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The efficacy of treatment with hydrogen and Ag-Cu co-deposition on TiO2 photocatalysts has been investigated computationally and experimentally. The hydrogenated Ag-Cu with co-loaded TiO2 (H:(Ag-Cu/TiO2)) achieved a photoactivity about 110 times that of pristine TiO2, which corresponds to a rate of 1.16 mmol h−1 g−1 for hydrogen generation. Soft X-ray spectra and quantum-chemical calculations indicate that the notable promotion of photoactivity on H:(Ag-Cu/TiO2) is ascribable to the synergy between new electronic states and a lattice distortion. The soft X-ray absorption spectra (XAS) indicated that the TiO6 octahedral symmetry and the Ti 3d- orbital orientation are significantly affected by the Ag-Cu decoration and the hydrogenation treatment. The mechanisms involved in this photocatalysis were studied with soft XAS in situ, which showed that the photoexcited electrons transfer from the bimetallic Ag-Cu to the TiO2 conduction band as the photoresponse of this composite photocatalyst. The strategy of coupling hydrogenation with bimetallic Ag-Cu onto TiO2-based photocatalysis provides a facile and promising solution to other environmental and energy applications.

Heterojunction nanostructures usually exhibit enhanced properties in compariosn with their building blocks and are promising catalyst candidates due to their combined surface and unique interface. Here, for the first time we realized the oriented growth of ultrasmall metal nanoparticles (NPs) on metal-organic framework nanosheets (MOF NSs) by precisely regulating the reduction kinetics of metal ions with solvents. In particular, a rapid reduction of metal ions leads to the random distribution of metal NPs on the surface of MOF NSs, while a slow reduction of metal ions results in the oriented growth of NPs on the edge of MOF NSs. Impressively, the strong synergy between Pt NPs and MOF NSs significantly enhances the hydrogen evolution reaction (HER) performance, and the optimal catalyst displays HER activities superior to those of a composite with a random growth of Pt NPs and commercial Pt/C under both acidic and alkaline conditions. Moreover, the versatility of such oriented growth has been extended to other metal NPs, such as Pd, Ag, and Au. We believe this work will promote research interest in material design for many potential applications.

The activity and accessibility of MoS2 edge sites are critical to deliver high hydrogen evolution reaction (HER) efficiency. Here, a porous carbon network confining ultrasmall N-doped MoS2 nanocrystals (N-MoS2/CN) is fabricated by a self-templating strategy, which realizes synergistically structural and electronic modulations of MoS2 edges. Experiments and density functional theory calculations demonstrate that the N dopants could activate MoS2 edges for HER, while the porous carbon network could deliver high accessibility of the active sites from N-MoS2 nanocrystals. Consequently, N-MoS2/CN possesses superior HER activity with an overpotential of 114 mV at 10 mA cm-2 and excellent stability over 10 h, delivering one of best MoS2-based HER electrocatalysts. Moreover, this study opens a new venue for optimizing materials with enhanced accessible catalytic sites for energy-related applications.

Despite the recent advances in electrochemical water splitting, developing cost-effective and highly efficient electrocatalysts for oxygen evolution reaction (OER) still remains a substantial chall...

Two-dimensional (2D) metal-organic framework nanosheets (MOF NSs) play a vital role in catalysis, but the most preparation is ultrasonication or solvothermal. Herein, a liquid-liquid interfacial synthesis method has been developed for the efficient fabrication of a series of 2D Ni MOF NSs. The active sites could be modulated by readily tuning the ratios of metal precursors and organic linkers (RM/L ). The Ni MOF NSs display highly RM/L dependent activities towards 2e oxygen reduction reaction (ORR) to hydrogen peroxide (H2 O2 ), where the Ni MOF NSs with the RM/L of 6 exhibit the optimal near-zero overpotential, ca. 98 % H2 O2 selectivity and production rate of ca. 80 mmol gcat -1 h-1 in 0.1 M KOH. As evidenced by X-ray absorption fine structure spectroscopy, the coordination environment of active sites changed from saturation to unsaturation, and the partially unsaturated metal atoms are crucial to create optimal sites for enhancing the electrocatalysis.

Developing efficient and stable non-noble electrocatalysts for the oxygen evolution reaction (OER) remains challenging for practical applications. While nickel-iron layered double hydroxides (NiFe-LDH) are emerging as prominent candidates with promising OER activity, their catalytic performance is still restricted by the limited active sites, poor conductivity and durability. Herein, hierarchical nickel-iron-cobalt LDH nanosheets/carbon fibers (NiFeCo-LDH/CF) are synthesized through solvent-thermal treatment of ZIF-67/CF. Extended X-ray adsorption fine structure analyses reveal that the Co substitution can stabilize the Fe local coordination environment and facilitate the π-symmetry bonding orbital in NiFeCo-LDH/CF, thus modifying the electronic structures. Coupling with the structural advantages, including the largely exposed active surface sites and facilitated charge transfer pathway ensured by CF, the resultant NiFeCo-LDH/CF exhibits excellent OER activity with an overpotential of 249 mV at 10 mA cm-1 as well as robust stability over 20 h.

The activity and accessibility of MoS

A well-steered coordination environment on photoelectrode can offer fruitful active sites and efficaciously alter atomic and electronic configuration to boost the performance in water oxidation. To enhance the performance of the photocatalytic oxygen-evolution reaction, enriched oxygenous-type carbon quantum dots (CQD) were combined with oxygen-deficient ZnO@H-ZnO1-x homojunctions for the first time. Specifically, hydrogenation created an unstoichiometric H-ZnO1-x surface through oxygen vacancies, which were responsible for the formation of coordinatively unsaturated Zn centers to drive the photoelectrochemical reaction by precise regulation of the charge density, valence-band edge, atomic geometric structure and electronic structure. The enriched photohole reservoir in carboxyl-conjugated CQD was a great benefit for super-rapid charge tunnels, thereby governing the rate of internal and interfacial charge separation and transport in the multijunction. Accordingly, the CQD/H-ZnO1-x/ZnO photoanodes showed a photoactivity enhanced five-fold relative to bare ZnO NR and maintained that high performance for 24 h of operation. Comprehensive analyses, involving electrochemical measurements, time-resolved photoluminescence, X-ray absorption spectra in situ and calculations with density-functional theory were undertaken to elucidate the underlying mechanism of enhancement and the route of directional charge transport as well as the interfacial charge dynamics over the CQD/H-ZnO1-x/ZnO photoelectrode. These findings provide a new track towards photoelectrodes that could yield not only strikingly enhanced photocatalysis but also satisfied stability for realistic application.