Interface, Inc.

Here, we present an efficient method for calculating adatom potential energy surfaces (PESs) and the activation barriers involved in the elementary steps of surface diffusion. Our method estimates a coupled potential energy profile based on the PESs of the decoupled processes and assumes bond order conservation. The associated barriers of migration were compared and validated against calculated barriers on common FCC(100) metal surfaces of Ag, Au, Cu, Pd, Pt, Rh, Ni, and Ir metals. The barrier prediction accuracy quantified by the mean absolute error (MAE) using the method is 0.12 eV, which is comparable to the accuracy of TS barriers by using Br & oslash;nsted-Evans-Polanyi (BEP) relations. Given their high accuracy, the approximated activation barriers have the potential to predict the sintering and restructuring of metallic systems on-the-fly. Therefore, we believe that the model will help to improve and speed up the understanding of surface restructuring and sintering in heterogeneous catalysis.

Electrochemical mass spectrometry (EC-MS) was used to investigate the coupled dynamics of surface hydride formation, the oxygen reduction reaction (ORR), and the hydrogen evolution reaction (HER) on Cu(111) in perchloric acid. Starting with an Ar-saturated electrolyte, hydride formation proceeds via two overlapping cathodic waves that evolve with cycling due to the restructuring of the electrode surface, associated with the removal of residual oxide species. Grand canonical free-energy calculations indicate that the surface hydride stabilizes pristine terraces against roughening and helps to anneal vacancy-adatom defects introduced during specimen preparation. Introducing controlled amounts of O2 markedly perturbs this behavior, shifting hydride formation to more negative potentials and accelerating HER kinetics, as revealed by EC-MS. Density functional theory and molecular dynamics simulations show that coadsorption of H with ORR intermediates (OH*/OOH*) promotes Cu(111) restructuring through adatom-vacancy formation and subsurface O incorporation. The resulting fluxional adatom sites enhance the HER activity and modulate the ORR kinetics under mixed control. Extended O2 exposure irreversibly restructures the surface and reshapes the hydride formation waves resulting in a lasting imprint on surface reactivity that remains even after returning to nominally O2-free conditions. These findings demonstrate that coupled adsorbates restructure Cu(111) under an electrochemical bias, generating new active sites with direct implications for the performance and stability of Cu electrocatalysts.

Transparent conducting materials exhibit a unique combination of high electrical conductivity and high optical transparency within the visible range, two seemingly impossible properties to be present in any solid-state material, simultaneously. This uniqueness makes them the backbone of the whole electronic and optoelectronic industries and is currently dominated by indium-based materials. High-performance aluminum-doped zinc oxide (AZO) nanocrystals could be a viable option for application in transparent electronics. This work focuses on the impact of in situ pressure on the AZO nanoparticles in driving their optoelectronic properties, which is being reported for the first time to the best of our knowledge. Thin film fabricated with AZO nanoparticles synthesized at 100 bar of pressure (AZO-100) has the highest figure of merit, optical transparency (>95%) and lowest sheet resistance (similar to 103 Omega sq(-1)), significantly lower than the AZO film fabricated from the nanoparticles synthesized at atmospheric pressure. These modifications could be attributed to the improved crystallinity, lowering of surface roughness, and shifts in band gaps, which facilitate electron transfer, as is evident from the optical and valence-band electronic structure measurements, suggesting a substantial influence of in situ pressure-controlled growth of AZO nanoparticles. The improved properties confirm the possibility of using AZO-100 as an n-type transparent conducting material, replacing indium tin oxide in various optoelectronic devices, as successfully demonstrated in laboratory-fabricated prototype liquid crystal display (LCD) and organic light-emitting diode (OLED) devices using the developed films.

Aqueous electro-reductive coupling of nitrogen oxides and cyclohexanone to produce cyclohexanone oxime (CYCO) has recently attracted much interest, but it is greatly challenging due to its low yield and poor energy efficiency. Herein, an intermetallic Pd3Bi metallene (i-Pd3Biene) catalyst was developed to drive the electrosynthesis of CYCO from nitrite and cyclohexanone at an almost 100% yield and Faradaic efficiency (FE) of 46.09%. Moreover, the i-Pd3Biene also performed well for the electro-reforming of polyethylene terephthalate to synthesize glycolic acid (GA, FE: 96.63%). Detailed mechanism studies demonstrated that the interatomic strong p-d orbital hybridization evokes electron transfer from Bi to Pd and leads to electron localization on ordered Pd atoms, which shows positive effects on optimizing the adsorption equilibrium of key intermediates and directionally switching the reaction pathways to synthesize desired products. With such fundamental understanding, the bifunctional i-Pd3Biene is further employed to assemble an asymmetric coupled electrocatalysis system, achieving simultaneous energy savings in electrosynthesis of CYCO and GA.

Photocatalytic nonoxidation coupling of methane reactions can directly convert methane into high-value C2 products under mild conditions. However, the efficient conversion of CH4 to C2H4 is severely limited by the high C-H bond energy of CH4 and the slow kinetic process of C-C coupling. Herein, Mo-WO3-x catalysts with dual active sites were constructed by the isomorphic substitution of Mo6+ for W in WO3. Among them, Mo doping not only induces the preferential formation of oxygen vacancies between Mo and W atoms, but also enhances the catalytic activity of frustrated Lewis pairs composed of unsaturated W and lattice oxygen. The results show that the asymmetric dual active sites of unsaturated Mo and FLPs accelerate the cleavage of CH4 molecules, reduce the coupling energy barrier of CH2 intermediates, and synergistically promote the desorption of C2H4. The catalyst presents a C2H4 yield of up to 152.19 mu mol g-1 h-1 with a selectivity of 95%. This work provides insights into the preparation of highly efficient NOCM photocatalysts with a bimetallic synergistic effect.