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Single-atoms (SAs) with atomically coordinated reaction centers are considered the next generation of catalysts that can exhibit exceptional catalytic efficiency. However, the general concern about thermodynamic vulnerabilities of SAs questions their practical value. Moreover, whether the inherent catalytic nature of SAs is superior compared with that of larger nanoparticles is still under debate. Here, we address two controversies by a comparative study using two catalysts: Pt/TiO2 and Pt/CeOx-TiO2. Based on a hierarchical study of density functional theory, time-resolved catalysis performance test, in situ infrared spectroscopy, and operando X-ray absorption spectroscopy, we could unveil the catalytic nature of Pt-SAs and their stability. By utilizing the heterogeneous interface formed between TiO2 supporting particles and CeOx clusters formed on the surface of TiO2, we preferentially synthesized Pt-SAs pinned at the CeOx-TiO2 interfaces on CeOx-TiO2 hybrid-oxide supports. The strong electronic coupling between the Pt-SAs and the Ce ions at the CeOx-TiO2 interfaces enhanced the catalytic activity toward CO oxidation of Pt-SAs and improved the long-term stability under CO oxidation conditions. The CO oxidation activity of Pt-SAs stabilized at CeOx-TiO2 was improved by 13.5 times at 200 °C compared with the Pt-SAs on TiO2. The results present how to easily improve the activity and stability of Pt-SAs using a simple interface control method. Moreover, we demonstrate that the catalytic activity and the stability of Pt-SAs can be monitored through the chemical state of the interfaces. Our study provides comprehensive understanding about the catalytic nature as well as a novel strategy toward applications of Pt-SAs, enabling sustainable use of Pt in heterogeneous catalysts.

Modulating the electronic structure of transition metal dichalcogenides (TMDs) via alloying is challenging despite the additional potential applications. In this study, a solvothermal reaction is used to synthesize composition‐tuned ReS2–VS2 (Re1‐xVxS2) alloy nanosheets featuring an expanded interlayer distance. Increasing x induces a phase transition from the semiconducting 1T″ phase ReS2 to the metallic 3R‐stacking 1T phase VS2. Alloying via homogeneous atomic mixing renders the nanosheets more metallic and with less oxidation than VS2. First‐principles calculations consistently predict the 1T″–1T phase transition of the atomically mixed alloy structures. The calculation also suggests that intercalation drives the 3R stacking of 1T phase VS2. The Re1‐xVxS2 nanosheets at x = 0.3–0.8 exhibit enhanced electrocatalytic activity toward water‐splitting hydrogen evolution reaction (HER) in an acid electrolyte. In situ X‐ray absorption fine structure measurements reveal that the metallicity of the alloys is fully retained during HER. The density of states and Gibbs free energy calculations show that alloying increases the metallicity and thus effectively activates the basal S atoms toward the HER, supporting the observed increased HER performance of the alloy nanosheets. [ABSTRACT FROM AUTHOR]

Green hydrogen (H2) production from solar water splitting necessitates photoelectrodes with superior photoelectrochemical (PEC) activity and durability. However, surface defects and photocorrosion instability—especially at high potentials—limit PEC performance and stability. Herein, the prototypical bismuth vanadate (BiVO4) photoanode is used to demonstrate a holistic approach to improve photocurrent density and long‐term stability. In this approach, high surface‐area nanostructuring of BiVO4 is combined with barium (Ba) doping with semi‐crystalline hafnium oxide (HfO2) surface passivation and single‐atom nickel platinum (NiPt) catalysts. The introduction of Ba2+ ions into BiVO4 increases the concentration of conductive V4+ ions or the ratio of V4+ ions to oxygen vacancies, avoiding V5+ dissolution during water oxidation. The semi‐crystalline HfO2, which serves as a passivation layer, prevents BiVO4 photocorrosion by suppressing harmful chemical reactions when holes are transferred to the electrolyte. The synergistic use of isolated single‐atom and Ni‐Pt coordination improves charge transfer at the photoanode/electrolyte interface, leading to enhanced PEC kinetics and stability. As a result, a photoelectrode is demonstrated with ≈6.5 mA cm−2 at 1.23 V versus a reversible hydrogen electrode (RHE) and continuous operation for 800 h with a negligible degradation rate. This work provides a promising approach to improve photoanodes for PEC H2 production. [ABSTRACT FROM AUTHOR]

Mo2C is an excellent electrocatalyst for hydrogen evolution reaction (HER). However, Mo2C is a poor electrocatalyst for oxygen evolution reaction (OER). Herein, two different elements, namely Co and Fe, are incorporated in Mo2C that, therefore, has a finely tuned electronic structure, which is not achievable by incorporation of any one of the metals. Consequently, the resulting electrocatalyst Co0.8Fe0.2–Mo2C‐80 displayed excellent OER catalytic performance, which is evidenced by a low overpotential of 214.0 (and 246.5) mV to attain a current density of 10 (and 50) mA cm−2, an ultralow Tafel slope of 38.4 mV dec−1, and long‐term stability in alkaline medium. Theoretical data demonstrates that Co0.8Fe0.2–Mo2C‐80 requires the lowest overpotential (1.00 V) for OER and Co centers to be the active sites. The ultrahigh catalytic performance of the electrocatalyst is attributed to the excellent intrinsic catalytic activity due to high Brunauer–Emmett–Teller specific surface area, large electrochemically active surface area, small Tafel slope, and low charge‐transfer resistance. [ABSTRACT FROM AUTHOR]

In this study, we performed the CO2 reduction reaction (CO2RR) using a structural composite catalyst of cuprous oxide (Cu2O) and silver (Ag) that was simultaneously electrodeposited. While the underneath Ag electrodeposits maintained their spiky backbone structures even after the CO2RR, the Cu2O deposits were reduced to Cu(111) and relocated on the backbone template. The structural changes in Cu2O to Cu increase the active area of the Cu–Ag interface, resulting in a remarkable production rate of 125.01 μmol h−1 of liquid C2+ chemicals via the stabilization of the C–C coupling of the key intermediate species of acetaldehyde. This study provides new insights into designing a bimetallic catalyst for producing sustainable C2+ products from CO2 without any selectivity towards the production of methane. [ABSTRACT FROM AUTHOR]

Atomically‐dispersed copper sites coordinated with nitrogen‐doped carbon (Cu–N–C) can provide novel possibilities to enable highly selective and active electrochemical CO2 reduction reactions. However, the construction of optimal local electronic structures for nitrogen‐coordinated Cu sites (Cu–N4) on carbon remains challenging. Here, we synthesized the Cu–N–C catalysts with atomically‐dispersed edge‐hosted Cu–N4 sites (Cu–N4C8) located in a micropore between two graphitic sheets via a facile method to control the concentration of metal precursor. Edge‐hosted Cu–N4C8 catalysts outperformed the previously reported M–N–C catalysts for CO2‐to‐CO conversion, achieving a maximum CO Faradaic efficiency (FECO) of 96%, a CO current density of –8.97 mA cm–2 at –0.8 V versus reversible hydrogen electrode (RHE), and over FECO of 90% from –0.6 to –1.0 V versus RHE. Computational studies revealed that the micropore of the graphitic layer in edge‐hosted Cu–N4C8 sites causes the d‐orbital energy level of the Cu atom to shift upward, which in return decreases the occupancy of antibonding states in the *COOH binding. This research suggests new insights into tailoring the locally coordinated structure of the electrocatalyst at the atomic scale to achieve highly selective electrocatalytic reactions. [ABSTRACT FROM AUTHOR]