocity of 30000 mL g^‒1 h^‒1. Such isolated-island strategy provides a meaningful reference for the efficient sulfur resistance catalyst design.

Key words: Sulfur resistance, Catalytic methane oxidation, Isolated island, Support-metal interaction, Alumina

武金玮, 陈俊妃, 张明康, 芮泽宝. Al₂O₃孤岛与Ir@Pt/TiO₂协同催化实现高活性耐硫甲烷氧化[J]. 催化学报, 2026, 83: 400-410.

Jinwei Wu, Junfei Chen, Mingkang Zhang, Zebao Rui. Engineering isolated Al₂O₃ island enables adjacent TiO₂-supported Ir@Pt nanoparticles for efficient and sulfur-resistant lean methane oxidation[J]. Chinese Journal of Catalysis, 2026, 83: 400-410.

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图/表 8

Fig. 1. Activity and stability of catalysts. Activity evaluation (a) and sulfur resistance evaluation (b) of Ir@Pt/TiAl at 325 °C under a low space velocity reaction condition (1% CH4, 20% O2, 50 ppm SO2 (when used), balance gas N2, GHSV of 30000 mL g?1 h?1). Activity evaluation (c) and sulfur-resistant stability evaluations (d) of catalysts under a high space velocity reaction condition (0.25% CH4, 5% O2, 10 ppm SO2 (when used), balance gas N2, GHSV of 600000 mL g?1 h?1).

Fig. 2. Morphology and structure information of catalysts. TEM (a) and HRTEM (b) with an inset fast Fourier transform (FFT) images of fresh Ir@Pt/TiAl. HAADF-STEM image with an inset partially enlarged image (c) and corresponding definitive EDS line-scan spectra (d) of Ir@Pt nanoparticles. (e) EDX mapping images of Ir@Pt/TiO2-used. EDX mapping images (f) and corresponding EDS analysis (g) of Ir@Pt/TiAl-used. (h) XRD patterns of fresh catalysts and the referenced PtO2 (PDF# 01-084-1439) and IrO2 (PDF# 00-015-0870).

Fig. 3. H2-TPR (a) and SO2-TPD (b) profiles of catalysts.

Fig. 4. Ir 4f (a), Pt 4d (b), Ti 2p (c), and Al 2p (d) XPS spectra of catalysts.

Fig. 5. CH4, H2, CO, CO2, and H2O mass signals over Ir@Pt/TiO2 (a) and Ir@Pt/TiAl (b) during in-situ CH4-TPSR experiments.

Fig. 6. In-situ DRIFTS spectra over Ir@Pt/TiO2 and Ir@Pt/TiAl versus temperatures without SO2 at an adsorption time of 10 min (a,b) and versus times at 500 °C with the addition of SO2 (c,d). Reactant gas: 1% CH4, 20% O2, 50 ppm SO2 (when used), N2 balance gas.

Fig. 7. In-situ DRIFTS spectra of SO2 + O2 + N2 gas mixture adsorption over Ir@Pt/TiO2 and Ir@Pt/TiAl versus temperatures at an adsorption time of 10 min (a,b) and versus times at 500 °C (c,d). Reactant gas: 1% CH4, 20% O2, 50 ppm SO2 (when used), balance gas N2.

Schematic 1. Schematic of sulfur-resistant mechanism of Al2O3 isolated Ir@Pt/TiO2.

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Al₂O₃孤岛与Ir@Pt/TiO₂协同催化实现高活性耐硫甲烷氧化

Engineering isolated Al₂O₃ island enables adjacent TiO₂-supported Ir@Pt nanoparticles for efficient and sulfur-resistant lean methane oxidation

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