Hua Yongbiao, Vikrant Kumar, Kim Ki-Hyun, Heynderickx Philippe M, Boukhvalov Danil W
Department of Civil and Environmental Engineering, Hanyang University, 222 Wangsimni-Ro, Seoul 04763, Republic of Korea.
Department of Civil and Environmental Engineering, Hanyang University, 222 Wangsimni-Ro, Seoul 04763, Republic of Korea.
J Colloid Interface Sci. 2024 Jul;665:1029-1042. doi: 10.1016/j.jcis.2024.04.005. Epub 2024 Apr 2.
Formaldehyde (FA), a carcinogenic oxygenated volatile organic compound, is present ubiquitously in indoor air. As such, it is generally regarded as a critical target for air quality management. The oxidative removal of FA under dark and room-temperature (RT) conditions is of practical significance. A series of ternary nickel-cobalt-manganese oxide-supported platinum catalysts (Pt/NiCoMnO) have been synthesized for FA oxidative removal at RT in the dark. Their RT conversion values for 50 ppm FA (X) at 5,964 h gas hourly space velocity (GHSV) decrease in the following order: 1 wt% Pt/NiCoMnO (100 %) > 0.5 wt% Pt/NiCoMnO (25 %) > 0.05 wt% Pt/NiCoMnO (14 %) > NiCoMnO (6 %). The catalytic performance of 1 wt% Pt/NiCoMnO has been examined further under the control of various process variables (e.g., catalyst mass, flow rate, relative humidity, FA concentration, time on stream, and molecular oxygen content). The catalytic oxidation of FA at low temperatures (e.g., RT and 60 °C) is accounted for by Langmuir-Hinshelwood mechanism (single-site competitive-adsorption), while Mars van Krevelen kinetics is prevalent at higher temperatures. In situ diffuse-reflectance infrared Fourier-transform spectroscopy reveals that FA oxidation proceeds through a series of reaction intermediates such as DOM, HCOO, and CO. Based on the density functional theory simulations, the unique electronic structures of the nearest surface atoms (platinum and nickel) are suggested to be responsible for the superior catalytic activity of Pt/NiCoMnO.
甲醛(FA)是一种致癌的含氧挥发性有机化合物,普遍存在于室内空气中。因此,它通常被视为空气质量管控的关键目标。在黑暗和室温(RT)条件下对FA进行氧化去除具有实际意义。已合成了一系列负载铂的三元镍钴锰氧化物催化剂(Pt/NiCoMnO),用于在黑暗中室温下氧化去除FA。在5964 h气体时空速(GHSV)下,它们对50 ppm FA的室温转化率(X)按以下顺序降低:1 wt% Pt/NiCoMnO(100%)> 0.5 wt% Pt/NiCoMnO(25%)> 0.05 wt% Pt/NiCoMnO(14%)> NiCoMnO(6%)。在各种工艺变量(如催化剂质量、流速、相对湿度、FA浓度、运行时间和分子氧含量)的控制下,对1 wt% Pt/NiCoMnO的催化性能进行了进一步研究。FA在低温(如室温及60°C)下的催化氧化遵循朗缪尔-欣谢尔伍德机理(单中心竞争吸附),而在较高温度下,Mars van Krevelen动力学占主导。原位漫反射红外傅里叶变换光谱表明,FA氧化通过一系列反应中间体进行,如DOM、HCOO和CO。基于密度泛函理论模拟,表明最接近表面的原子(铂和镍)独特的电子结构是Pt/NiCoMnO具有优异催化活性的原因。