Abstract
Metal co-catalysts tipped at a photocatalyst surface form a crucial component in the nanoheterostructures designed for the photocatalytic hydrogen evolution reaction. To examine the intermetallic differences and size effects at these interfaces, we use spin-polarized density functional theory to study single-atom, 13-atom, and 55-atom cluster depositions of Ni, Pd, Pt, and Au on the CdS(1010) surface. For the single metal atoms, the ground-state configuration was the same site for all of the elements. Analysis of the metal-CdS bonding and of the charge transfers revealed a Ni-Cd bonding complex leading to depletion of electronic charge at the Ni single atom and at deposited Ni clusters, in contrast to charge accumulation observed for the other three metals Pd, Pt, and Au. For scaling up sizes of the metal deposition, six subnanometer cluster types were selected over a wide range of cluster's effective coordination number, and their interfaces were differentiated by charge redistributions, structure and adhesion energies, highest occupied molecular orbital-lowest occupied molecular orbital (HOMO-LUMO) gaps, and Schottky barrier heights. Although all considered clusters are semiconducting in the gas phase, 9 out of 28 clusters became (semi)metallic after deposition on the CdS semiconductor surface. Intermetallic differences and common trends are discussed.
Original language | English |
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Pages (from-to) | 9298-9310 |
Number of pages | 13 |
Journal | Journal of Physical Chemistry C |
Volume | 123 |
Issue number | 14 |
DOIs | |
Publication status | Published - 11 Apr 2019 |
Funding
M.A.v.H. acknowledges support from the European Research Council (ERC Consolidator Grant No. 683076 NANO-INSITU). This work is part of the Industrial Partnership Programme “Computational Sciences for Energy Research” (Grant No. 13CSER067) of the Netherlands Organization for Scientific Research NWO-i. This research program was cofinanced by Shell Global Solutions International B.V.