Insight into hydroxyl groups in anchoring Ir single–atoms on vacancy–deficient rutile TiO2 supports for selective catalytic oxidation of ammonia

IF 20.2 1区 化学 Q1 CHEMISTRY, PHYSICAL Applied Catalysis B: Environmental Pub Date : 2024-01-02 DOI:10.1016/j.apcatb.2023.123684
Wenqing Xu , Yixi Wang , Hong He , Jun Yang , Yang Yang , Jinzhu Ma , Chaoqun Li , Tingyu Zhu
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Abstract

High–performance catalysts are extremely required for controlling NH3 emission via selective catalytic oxidation (SCO), and the anchoring structural feature of active sites is a key prerequisite for developing them. This study confirms the importance of hydroxyl groups on vacancy–deficient reducible oxides as active groups. On the one hand, spontaneous atomic dispersion of active metal Ir is promoted by the abundant terminal hydroxyl groups. On the other hand, Ir cations anchor on the TiO2 surface through exchange with H+ in Ti–OH groups, and thus occupy the Brönsted acid sites. The adsorption strength of NH3 is another key factor affecting the reaction rate–determining step, namely NH3 dehydrogenation, which occurs at a faster rate in the coordinated L–NH3 rather than the ionic B–NH4+. Meanwhile, the coordinated L–NH3 significantly avoids the competitive adsorption of water vapor in the NH3–SCO reaction by reducing the number of hydrogen bonding. The TOF of preferred 0.8Ir/TiO2 sample is significantly higher than 0.2Ir/TiO2 sample, although Ir is almost always atomic dispersed. Finally, NH3 conversion is 85% in a wet circumstance (5% H2O) at 240 °C (GHSV = 85 000 h–1), with a N2 selectivity of up to 65% on 0.8Ir/TiO2 sample.

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洞察羟基在空位缺陷的金红石二氧化钛支撑物上锚定铱单原子以选择性催化氧化氨的作用
通过选择性催化氧化(SCO)来控制 NH3 的排放极其需要高性能的催化剂,而活性位点的锚定结构特征是开发催化剂的关键前提。本研究证实了空位缺陷可还原氧化物上羟基作为活性基团的重要性。一方面,大量的末端羟基促进了活性金属 Ir 的自发原子分散。另一方面,Ir 阳离子通过与 Ti-OH 基团中的 H+ 交换而锚定在二氧化钛表面,从而占据了勃氏酸位点。NH3 的吸附强度是影响反应速率决定步骤(即 NH3 脱氢)的另一个关键因素,在配位的 L-NH3 而不是离子型的 B-NH4+ 中,NH3 脱氢的速率更快。同时,配位的 L-NH3 通过减少氢键数量,大大避免了 NH3-SCO 反应中水蒸气的竞争性吸附。虽然 Ir 几乎都是原子分散的,但优选的 0.8Ir/TiO2 样品的 TOF 明显高于 0.2Ir/TiO2 样品。最后,在 240 °C(GHSV = 85 000 h-1)的湿环境(5% H2O)中,0.8Ir/TiO2 样品的 NH3 转化率为 85%,N2 选择性高达 65%。
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来源期刊
Applied Catalysis B: Environmental
Applied Catalysis B: Environmental 环境科学-工程:化工
CiteScore
38.60
自引率
6.30%
发文量
1117
审稿时长
24 days
期刊介绍: Applied Catalysis B: Environment and Energy (formerly Applied Catalysis B: Environmental) is a journal that focuses on the transition towards cleaner and more sustainable energy sources. The journal's publications cover a wide range of topics, including: 1.Catalytic elimination of environmental pollutants such as nitrogen oxides, carbon monoxide, sulfur compounds, chlorinated and other organic compounds, and soot emitted from stationary or mobile sources. 2.Basic understanding of catalysts used in environmental pollution abatement, particularly in industrial processes. 3.All aspects of preparation, characterization, activation, deactivation, and regeneration of novel and commercially applicable environmental catalysts. 4.New catalytic routes and processes for the production of clean energy, such as hydrogen generation via catalytic fuel processing, and new catalysts and electrocatalysts for fuel cells. 5.Catalytic reactions that convert wastes into useful products. 6.Clean manufacturing techniques that replace toxic chemicals with environmentally friendly catalysts. 7.Scientific aspects of photocatalytic processes and a basic understanding of photocatalysts as applied to environmental problems. 8.New catalytic combustion technologies and catalysts. 9.New catalytic non-enzymatic transformations of biomass components. The journal is abstracted and indexed in API Abstracts, Research Alert, Chemical Abstracts, Web of Science, Theoretical Chemical Engineering Abstracts, Engineering, Technology & Applied Sciences, and others.
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