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Surface hydroxyls (OH) are crucial for heterogeneous catalysis in water. However, they are commonly characterized at solid–gas interfaces (e.g., FTIR, XPS, TGA), which may not represent the surface in aqueous environments. Here, the surface OH of five catalytically relevant oxides (Al2O3, ZrO2, TiO2, Fe2O3, Co3O4) are quantified by substituting them with F− ions at pH 3–10, where the surface fluoride (F) density is evaluated by XPS using the geometry factor for spherical particles. These results show that the surface F density peaks at around pH 4 across all oxides, but decreases at more basic pH due to increased OH− competition. Generally, oxides more abundant in surface OH can also accommodate more surface F, establishing F− ions as effective probes. While terminal F are likely the preferential substitution product, bridging F also appear to form at lower pH levels. Furthermore, fluoride substitution is applied to a series of Co3O4 gradually enriched with defects using pulsed laser defect engineering in liquid (PUDEL). This approach reveals a linear correlation between laser processing and surface OH density, which aligns with a previously observed improvement in OER activity, and is supported by additional DFT calculations here. This work will stimulate further studies adopting fluoride substitution to better understand the relationship between surface chemistry and catalytic processes in aqueous environments. [ABSTRACT FROM AUTHOR]

Two‐dimensional transistors are promising candidates for the next generation of nanoscale devices. Like the other alternatives, they also encounter problems such as instability under standard condition (STP), low channel mobility, small band gaps, and difficulty to integrate metal contacts. The latter poses a great challenge since metal/semiconductor interface significantly affects the transistor's performance. Some of these obstacles can be solved by using two‐dimensional transition metal di‐chalcogenides (TMDC) materials. In this study, we performed charge transport calculation based on density functional theory (DFT) followed by wave dynamics to evaluate the performance of six two‐dimensional TMDC metal/semiconductor/metal systems. Each semiconductor monolayer was laterally connected, at both ends to metal contacts consisting of VS2 or FeS2 monolayers. We found that charge transport was more efficient in systems containing a CrS2 semiconductor monolayer compared to systems with MoS2 or WS2 as the semiconductor monolayer. The electronic characterization of the monolayer TMDC materials by DFT estimates well the trend in charge transport efficiency calculated using wave packet dynamics. [ABSTRACT FROM AUTHOR]

Ammonia has attracted considerable interest as a hydrogen carrier that can help decarbonize global energy networks. Key to realizing this is the development of low temperature ammonia fuel cells for the on-demand generation of electricity. However, the efficiency of such systems is significantly impaired by the sluggish ammonia oxidation reaction (AOR) and oxygen reduction reaction (ORR). Here, we report the design of a bifunctional Ag2Pt3TiS6 electrocatalyst that facilitates both reactions at activities exceeding that of commercial Pt/C. Through comprehensive density functional theory simulations, we identify that active site motifs composed of Pt and Ti atoms work cooperatively to catalyze ORR and AOR. Notably, in-situ shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) experiments indicate a decreased propensity for *NOx formation and hence an increased resistance toward catalyst poisoning for AOR. Employing Ag2Pt3TiS6 as both the cathode and anode, we constructed a low temperature ammonia fuel cell with a high peak power density of 8.71 mW cm-2 and low Pt loading of 0.45 mg cm-2. Our findings demonstrate a pathway towards the rational design of effective electrocatalysts with multi-element active sites that work cooperatively., (© 2024 Wiley‐VCH GmbH.)

Trimetallic double hydroxide NiFeCo-OH is prepared by coprecipitation, from which three different catalysts are fabricated by different heat treatments, all at 350 °C maximum temperature. Among the prepared catalysts, the one prepared at a heating and cooling rate of 2 °C min -1 in N 2 atmosphere (designated NiFeCo-N 2 -2 °C) displays the best catalytic properties after stability testing, exhibiting a high current density (9.06 mA cm -2 at 320 mV), low Tafel slope (72.9 mV dec -1 ), good stability (over 20 h), high turnover frequency (0.304 s -1 ), and high mass activity (46.52 A g -1 at 320 mV). Stability tests reveal that the hydroxide phase is less suitable for long-term use than catalysts with an oxide phase. Two causes are identified for the loss of stability in the hydroxide phase: a) Modeling of the distribution function of relaxation times (DFRT) reveals the increase in resistance contributed by various relaxation processes; b) density functional theory (DFT) surface energy calculations reveal that the higher surface energy of the hydroxide-phase catalyst impairs the stability. These findings represent a new strategy to optimize catalysts for water splitting., (© 2021 Wiley-VCH GmbH.)