Unravelling the role of metal-metal oxide interfaces of Cu/ZnO/ZrO2/Al2O3 catalyst for methanol synthesis from CO2: Insights from experiments and DFT-based microkinetic modeling

Exploring CO2hydrogenation to methanol at a CuZn–ZrO2interfaceviaDFT calculations

“…81 The basic assumptions of the ESM include that: (i) Eyring's transition state theory is valid, (ii) a steady-state regime is applicable, and (iii) the intermediates undergo fast relaxation to the thermodynamic equilibrium described by the Boltzmann distribution. 78 While the reaction kinetics for heterogeneous catalyst systems is often studied via microkinetic modelling or kinetic Monte Carlo simulations, 23,26–28,48,49,82 the ESM offers a simplified way to estimate which pathway is optimal. We used the gTOFfee software, 81,83 which was slightly modified to improve the performance for the present reaction network.…”

“…Very recently, an inverse ZrZn 2 O 3 /Cu(111) system was used to model ZrO 2 /Cu and ZnO/Cu interfaces. 49 Purely metallic Cu or CuZn models have also been used to mimic active sites at facets and edges of nanoparticles. 9,23,27,46,50 Even though a CuZn(211) surface is unable to activate CO 2 and the intermediates bound to it are thermodynamically less stable than the gas-phase reagents, 9 the hydrogenation intermediates are nevertheless more strongly bound to an alloyed CuZn surface than to a pure Cu surface.…”

The influence of Mg/Al molar ratio on the performance of CuMgAl-x catalysts for CO2 hydrogenation to methanol

“…As shown in Figure 10A , there was a positive correlation between STY CH3OH and S Cu . The high S Cu provided more active sites for the adsorption and activation of CO 2 and H 2 , thus obtaining higher catalytic activity ( Dharmalingam et al, 2023 ). However, the relationship between STY CH3OH and S Cu was not linear, which proved that not only does the S Cu have an effect on catalytic activity, but other factors also have an effect on catalytic activity.…”

“…SMSI plays a crucial role in determining metal particle size, metal dispersion, electron transfer, and oxygen vacancy formation, resulting in large differences in catalyst activity, selectivity, and stability. In recent years, to investigate the SMSI, many scholars have carried out a series of studies on the identification of catalytic active sites or interfaces, the establishment of structure-performance relationships, and the exploration of reaction mechanisms ( Yao et al, 2019 ; Dharmalingam et al, 2023 ; Liang et al, 2023 ). Xu et al (2023) adjusted the interfacial structure of the Cu/ZrO 2 catalyst by changing the molar ratio and precipitation sequence of Cu and Zr precursors in the oxalate precipitation method and found that the interfacial structure gradually changed from the traditional ZrO 2 -Cu interface to the Cu-ZrO 2 inverse interface with higher catalytic performance as the Cu/Zr ratio increased.…”

Computational Exploration of Subnano Zn and Cu Species on Cu/ZrO2: Implications for Methanol Synthesis

“…Threecomponent models have emerged recently in order to represent those kinds of active sites. 16,17,23 In our previous study, we employed a zirconia-supported Cu nanorod with and without Zn incorporated into the interface between the rod and support. 17 The model served as a representative of twoand three-component metal support interface sites and was used to elucidate the role of a dilute interfacial CuZn alloy.…”