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Transition metal oxide (TMO)‐based anodes attract much attention for lithium storage due to the merits of high theoretical capacity, facile synthesis, and easy scale‐up. Moreover, the increased working potential avoids the issue of lithium dendrites formation and thus improves battery safety. Herein, we propose a route to significantly improve the electrochemical performance of TMO anodes through configurational entropy optimization. For example, high‐entropy oxide (FeCoNiCrCu)3O4 is synthesized by carefully selecting metal elements. The (FeCoNiCrCu)3O4 electrode ensures not only low potential but also holds high capacity. In the half‐cell configuration, the (FeCoNiCrCu)3O4 electrode provides a specific capacity of 575.7 mAh g−1 after 200 cycles at 0.2 A g−1. More importantly, the electrode showed a relatively low discharge voltage of 0.39 V at 0.5 A g−1, which is caused by the configuration entropy optimization. The assembled (FeCoNiCrCu)3O4//LCO coin‐type full cell exhibits a high capacity of 266.3 mAh g−1 after 100 cycles at 0.2 A g−1 and an operating voltage up to 3.9 V. [ABSTRACT FROM AUTHOR]

Perovskite oxides are regarded as promising electrocatalysts for water splitting due to their cost‐effectiveness, high efficiency and durability in the oxygen evolution reaction (OER). Despite these advantages, a fundamental understanding of how critical structural parameters of perovskite electrocatalysts influence their activity and stability is lacking. Here, we investigate the impact of structural defects on OER performance for representative LaNiO3 perovskite electrocatalysts. Hydrogen reduction of 700 °C calcined LaNiO3 induces a high density of surface oxygen vacancies, and confers significantly enhanced OER activity and stability compared to unreduced LaNiO3; the former exhibit a low onset overpotential of 380 mV at 10 mA cm−2 and a small Tafel slope of 70.8 mV dec−1. Oxygen vacancy formation is accompanied by mixed Ni2+/Ni3+ valence states, which quantum‐chemical DFT calculations reveal modify the perovskite electronic structure. Further, it reveals that the formation of oxygen vacancies is thermodynamically more favourable on the surface than in the bulk; it increases the electronic conductivity of reduced LaNiO3 in accordance with the enhanced OER activity that is observed. [ABSTRACT FROM AUTHOR]

While direct solar‐driven water splitting has been investigated as an important technology for low‐cost hydrogen production, the systems demonstrated so far either required expensive materials or presented low solar‐to‐hydrogen (STH) conversion efficiencies, both of which increase the levelized cost of hydrogen (LCOH). Here, a low‐cost material system is demonstrated, consisting of perovskite/Si tandem semiconductors and Ni‐based earth‐abundant catalysts for direct solar hydrogen generation. NiMo‐based hydrogen evolution reaction catalyst is reported, which has innovative "flower‐stem" morphology with enhanced reaction sites and presents very low reaction overpotential of 6 mV at 10 mA cm−2. A perovskite solar cell with an unprecedented high open circuit voltage (Voc) of 1.271 V is developed, which is enabled by an optimized perovskite composition and an improved surface passivation. When the NiMo hydrogen evolution catalyst is wire‐connected with an optimally designed NiFe‐based oxygen evolution catalyst and a high‐performance perovskite‐Si tandem cell, the resulting integrated water splitting cell achieves a record 20% STH efficiency. Detailed analysis of the integrated system reveals that STH efficiencies of 25% can be achieved with realistic improvements in the perovskite cell and an LCOH below ≈$3 kg−1 is feasible. [ABSTRACT FROM AUTHOR]

Critical catalysis studies often lack elucidation of the mechanistic role of defect equilibria in solid solubility and charge compensation. This approach is applied to interpret the physicochemical properties and catalytic performance of a free‐standing 2D–3D CeO2−x scaffold, which is comprised of holey 2D nanosheets, and its heterojunctions with MoO3−x and RuO2. The band gap alignment and structural defects are engineered using density functional theory (DFT) simulations and atomic characterization. Further, the heterojunctions are used in hydrogen evolution reaction (HER) and catalytic ozonation applications, and the impacts of the metal oxide heteroatoms are analyzed. A key outcome is that the principal regulator of the ozonation performance is not oxygen vacancies but the concentration of Ce3+ and Ce vacancies. Cation vacancy defects are measured to be as high as 8.1 at% for Ru‐CeO2−x. The homogeneous distribution of chemisorbed, Mo‐oxide, heterojunction nanoparticles on the CeO2−x holey nanosheets facilitates intervalence charge transfer, resulting in the dominant effect and resultant ≈50% decrease in overpotential for HER. The heterojunctions are tested for aqueous‐catalytic ozonation of salicylic acid, revealing excellent catalytic performance from Mo doping despite the adverse impact of Ce vacancies. The present study highlights the use of defect engineering to leverage experimental and DFT results for band alignment. [ABSTRACT FROM AUTHOR]

Metal–organic frameworks (MOFs) are considered to be promising candidates for electrochemical water splitting. However, most MOFs are characterized by low electronic conductivity limiting their use as bulk materials for anodes and cathodes. Furthermore, the understanding of the critical parameters controlling the activity and stability of MOF electrocatalysts is still insufficient. Herein, a systematic analysis is presented of the key structural parameters controlling the oxygen evolution reaction (OER) performance and stability of a representative family of bimetallic NiFe‐MOFs, where the role of the metal cations on the accessible active sites and intrinsic activity can be investigated independently from the crystal structure. The models and in‐depth structural and morphological characterizations reveal a hierarchy of properties affecting the OER activity with accessible sites and intrinsic activity playing a major role in the charge transfer efficiency. Optimization of these properties and addition of a conductive support substrate leads to efficient MOF‐nanocomposite electrocatalysts achieving a low overpotential of 258 mV at a current density of 10 mA cm−2 with a small Tafel slope of 49 mV dec−1 and excellent stability for more than 32 h of continuous OER in alkaline medium. [ABSTRACT FROM AUTHOR]

Three structurally distinct interfaces, i. e. Au/α-Fe2O3-THB-Air, Au/α-Fe2O3-HS-Air, and Au/α-Fe2O3-QC-Air, with the major substrate facet being {113}, {001}, and {012} respectively, were controllably prepared. The low temperature water gas shift (WGS) reaction (100-260 °C) was applied to these unique systems to reveal how these structurally distinct interfaces can impact on the reaction behavior. With the detailed performance evaluation plus the characterizations of CO-TPSR, XPS, and in situ-FTIR in particular, the correlations between the evolution of different intermediates and the distinct catalytic behaviors have been established. The substrate facet structure and the Au entity largely determine the form and reactivity of surface OH/ H2O species which in turn determine the formation of different intermediates and eventually the product formation. The Au/α-Fe2O3-THB-Air is enriched with oxygen vacant sites, favorable for dissociative adsorption of H2O, carboxyl intermediate formation and H2 production. The Au/α-Fe2O3-HS-Air is enriched with surface lattice oxygen, favorable for molecular adsorption of H2O, formate intermediate formation, and CO2 production. The Au/α-Fe2O3-QC-Air interface is enriched with surface Fe sites, favorable for dissociative adsorption of H2O and evolution of stable carboxyl intermediate as well as isolated OH species at low reaction temperatures. The findings are informative to control the interfacial structure for the WGS and other reactions. [ABSTRACT FROM AUTHOR]

The interactions between the reactants and catalysts surfaces play a significant role in heterogeneous catalysis, thus to tune the interfacial properties between them has emerged as an important topic. This review has summarised some recent advances about the effects of wettability on the catalytic reactions, including hydrophilicity, hydrophobicity, and dewetting properties. In addition, the effect of coalescence dynamics among the catalyst particles is also discussed based on a series of investigations. Although the researchers have realised the importance of wettability, the ability to tune the wettability in their work needs to be further enhanced. Therefore, we finally highlighted considerable useful approaches to achieve controllable wettability and coalescence. It is expected that in the future design of catalysts, researchers should pay more attention to tuning the interfacial structure to achieve the enhanced catalysts behaviours. Wet wet wet: Surface wettability and coalescence dynamics have a great impact on the catalyst activity and the preparation of catalyst, and the catalytic performances could be significantly improved by the fine control of surface wettability and coalescence dynamics. Here, the authors provide many effective approaches to achieve the controllable surface wettability and coalescence, which is expected to be applied in the catalytic field. [ABSTRACT FROM AUTHOR]

Abstract: The rational design of low‐cost transition metal catalysts that exhibit high activity and selectivity may be the most significantly investigated in heterogeneous catalysis. In this study, Co3‐xMnxO4 (x=0.75, 1.0, and 1.5) mixed metal oxides were successfully synthesized by a controlled template‐free autoclave strategy and studied for toluene oxidation. It is found that the Co‐rich sample showed markedly enhanced activity and the 3D dandelion‐like Co2.25Mn0.75O4 catalyst exhibited in the highest toluene oxidation rate (8.9 μmol/(gcats)) and a 100 % toluene conversion at 239 °C. In situ DRIFTS study indicates that toluene was sequentially oxidized to benzyl radical, benzaldehyde, benzene, oxalic acid, and finally to CO2 and H2O. The interaction between Co and Mn, in conjunction with the high concentration of surface oxygen species and rich surface oxygen vacancies, reasonably explains the elevated catalytic activity and thermal stability for toluene oxidation over 3D flower‐like Co3‐xMnxO4 spinel catalysts. [ABSTRACT FROM AUTHOR]

Using [Ni{(POEt)3}4] as catalyst precursor for the catalytic isomerization of allylbenzene to beta‐methylstyrene, time‐course studies suggest a mechanism that is consistent with an autocatalytic reaction. The sigmoidal curve observed when plotting conversion vs. time fits exceptionally well to a kinetic model of an autocatalytic process (R2 = 0.998). We show that the uncoordinated phosphite, generated during the catalyst activation, reduces the acid concentration and, consequently, has a detrimental effect on the formation of the protonated active nickel catalyst. The nickel complex protonation is seen as a key step in forming the active catalytic species. The novel use of a mercury salt as a phosphite scavenger leads to inhibition of the free phosphite's capability to lower acid concentration, improving the catalytic performance of the system, consistent with the mechanism proposed. [ABSTRACT FROM AUTHOR]

Highly dispersed Ni nanoparticles supported on high-surface-area mesoporous nanocrystalline MgAl2O4 powder was generated by a facile and simple propylene oxide assisted gelation agent route. The mesoporous spinel materials exhibited enhanced catalytic performance for hydrogen production in biogas dry reforming. The obtained spinel catalysts with different Ni loadings after calcination at 700 °C possessed high BET surface areas (236-224 m2 g−1). A narrow pore size distribution in the mesopore range was observed in the samples, and all the samples except 2.5 wt % Ni showed a mesoporous-macroporous structure. The 5 wt % Ni/MgAl2O4 sample showed the highest activity for the biogas dry reforming reaction because of the high dispersion of Ni on the mesoporous surface of the spinel support. X-ray photoelectron spectroscopy revealed that the catalysts with a low Ni loading undergo the exchange of Mg2+ by Ni2+, whereas catalysts with a higher Ni loading undergo the substitution of Al3+ by Ni3+. Thus, appropriate partial Ni substitution in the MgAl2O4 support may play a role in the elevated catalytic performance. [ABSTRACT FROM AUTHOR]

The polymerization of the photocleavable monomer, o-nitrobenzyl methacrylate (NBMA), is investigated using photoinduced electron/energy transfer reversible addition-fragmentation chain transfer polymerization. The polymerizations under visible red ( λmax = 635 nm, 0.7 mW cm−2) and yellow ( λmax = 560 nm, 9.7 mW cm−2) light are performed and demonstrate rational evidence of a controlled/living radical polymerization process. Well-defined poly( o-nitrobenzyl methacrylate) (PNBMA) homopolymers with good control over the molecular weight and polymer dispersity are successfully synthesized by varying the irradiation time and/or targeted degree of polymerization. Chain extension of a poly(oligo(ethylene glycol) methyl ether methacrylate) macro-chain transfer agent with NBMA is carried out to fabricate photocleavable amphiphilic block copolymers (BCP). Finally, these self-assembled BCP rapidly dissemble under UV light suggesting the photoresponsive character of NBMA is not altered during the polymerization under yellow or red light. Such photoresponsive polymers can be potentially used for the remote-controlled delivery of therapeutic compounds. [ABSTRACT FROM AUTHOR]

BACKGROUND The effect of the B cation on the surface properties and catalytic activity in the dry reforming reaction over La0. 4M0. 6Al0. 2Ni0. 8O3 (M=noble metal) perovskite-type oxides with surface area 3.26-4.14 m2 g-1 and rhombohedral structure was studied. RESULTS Among LaAlxNi1- xO3 series, LaAl0. 2Ni0. 8O3 had the highest catalytic activity, but suffered a slow deactivation with time-on-stream ( TOS). It is observed that all samples presented similar activity at low reaction temperatures (500-600°C), while at higher temperatures (600-850°C) the prepared solid was more active and perovskite phase was transformed into Ni0 or La2O2CO3. It was found that among the noble metal samples, La0. 4Rh0. 6Al0. 2Ni0. 8O3 possessed the highest surface area and surface oxygen concentration and the best low-temperature reducibility. For the Rh catalyst the CH4 and CO2 conversions were 89.1 and 86.2%, which were the most resistant against coke deposition and showed very high stability without decrease in reforming and remained constant during the 3000 min TOS. The following order of activity was observed: La0. 4Rh0. 6Al0. 2Ni0. 8O3 > La0. 4Ru0. 6Al0. 2Ni0. 8O3 > LaAl0. 2Ni0. 8O3> La0. 4Ir0. 6Al0. 2Ni0. 8O3 ≥La0. 4Pt0. 6Al0. 2Ni0. 8O3 > La0. 4Pd0. 6Al0. 2Ni0. 8O3. CONCLUSIONS It is believed that the high surface area and surface oxygen concentration and good low-temperature reducibility were responsible for the good catalytic performance of the La0. 4Rh0. 6Al0. 2Ni0. 8O3 sample. © 2013 Society of Chemical Industry [ABSTRACT FROM AUTHOR]

Keywords: graphene; MOF grains; nanocomposites; ultrafine structure; water oxidation EN graphene MOF grains nanocomposites ultrafine structure water oxidation 1 1 1 04/29/21 20210428 NES 210428 In article number 2003759, Antonio Tricoli, Chuan Zhao and co-workers design well-dispersed bimetallic NiFe-MOF nanograins homogeneously grafted on graphene for use in the oxygen evolution reaction (OER). Oxygen Evolution Reaction: Engineering the Activity and Stability of MOF-Nanocomposites for Efficient Water Oxidation (Adv. Graphene, MOF grains, nanocomposites, nanocomposites, ultrafine structure, water oxidation. [Extracted from the article]

Nano‐sized perovskites were synthesized in a spray flame from nitrate precursors dissolved in ethanol and in ethanol/2‐ethylhexanoic acid (2‐EHA) mixtures. Experiments with ethanol led to a broad particle‐size distribution and to the formation of undesired phases such as La2CoO4, La2O3, and Co3O4. The addition of 2‐EHA can initiate micro explosions of the burning droplets and has been systematically investigated toward the formation of single‐phase, high‐surface‐area LaCoO3 and LaFeO3 with a narrow size distribution. To investigate the effect of 2‐EHA, temperature‐dependent changes of the chemical composition of the precursor solutions were analyzed with ATR‐FTIR between 23 and 70°C. In all cases, the formation of esters was identified while in the solutions containing iron, additional formation of carboxylates was observed. The synthesized materials were characterized by BET SSA, XRD, SAED and EDX‐TEM and their catalytic activity was analyzed, reaching 50% CO conversion at temperatures below 160 and 300°C for LaCoO3 and LaFeO3, respectively. [ABSTRACT FROM AUTHOR]

Back Cover: Polymers featuring photoresponsive groups have been exploited as promising drug delivery systems. Light as spatially and temporally controllable external stimulus can be readily tuned and focused to trigger changes in the structure of polymer chains to provide “on‐command” drug delivery. A benign synthesis route for a novel controlled polymerization, known as photoinduced electron/energy transfer–reversible addition–fragmentation (PET‐RAFT) polymerization, is presented. Further details can be found in the article by A. Bagheri, J. Yeow, H. Arandiyan, J. Xu, C. Boyer,* and M. Limon page 905. [ABSTRACT FROM AUTHOR]