Effects of Potassium and Manganese Promoters on Nitrogen-Doped Carbon Nanotube-Supported Iron Catalysts for CO_2 Hydrogenation

Nitrogen-doped carbon nanotubes （NCNTs） were used as a support for iron （Fe） nanoparticles applied in car- bon dioxide （CO_2） hydrogenation at 633 K and 25 bar （1 bar = 10-5 Pa）. The Fe/NCNT catalyst promoted with both potassium （K） and manganese （Mn） showed high performance in CO_2 hydrogenation, reaching 34.9% conversion with a gas hourly space velocity （GHSV） of 3.1 L-（g·h）-1. Product selectivities were high for olefin products and low for short-chain alkanes for the K-promoted catalysts. When Fe/NCNT catalyst was promot- ed with both K and Mn, the catalytic activity was stable for 60 h of reaction time. The structural effect of the Mn promoter was demonstrated by X-ray diffraction （XRD）, temperature-programmed reduction （TPR） with molecular hydrogen （H2）, and in situ X-ray absorption near-edge structure （XANES） analysis. The Mn pro- moter stabilized wtistite （FeO） as an intermediate and lowered the TPR onset temperature. Catalytic ammo- nia （NH_3） decomposition was used as an additional probe reaction for characterizing the promoter effects. The Fe/NCNT catalyst promoted with both K and Mn had the highest catalytic activity, and the Mn-promoted Fe/NCNT catalysts had the highest thermal stability under reducing conditions.

氮掺杂碳纳米管(NCNTs)作为载体负载铁(Fe)纳米颗粒,可应用于CO_2多相催化加氢反应(633 K和25 bar)。当将钾(K)和锰(Mn)作为助催化剂时,Fe/NCNT展现出优异的CO_2加氢性能,在体积空速(GHSV)为3.1 L·g^(–1)·h^(–1)时转化率可达34.9%。当使用K作为助催化剂时,反应对烯烃和短链烷烃具有高的选择性。当K和Mn同时作为助催化剂时,其催化活性能够稳定地维持60 h。助催化剂Mn的结构效应通过X射线衍射、氢气程序升温还原以及近边X射线吸收精细结构进行表征。助催化剂Mn不仅能够稳定中间态FeO,且能降低程序升温还原的起始温度。通过探针反应NH3的催化分解来表征助催化剂效应。当K和Mn作为助催化剂时,Fe/NCNT具有最好的催化活性。在还原条件下,当K作为助催化剂时,Fe/NCNT具有最优异的热稳定性。