Key Laboratory of Aerosol Chemistry & Physics, State Key Laboratory of Loess and Quaternary Geology (SKLLQG), Institute of Earth Environment, Chinese Academy of Sciences (CAS), Xi'an 710061, P. R. China.
CAS Center for Excellence in Quaternary Science and Global Change, Xi'an 710061, P. R. China.
Environ Sci Technol. 2023 Nov 14;57(45):17598-17609. doi: 10.1021/acs.est.3c05431. Epub 2023 Oct 31.
Activating surface lattice oxygen (O) through the modulation of metal-oxygen bond strength has proven to be an effective route for facilitating the catalytic degradation of volatile organic compounds (VOCs). Although this strategy has been implemented the construction of the TM-O-TM (TM represents a transition metal) structure in various reactions, the underlying principle requires exploration when using different TMs. Herein, the Cu-O-Fe structure was created by developing CuO-FeO composites with enhanced interfacial effect, which exhibited superior catalytic activity to their counterparts, with (the temperature of toluene conversion reaching 90%) decreasing by approximately 50 °C. Structural analyses and theoretical calculations demonstrated that the active Cu-O-Fe sites at the CuO-FeO interface improved low-temperature reducibility and oxygen species activity. Particularly, X-ray absorption fine structure spectroscopy revealed the contraction and expansion of Cu-O and Fe-O bonds, respectively, which were responsible for the activation of the surface O. A mechanistic study revealed that toluene can be oxidized by rapid dehydrogenation of methyl assisted by the highly active surface O and subsequently undergo ring-opening and deep mineralization into CO following the Mars-van Krevelen mechanism. This study provided a novel strategy to explore interface-enhanced TM catalysts for efficient surface O activation and VOCs abatement.
通过调节金属-氧键强度来激活表面晶格氧(O)已被证明是促进挥发性有机化合物(VOCs)催化降解的有效途径。尽管在各种反应中已经采用了这种策略来构建 TM-O-TM(TM 代表过渡金属)结构,但在使用不同 TM 时,需要探索其背后的原理。在此,通过开发具有增强界面效应的 CuO-FeO 复合材料,构建了 Cu-O-Fe 结构,其表现出优于其对应物的催化活性,(甲苯转化率达到 90%的温度)降低了约 50°C。结构分析和理论计算表明,CuO-FeO 界面上的活性 Cu-O-Fe 位提高了低温还原性和氧物种活性。特别是,X 射线吸收精细结构光谱揭示了 Cu-O 和 Fe-O 键的收缩和扩张,分别负责表面 O 的激活。机理研究表明,甲苯可以通过甲基的快速脱氢作用被氧化,表面活性 O 的协助,随后根据 Mars-van Krevelen 机理进行开环和深度矿化生成 CO。这项研究提供了一种新的策略,用于探索用于高效表面 O 激活和 VOCs 减排的界面增强 TM 催化剂。