Jin Qijie, Shen Yuesong, Cai Yi, Chu Lin, Zeng Yanwei
College of Materials Science and Engineering, Nanjing Tech University, Nanjing, 210009, China; Jiangsu Collaborative Innovation Center for Advanced Inorganic Function Composites, Nanjing Tech University, Nanjing, 210009, China; Jiangsu National Synergetic Innovation Center for Advanced Materials, Nanjing Tech University, Nanjing, 210009, China.
College of Materials Science and Engineering, Nanjing Tech University, Nanjing, 210009, China; Jiangsu Collaborative Innovation Center for Advanced Inorganic Function Composites, Nanjing Tech University, Nanjing, 210009, China; Jiangsu National Synergetic Innovation Center for Advanced Materials, Nanjing Tech University, Nanjing, 210009, China.
J Hazard Mater. 2020 Jan 5;381:120934. doi: 10.1016/j.jhazmat.2019.120934. Epub 2019 Jul 25.
The harmless disposal of abandoned and toxic VO(WO)/TiO (VWT) deNO catalysts has become a worldwide great demand, a new resource path for hydrogen production from steam reforming of formaldehyde and water using the waste VWT deNOx catalysts as catalyst carriers was proposed. The waste VO-based catalysts supported NiO (N/VWT) catalysts prepared by impregnation method were comparatively studied for hydrogen production. The H and CO selectivity of the optimum N/VWT separately reached 100% and 72.5%, and the formaldehyde conversion of the N/VWT reached 86.3% at 400 ℃ and higher than 93.0% at 450-600 ℃. Analysis showed that the hydroxyl species played the most important role, and its richness determined the catalytic performance directly. The high acid sites and excellent redox properties were beneficial to enhance the catalytic performance. The in situ DRIFT study verified that the hydrogen bonds between formate species and hydroxyl groups reduced reaction steps, which accelerated the progress of the reaction. The adsorbed formaldehyde transformed to formate species firstly, and then produced H and CO (or CO) by dehydrogenation. Ultimately, the resource utilization path not only completely solved the harmless problems of the waste VO-based deNO catalysts and formaldehyde, but also contributed to the hydrogen production.
废弃有毒的VO(WO)/TiO（VWT）脱硝催化剂的无害化处理已成为全球的迫切需求，提出了一种以废弃VWT脱硝催化剂为催化剂载体，通过甲醛与水蒸汽重整制氢的新资源路径。对采用浸渍法制备的负载NiO的废弃VO基催化剂（N/VWT）进行了制氢性能的对比研究。最佳N/VWT的H和CO选择性分别达到100%和72.5%，在400℃时N/VWT的甲醛转化率达到86.3%，在450-600℃时高于93.0%。分析表明，羟基物种起最重要作用，其丰富程度直接决定催化性能。高酸位点和优异的氧化还原性能有利于提高催化性能。原位漫反射红外傅里叶变换光谱（DRIFT）研究证实，甲酸盐物种与羟基之间的氢键减少了反应步骤，加速了反应进程。吸附的甲醛首先转化为甲酸盐物种，然后通过脱氢生成H和CO（或CO）。最终，该资源利用路径不仅完全解决了废弃VO基脱硝催化剂和甲醛的无害化问题，还实现了制氢。
