CO₂ adsorption on gas-phase Cu_4−xPt_x (x = 0–4) clusters: a DFT study

Abstract

Transition and noble metal clusters have proven to be critical novel materials, potentially offering major advantages over conventional catalysts in a range of value-added catalytic processess such as carbon dioxide transformation to methanol. In this work, a systematic computational study of CO2 adsorption on gas-phase Cu4-xPtx (x = 0-4) clusters is performed. An exhaustive potential energy surface exploration is initially performed using our recent density functional theory basin-hopping global optimization implementation. Ground-state and low-lying energy isomers are identified for Cu4-xPtx clusters. Secondly, a CO2 molecule adsorption process is analyzed on the ground-state Cu4-xPtx configurations, as a function of cluster composition. Our results show that the gas-phase linear CO2 molecule is deformed upon adsorption, with its bend angle varying from about 132° to 139°. Cu4-xPtx cluster geometries remain unchanged after CO2 adsorption, with the exception of Cu3Pt1 and Pt4 clusters. For these particular cases, a structural conversion between the ground-state geometry and the corresponding first isomer configurations is found to be assisted by the CO2 adsorption. For all clusters, the energy barriers between the ground-state and first isomer structures are explored. Our calculated CO2 adsorption energies are found to be larger for Pt-rich clusters, exhibiting a volcano-type plot. The overall effect of a hybrid functional including dispersion forces is also discussed.

Screening of transition metal doped copper clusters for CO2 activation

“…80 CO 2 adsorption on gas-phase Cu 4Àx Pt x (x = 0-4) was investigated using DFT calculations. High adsorption energies (from À78 to À158 kJ mol À1 ) and CO 2 adsorption in a bent mode were found, 81 and could be explained by charge transfer towards the cluster's LUMO. 82 Based on the reversible structural transformation, the optimal strength of the interaction between the cluster and the adsorbent, and the low CO 2 dissociation barrier, Cu 3 Pt is a promising catalyst.…”

“…82 Based on the reversible structural transformation, the optimal strength of the interaction between the cluster and the adsorbent, and the low CO 2 dissociation barrier, Cu 3 Pt is a promising catalyst. 81 It was shown, that Ni-or Pd-doped Cu 4 clusters exhibit higher adsorption energy and promote the CO 2 activation, because the dopant enhances the charge transfer between the cluster and the adsorbent. 83 Although none of these clusters decrease the CO 2 dissociation barrier.…”

Recent Advances and Challenges of Deep Eutectic Solvent based Supported Liquid Membranes

“…The adsorption technology is costly and requires a high amount of energy (3). Meanwhile, membrane separation technologies hold promise of great energy savings, high selectivity, and therefore lower costs when compared to other conventional methods (7)(8)(9)(10). This technology combines the membrane separation capability with adsorption activities of adsorbents for gas/liquid molecules separation and thus, it is considered as a most efficient technique compared to solo adsorption (7).…”

“…Meanwhile, membrane separation technologies hold promise of great energy savings, high selectivity, and therefore lower costs when compared to other conventional methods (7)(8)(9)(10). This technology combines the membrane separation capability with adsorption activities of adsorbents for gas/liquid molecules separation and thus, it is considered as a most efficient technique compared to solo adsorption (7). Further benefits of membrane systems are smaller footprints and easy to scale-up making this technology an appropriate candidate for industrial applications (11)(12)(13)(14)(15)(16)(17).…”

>i<Ab Initio>/i< investigation of the adsorption of molecules, involved in carbon dioxide and glycerol utilization, on transition-metal substrates

“…12,[202][203][204] For 4-atom clusters based on Cu or Pt, it was reported that bimetallic systems affect the OCO angle of adsorbed CO 2 differently than the unary nanoclusters and extended surfaces. [205][206][207] For Pt nanoparticles, alloying with Co atoms to form Pt 3 Co octapods can promote CO 2 activation and improve the catalytic activity in comparison to unary Pt systems. 208 Besides the type of TM, the proportion of each component of the nanoalloy is critical to design better catalysts; for example, the composition of PdAg alloys can be tuned to weaken the binding of CO with respect to other intermediates during the electroreduction of CO 2 .…”