Electrified non-thermal plasma (NTP) catalytic hydrogenation is the promising alternative to the thermal counterparts, being able to be operated under mild conditions and compatible with green electricity/hydrogen. Ra...Electrified non-thermal plasma (NTP) catalytic hydrogenation is the promising alternative to the thermal counterparts, being able to be operated under mild conditions and compatible with green electricity/hydrogen. Rational design of the catalysts for such NTP-catalytic systems is one of the keys to improve the process efficiency. Here, we present the development of siliceous mesocellular foam (MCF) supported Cu catalysts for NTP-catalytic CO_(2) hydrogenation to methanol. The findings show that the pristine MCF support with high specific surface area and large mesopore of 784 m2·g−1 and ~8.5 nm could promote the plasma discharging and the diffusion of species through its framework, outperforming other control porous materials (viz., silicalite-1, SiO_(2), and SBA-15). Compared to the NTP system employing the bare MCF, the inclusion of Cu and Zn in MCF (i.e., Cu1Zn1/MCF) promoted the methanol formation of the NTP-catalytic system with a higher space-time yield of methanol at ~275 μmol·g_(cat)^(−1)·h^(−1) and a lower energy consumption of 26.4 kJ^(−1)·mmol_(CH_(3)OH)^(-1) (conversely, ~225 μmol·g_(cat)^(−1)·h^(−1) and ~71 kJ^(−1)·mmol_(CH_(3)OH)^(-1), respectively, for the bare MCF system at 10.1 kV). The findings suggest that inclusion of active metal sites (especially Zn species) could stabilize the CO_(2)/CO-related intermediates to facilitate the surface reaction toward methanol formation.展开更多
基金funding from the International Science and Technology Cooperation Project of Innovative Supporting Plan from Jiangsu Provincial Department of Science and Technology(Grant No.BZ2022040)the National Natural Science Foundation of China(Grant No.22278204)+1 种基金the Jiangsu Specially-Appointed Professors Program.This Project was also partially supported by Ningbo Natural Science Foundation(Project ID 2023J245)the special innovation project fund(Grant No.XMGL-KJZX-202204,52376207,52276211)from the Institute of Wenzhou,Zhejiang University.
文摘Electrified non-thermal plasma (NTP) catalytic hydrogenation is the promising alternative to the thermal counterparts, being able to be operated under mild conditions and compatible with green electricity/hydrogen. Rational design of the catalysts for such NTP-catalytic systems is one of the keys to improve the process efficiency. Here, we present the development of siliceous mesocellular foam (MCF) supported Cu catalysts for NTP-catalytic CO_(2) hydrogenation to methanol. The findings show that the pristine MCF support with high specific surface area and large mesopore of 784 m2·g−1 and ~8.5 nm could promote the plasma discharging and the diffusion of species through its framework, outperforming other control porous materials (viz., silicalite-1, SiO_(2), and SBA-15). Compared to the NTP system employing the bare MCF, the inclusion of Cu and Zn in MCF (i.e., Cu1Zn1/MCF) promoted the methanol formation of the NTP-catalytic system with a higher space-time yield of methanol at ~275 μmol·g_(cat)^(−1)·h^(−1) and a lower energy consumption of 26.4 kJ^(−1)·mmol_(CH_(3)OH)^(-1) (conversely, ~225 μmol·g_(cat)^(−1)·h^(−1) and ~71 kJ^(−1)·mmol_(CH_(3)OH)^(-1), respectively, for the bare MCF system at 10.1 kV). The findings suggest that inclusion of active metal sites (especially Zn species) could stabilize the CO_(2)/CO-related intermediates to facilitate the surface reaction toward methanol formation.
文摘文章采用巯基丙基三甲氧基硅烷(MPTMS)对介孔泡沫二氧化硅(mesocellular silica foam,MCF)进行接枝磺化,制备了Pr-SO3H/MCF固体酸催化剂,并考察了苯基三甲氧基硅烷疏水改性对苯甲酸甲酯合成的影响。采用氮气吸附脱附(BET)、透射电子显微镜(transmission electron microscope,TEM)、接触角、元素分析仪等手段对催化剂进行表征。结果表明,苯基三甲氧基硅烷改性后的Ph/Pr-SO3H/MCF催化剂,比表面积略有降低,疏水性明显提高。由于苯环与苯环之间形成π-π键,增加了对反应物苯甲酸的吸附能力,在催化剂表面形成了高浓度苯甲酸微区,从而增加了酯化反应速率。同时由于表面的疏水性使得副产物水快速排出催化剂表面,避免催化剂水合,提高了催化剂的耐水性及稳定性。
