Tuning of Catalytic Activity by Thermoelectric Materials for Carbon Dioxide Hydrogenation

Abstract

An innovative use of a thermoelectric material (BiCuSeO) as a support and promoter of catalysis for CO2 hydrogenation is reported here. It is proposed that the capability of thermoelectric materials to shift the Fermi level and work function of a catalyst lead to an exponential increase of catalytic activity for catalyst particles deposited on its surface. Experimental results show that the CO2 conversion and CO selectivity are increased significantly by a thermoelectric Seebeck voltage. This suggests that the thermoelectric effect can not only increase the reaction rate but also change chemical equilibrium, which leads to the change of thermodynamic equilibrium for the conversion of CO2 in its hydrogenation reactions. It is also shown that this thermoelectric promotion of catalysis enables BiCuSeO oxide itself to have a high catalytic activity for CO2 hydrogenation. The generic nature of the mechanism suggests the possibility that many catalytic chemical reactions can be tuned in situ to achieve much higher reaction rates, or at lower temperatures, or have better desired selectivity through changing the backside temperature of the thermoelectric support.

Thermocatalytic hydrogen peroxide generation and environmental disinfection by Bi2Te3 nanoplates

“…In general, thermoelectric materials can convert thermal energy to electrical energy by means of the temperature difference-induced separation of positive and negative charges 27 . Temperature difference-induced charge separation and consequent voltage generation inside a thermoelectric material can also be expected to realize ROS generation and the corresponding catalytic activity 28 , 29 . Thermoelectric materials that can be used as catalysts are called thermocatalysts and are endowed with multiple advantages over traditional photo/piezocatalysts.…”

Enhanced CO2 Reduction Performance of BiCuSeO‐Based Hybrid Catalysts by Synergetic Photo‐Thermoelectric Effect

“…[ 41,44 ] Seebeck voltage caused by temperature difference (when T h > 500 K, using hot plate in the dark) has also been confirmed to be beneficial for CO 2 hydrogenation and ethylene oxidation, via modifying the work function of catalysts’ surface, in other thermoelectric based catalysts reported by Prof. Huang group. [ 45,46 ] In our work, a modified heterojunction will better facilitate electrons’ transport to overcome the offset at the conduction band using both light and heat, as can also be proven by a higher open potential in stage VI in Figure 4b and Figure S13, Supporting Information. Charges caused by Seebeck effect, labeled as green solid circles in Figure 4d may contribute to modify the band structure of hybrid catalysts, for the majority carriers in p‐type BiCuSeO are generally recognized as holes.…”

Heat-fueled enzymatic cascade for selective oxyfunctionalization of hydrocarbons

“…Recent reports substantiated the influence of thermoelectric effect on catalysis, where the generation of Seebeck potential within TE materials (as a catalyst support or promoter) alters the electron work functions of catalysts, resulting in so-called thermoelectric promotion of catalysis (TEPOC) 19 , 20 . We hypothesized that thermoelectrobiocatalysis (TEBC), where the TE material (i.e., Bi 2 Te 3 ) plays a role as a stand-alone catalyst itself, could be also promoted by the Seebeck effect based on the TEPOC model.…”