Abstract Industrial catalysts usually encounter great challenges in Cl· deactivation, toxic by-products generation, and stability with a long running operation for catalytic oxidation of chlorinated volatile organic compounds (CVOCs). In this research, spinel-type oxides with transition metal substituted as active oxides supported on cordierite (Crd) was identified to catalytic degradation of chlorobenzene (CB). The Cu 1.4 Mn 1.6 O 4 spinel-type oxides considered as the main active oxides have been identified, which were confirmed by XRD and TEM. The activities of these CuM x Mn 2−x O 4 catalysts were markedly improved by lower calcining temperature and shorter time. CuCe 0.25 Mn 1.75 O 4 /Crd catalyst displayed the highest activity and good stability due to that CeO 2 nano-rods structure conducive to increase the O ads amount, the dispersion of active oxides, the strength of weak acidity, the surface areas and pore volume. Moreover, spinel-type with CeO 2 doping exhibited high performance in CVOCs elimination attributed to the high storage capacity of oxygen, plentiful oxygen vacancies, good efficiency in breaking C–Cl bond and the easy shuttles between Ce 3+ and Ce 4+ , which were demonstrated by XPS. The results indicate that CeO 2 , O ads , and ·OH have beneficial effects on the removing Cl· into benzene, and then improving the ring-opening of CB for CB degradation. Graphic Abstract

中文翻译：

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堇青石负载过渡金属取代尖晶石型催化剂上氯苯氧化的活性和稳定性的提高

摘要 工业催化剂在催化氧化氯化挥发性有机化合物（CVOCs）时常遇到Cl·失活、有毒副产物产生和长期运行稳定性等方面的巨大挑战。在这项研究中，将过渡金属取代的尖晶石型氧化物作为负载在堇青石 (Crd) 上的活性氧化物被确定为催化降解氯苯 (CB)。被认为是主要活性氧化物的Cu 1.4 Mn 1.6 O 4 尖晶石型氧化物已被鉴定，并通过XRD和TEM得到证实。这些CuM x Mn 2-x O 4 催化剂的活性通过更低的煅烧温度和更短的时间得到显着提高。CuCe 0.25 Mn 1.75 O 4 /Crd催化剂由于CeO 2 纳米棒结构有利于增加O的吸附量，表现出最高的活性和良好的稳定性，活性氧化物的分散性、弱酸性的强度、表面积和孔体积。此外，掺杂CeO 2 的尖晶石型由于氧的高存储容量、丰富的氧空位、良好的C-Cl键断裂效率以及Ce 3+ 和Ce 4+ 之间的容易穿梭，在消除CVOCs方面表现出优异的性能， XPS 证明了这一点。结果表明，CeO 2 、O ads 和·OH 有利于去除Cl· 进入苯，进而改善CB 的开环降解CB。图形摘要 XPS 证明了在破坏 C-Cl 键和 Ce 3+ 和 Ce 4+ 之间容易穿梭方面的良好效率。结果表明，CeO 2 、O ads 和·OH 有利于去除Cl· 进入苯，进而改善CB 的开环降解CB。图形摘要 XPS 证明了在破坏 C-Cl 键和 Ce 3+ 和 Ce 4+ 之间容易穿梭方面的良好效率。结果表明，CeO 2 、O ads 和·OH 有利于去除Cl· 进入苯，进而改善CB 的开环降解CB。图形摘要