Chen Yongjie, Jiang Lei, Lin Simin, Dong Pei, Fu Xiaoli, Wang Yang, Liu Qiang, Wu Mingbo
State Key Laboratory of Heavy Oil Processing, College of New Energy, China University of Petroleum (East China), Qingdao 266580, China.
Shandong Energy Group Co., Ltd., Jinan 250014, China.
Molecules. 2024 Sep 29;29(19):4628. doi: 10.3390/molecules29194628.
Carbon materials supported Fe-based catalysts possess great potential for the thermal-catalytic hydrogenation of CO into valuable chemicals, such as alkenes and oxygenates, due to the excellent active sites' accessibility, appropriate interaction between the active site and carbon support, as well as the excellent capacities in C-O bond activation and C-C bond coupling. Even though tremendous progress has been made to boost the CO hydrogenation performance of carbon-supported Fe-based catalysts, e.g., additives modification, the choice of different carbon materials (graphene or carbon nanotubes), electronic property tailoring, etc., the effect of carbon support porosity on the evolution of Fe-based active sites and the corresponding catalytic performance has been rarely investigated. Herein, a series of porous carbon samples with different porosities are obtained by the KCO activation of petroleum pitch under different temperatures. Fe-based active sites and the alkali promoter Na are anchored on the porous carbon to study the effect of carbon support porosity on the physicochemical properties of Fe-based active sites and CO hydrogenation performance. Multiple characterizations clarify that the bigger meso/macro-pores in the carbon support are beneficial for the formation of the FeC crystal phase for C-C bond coupling, therefore boosting the synthesis of C chemicals, especially C alcohols (COH), while the limited micro-pores are unfavorable for C chemicals synthesis owing to the sluggish crystal phase evolution and reactants' inaccessibility. We wish our work could enrich the horizon for the rational design of highly efficient carbon-supported Fe-based catalysts.
碳材料负载的铁基催化剂在将CO热催化氢化为有价值的化学品(如烯烃和含氧化合物)方面具有巨大潜力,这归因于其优异的活性位点可及性、活性位点与碳载体之间适当的相互作用,以及在C-O键活化和C-C键偶联方面的出色能力。尽管在提高碳负载铁基催化剂的CO加氢性能方面已经取得了巨大进展,例如添加剂改性、不同碳材料(石墨烯或碳纳米管)的选择、电子性质调控等,但碳载体孔隙率对铁基活性位点演变及相应催化性能的影响却鲜有研究。在此,通过在不同温度下对石油沥青进行KCO活化,获得了一系列具有不同孔隙率的多孔碳样品。将铁基活性位点和碱促进剂Na锚定在多孔碳上,以研究碳载体孔隙率对铁基活性位点物理化学性质和CO加氢性能的影响。多种表征结果表明,碳载体中较大的中孔/大孔有利于形成用于C-C键偶联的FeC晶相,从而促进C化学品的合成,尤其是C醇(COH),而有限的微孔由于晶相演变缓慢和反应物难以接近,不利于C化学品的合成。我们希望我们的工作能够拓宽高效碳负载铁基催化剂合理设计的视野。