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Producing green hydrogen in a cost-competitive manner via water electrolysis will make the long-held dream of hydrogen economy a reality. Although platinum (Pt)-based catalysts show good performance toward hydrogen evolution reaction (HER), the high cost and scarce abundance challenge their economic viability and sustainability. Here, a non-Pt, high-performance electrocatalyst for HER achieved by engineering high fractions of stacking fault (SF) defects for MoNi 4 /MoO 2 nanosheets (d-MoNi) through a combined chemical and thermal reduction strategy is shown. The d-MoNi catalyst offers ultralow overpotentials of 78 and 121 mV for HER at current densities of 500 and 1000 mA cm -2 in 1 M KOH, respectively. The defect-rich d-MoNi exhibits four times higher turnover frequency than the benchmark 20% Pt/C, together with its excellent durability (> 100 h), making it one of the best-performing non-Pt catalysts for HER. The experimental and theoretical results reveal that the abundant SFs in d-MoNi induce a compressive strain, decreasing the proton adsorption energy and promoting the associated combination of *H into hydrogen and molecular hydrogen desorption, enhancing the HER performance. This work provides a new synthetic route to engineer defective metal and metal alloy electrocatalysts for emerging electrochemical energy conversion and storage applications., (© 2024 The Author(s). Advanced Materials published by Wiley‐VCH GmbH.)

Water electrolysis is a promising method for efficiently producing hydrogen and oxygen, crucial for renewable energy conversion and fuel cell technologies. The hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are two key electrocatalytic reactions occurring during water splitting, necessitating the development of active, stable, and low-cost electrocatalysts. Transition metal (TM)-based electrocatalysts, spanning noble metals and TM oxides, phosphides, nitrides, carbides, borides, chalcogenides, and dichalcogenides, have garnered significant attention due to their outstanding characteristics, including high electronic conductivity, tunable valence electron configuration, high stability, and cost-effectiveness. This timely review discusses developments in TM-based electrocatalysts for the HER and OER in alkaline media in the last 10 years, revealing that the exposure of more accessible surface-active sites, specific electronic effects, and string effects are essential for the development of efficient electrocatalysts towards electrochemical water splitting application. This comprehensive review serves as a guide for designing and constructing state-of-the-art, high-performance bifunctional electrocatalysts based on TMs, particularly for applications in water splitting.

Metal-organic frameworks (MOFs) are highly regarded as valuable adsorbent materials in materials science, particularly in the field of CO 2 capture. While numerous single-metal-based MOFs have demonstrated exceptional CO 2 adsorption capabilities, recent advancements have explored the potential of bimetallic MOFs for enhanced performance. In this study, a CuCe-BTC MOF was synthesized through a straightforward hydrothermal method, and its improved properties, such as high surface area, smaller pore size, and larger pore volume, were compared with those of the bare Ce-BTC. The impact of the Cu/Ce ratio (1:4, 1:2, 1:1, and 3:2) was systematically investigated to understand how adding a second metal influences the CO 2 adsorption performance of the Ce-BTC MOF. Various characterization techniques, including scanning electron microscopy, transmission electron microscopy, powder X-ray diffraction, thermogravimetric analysis, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and N 2 BET surface area analysis, were employed to assess the physical and chemical properties of the bare Ce-BTC and CuCe-BTC samples. Notably, CuCe-BTC-1:2 exhibited superior surface area (133 m 2 g -1 ), small pore size (3.3 nm), and large pore volume (0.14 cm 3 g -1 ) compared to the monometallic Ce-BTC. Furthermore, CuCe-BTC-1:2 demonstrated a superior CO 2 adsorption capacity (0.74 mmol g -1 ), long-term stability, and good CO 2 /N 2 selectivity. This research provides valuable insights into the design of metal-BTC frameworks and elucidates how introducing a second metal enhances the properties of the monometallic Ce-BTC-MOF, leading to improved CO 2 capture performance.

Green hydrogen, derived from water splitting powered by renewable energy such as solar and wind energy, provides a zero-emission solution crucial for revolutionizing hydrogen production and decarbonizing industries. Catalysts, particularly those utilizing defect engineering involving the strategical introduction of atomic-level imperfections, play a vital role in reducing energy requirements and enabling a more sustainable transition toward a hydrogen-based economy. Stacking fault (SF) defects play an important role in enhancing the electrocatalytic processes by reshaping surface reactivity, increasing active sites, improving reactants/product diffusion, and regulating electronic structure due to their dense generation ability and profound impact on catalyst properties. This review explores SF in metal-based materials, covering synthetic methods for the intentional introduction of SF and their applications in hydrogen production, including oxygen evolution reaction, photo- and electrocatalytic hydrogen evolution reaction, overall water splitting, and various other electrocatalytic processes such as oxygen reduction reaction, nitrate reduction reaction, and carbon dioxide reduction reaction. Finally, this review addresses the challenges associated with SF-based catalysts, emphasizing the importance of a detailed understanding of the properties of SF-based catalysts to optimize their electrocatalytic performance. It provides a comprehensive overview of their various applications in electrocatalytic processes, providing valuable insights for advancing sustainable energy technologies., (© 2024 The Authors. Advanced Materials published by Wiley‐VCH GmbH.)

Developing sustainable energy solutions to safeguard the environment is a critical ongoing demand. Electrochemical water splitting (EWS) is a green approach to create effective and long-lasting electrocatalysts for the water oxidation process. Metal organic frameworks (MOFs) have become commonly utilized materials in recent years because of their distinguishing pore architectures, metal nodes easy accessibility, large specific surface areas, shape, and adaptable function. This review outlines the most significant developments in current work on developing improved MOFs for enhancing EWS. The benefits and drawbacks of MOFs are first discussed in this review. Then, some cutting-edge methods for successfully modifying MOFs are also highlighted. Recent progress on nickel (Ni) and iron (Fe) based MOFs have been critically discussed. Finally, a comprehensive analysis of the existing challenges and prospects for Ni- and Fe-based MOFs are summarized.

The diffusive gradients in thin films (DGT) technique serves as a passive sampling method, inducing analyte transport and concentration. Its application is widespread in assessing labile components of metals, organic matter, and nutrients across various environmental media such as water, sediments, and saturated soils. The DGT devices effectively reduce the porewater concentration through irreversible binding of solutes, consequently promoting the release of labile species from the soil/sediment solid phase. However, the precise quantification of simultaneous adsorption and desorption of labile species using DGT devices alone remains a challenge. To address this challenge, the DGT-Induced Fluxes in Soils and Sediments (DIFS) model was developed. This model simulates analyte kinetics in solid phases, solutions, and binding resins by incorporating factors such as soil properties, resupply parameters, and kinetic principles. While the DIFS model has been iteratively improved to increase its accuracy in portraying kinetic behavior in soil/sediment, researchers' incomplete comprehension of it still results in unrealistic fitting outcomes and an oversight of the profound implications posed by kinetic parameters during implementation. This review provides a comprehensive overview of the optimization and utilization of DIFS models, encompassing fundamental concepts behind DGT devices and DIFS models, the kinetic interpretation of DIFS parameters, and instances where the model has been applied to study soils and sediments. It also highlights preexisting limitations of the DIFS model and offers suggestions for more precise modeling in real-world environments., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

Mesoporous carbon spheres (MCSs) show great potential for using as high-performance anodes in potassium-ion batteries (PIBs). Design and synthesis of MCSs with suitable multiscale structures and heteroatom doping or co-doping in MCSs are successfully employed to optimize the ion and electron transportation, however, it is still a challenge to explore MCS-based anodes with satisfactory potassium storage performance. In this work, we report novel S-doped MCS samples with abundant internal surfaces for potassium storage. The S doping sites are controlled during the synthesis, and the effect of different doping sites on the potassium storage is systematically studied. It is found that S doping between the carbon layers enlarges interlayer spacing and facilitates potassium ion adsorption. Consequently, the optimized sample shows an excellent rate capability of 144 mAh/g at 5.0 A/g, and a high reversible specific capacity of 325 mAh/g after 100 cycles at 0.1 A/g with a capacity retention of 91.2%. The important role of element doping sites on ion adsorption and ion storage performance is confirmed by theoretical investigations. Controlling the doping sites in MCSs provides a new approach to designing high-performance electrodes for energy storage and conversion applications., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

Materials derived from metal-organic frameworks (MOFs) have demonstrated exceptional structural variety and complexity and can be synthesized using low-cost scalable methods. Although the inherent instability and low electrical conductivity of MOFs are largely responsible for their low uptake for catalysis and energy storage, a superior alternative is MOF-derived metal-based derivatives (MDs) as these can retain the complex nanostructures of MOFs while exhibiting stability and electrical conductivities of several orders of magnitude higher. The present work comprehensively reviews MDs in terms of synthesis and their nanostructural design, including oxides, sulfides, phosphides, nitrides, carbides, transition metals, and other minor species. The focal point of the approach is the identification and rationalization of the design parameters that lead to the generation of optimal compositions, structures, nanostructures, and resultant performance parameters. The aim of this approach is to provide an inclusive platform for the strategies to design and process these materials for specific applications. This work is complemented by detailed figures that both summarize the design and processing approaches that have been reported and indicate potential trajectories for development. The work is also supported by comprehensive and up-to-date tabular coverage of the reported studies., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Li 7 La 3 Zr 2 O 12 (LLZO)-based solid-state Li batteries (SSLBs) have emerged as one of the most promising energy storage systems due to the potential advantages of solid-state electrolytes (SSEs), such as ionic conductivity, mechanical strength, chemical stability and electrochemical stability. However, there remain several scientific and technical obstacles that need to be tackled before they can be commercialised. The main issues include the degradation and deterioration of SSEs and electrode materials, ambiguity in the Li + migration routes in SSEs, and interface compatibility between SSEs and electrodes during the charging and discharging processes. Using conventional ex situ characterization techniques to unravel the reasons that lead to these adverse results often requires disassembly of the battery after operation. The sample may be contaminated during the disassembly process, resulting in changes in the material properties within the battery. In contrast, in situ / operando characterization techniques can capture dynamic information during cycling, enabling real-time monitoring of batteries. Therefore, in this review, we briefly illustrate the key challenges currently faced by LLZO-based SSLBs, review recent efforts to study LLZO-based SSLBs using various in situ / operando microscopy and spectroscopy techniques, and elaborate on the capabilities and limitations of these in situ / operando techniques. This review paper not only presents the current challenges but also outlines future developmental prospects for the practical implementation of LLZO-based SSLBs. By identifying and addressing the remaining challenges, this review aims to enhance the comprehensive understanding of LLZO-based SSLBs. Additionally, in situ / operando characterization techniques are highlighted as a promising avenue for future research. The findings presented here can serve as a reference for battery research and provide valuable insights for the development of different types of solid-state batteries.

Graphite is a widely used anode material in commercial lithium-ion batteries (LIBs), but its low theoretical specific capacity and extremely low redox potential limit its application in high-performance lithium-ion batteries. However, developing lithium-ion battery anode with high specific capacity and suitable working potential is still challenging. At present, conductive polymers with excellent properties and graphite-like structures are widely used in the field of electrochemistry, but their Li + storage mechanism and kinetics are still unclear and need to be further investigated. Therefore, we synthesized the conducting polymer Fe 3 (2, 3, 6, 7, 10, 11-hexahydroxytriphenylene) 2 (Fe-CAT) by the liquid phase method, in which the d-π conjugated structure and pores facilitate electron transfer and electrolyte infiltration, improving the comprehensive electrochemical performance. The Fe-CAT electrode displays a high capacity of 950 mA h g -1 at 200 mA g -1 . At the current density of 5.0 A g -1 , the electrode shows a reversible capacity of 322 mA h g -1 after 1000 cycles. The average lithiation voltage plateau is ∼ 0.79 V. The combination of ex-situ characterization techniques and electrochemical kinetic analysis reveals the source of the excellent electrochemical performance of Fe-CAT. During the charging/discharging process, the aromatic ring in the organic ligand is involved in the redox reaction. Such results will provide new insights for the design of next-generation high-performance electrode materials for LIBs., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Yanguo Liu reports financial support was provided by National Natural Science Foundation of China (52177208, 52171202, 51971055, 51871046). Yanguo Liu reports a relationship with National Natural Science Foundation of China that includes: funding grants. There are no conflicts to declare., (Copyright © 2022 Elsevier Inc. All rights reserved.)

Liquid phase transmission electron microscopy (TEM) provides a useful means to study a wide range of dynamics in solution with near-atomic spatial resolution and sub-microsecond temporal resolution. However, it is still a challenge to control the chemical environment (such as the flow of liquid, flow rate, and the liquid composition) in a liquid cell, and evaluate its effect on the various dynamic phenomena. In this work, we have systematically demonstrated the flow performance of an in situ liquid TEM system, which is based on 'on-chip flow' driven by external pressure pumps. We studied the effects of different chemical environments in the liquid cell as well as the electrochemical potential on the deposition and dissolution behavior of Cu crystals. The results show that uniform Cu deposition can be obtained at a higher liquid flow rate (1.38 μ l min -1 ), while at a lower liquid flow rate (0.1 μ l min -1 ), the growth of Cu dendrites was observed. Dendrite formation could be further promoted by in situ addition of foreign ions, such as phosphates. The generality of this technique was confirmed by studying Zn electrodeposition. Our direct observations not only provide new insights into understanding the nucleation and growth but also give guidelines for the design and synthesis of desired nanostructures for specific applications. Finally, the capability of controlling the chemical environment adds another dimension to the existing liquid phase TEM technique, extending the possibilities to study a wide range of dynamic phenomena in liquid media., (© 2022 IOP Publishing Ltd.)

Metal tellurides (MTs) have emerged as highly promising candidate anode materials for state-of-the-art lithium-ion batteries (LIBs) and sodium ion batteries (SIBs). This is owing to the unique crystal structure, high intrinsic conductivity, and high trap density of such materials. The present work delivers a detailed discussion on the latest research and progress associated with the use of MTs for LIBs/SIBs with a focus on reaction mechanisms, challenges, electrochemical performance, and synthesis strategies. Further, the prospects and future development of MT anode materials are discussed in terms of strategies to overcome the existing limitations. This review provides both an in-depth understanding of MTs and provides the driving force for expanding research on MTs for energy storage and conversion applications.

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 LaNiO 3 perovskite electrocatalysts. Hydrogen reduction of 700 °C calcined LaNiO 3 induces a high density of surface oxygen vacancies, and confers significantly enhanced OER activity and stability compared to unreduced LaNiO 3 ; 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 Ni 2+ /Ni 3+ 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 LaNiO 3 in accordance with the enhanced OER activity that is observed., (© 2021 Wiley-VCH GmbH.)

Oxide perovskites have emerged as an important class of materials with important applications in many technological areas, particularly thermocatalysis, electrocatalysis, photocatalysis, and energy storage. However, their implementation faces numerous challenges that are familiar to the chemist and materials scientist. The present work surveys the state-of-the-art by integrating these two viewpoints, focusing on the critical role that defect engineering plays in the design, fabrication, modification, and application of these materials. An extensive review of experimental and simulation studies of the synthesis and performance of oxide perovskites and devices containing these materials is coupled with exposition of the fundamental and applied aspects of defect equilibria. The aim of this approach is to elucidate how these issues can be integrated in order to shed light on the interpretation of the data and what trajectories are suggested by them. This critical examination has revealed a number of areas in which the review can provide a greater understanding. These include considerations of (1) the nature and formation of solid solutions, (2) site filling and stoichiometry, (3) the rationale for the design of defective oxide perovskites, and (4) the complex mechanisms of charge compensation and charge transfer. The review concludes with some proposed strategies to address the challenges in the future development of oxide perovskites and their applications.

The architectural design of nanocatalysts plays a critical role in the achievement of high densities of active sites but current technologies are hindered by process complexity and limited scaleability. The present work introduces a rapid, flexible, and template-free method to synthesize three-dimensional (3D), mesoporous, CeO 2-x nanostructures comprised of extremely thin holey two-dimensional (2D) nanosheets of centimetre-scale. The process leverages the controlled conversion of stacked nanosheets of a newly developed Ce-based coordination polymer into a range of stable oxide morphologies controllably differentiated by the oxidation kinetics. The resultant polycrystalline, hybrid, 2D-3D CeO 2-x exhibits high densities of defects and surface area as high as 251 m 2 g -1 , which yield an outstanding CO conversion performance (T 90% = 148 °C) for all oxides. Modification by the creation of heterojunction nanostructures using transition metal oxides (TMOs) results in further improvements in performance (T 90% = 88 °C), which are interpreted in terms of the active sites associated with the TMOs that are identified through structural analyses and density functional theory (DFT) simulations. This unparalleled catalytic performance for CO conversion is possible through the ultra-high surface areas, defect densities, and pore volumes. This technology offers the capacity to establish efficient pathways to engineer nanostructures of advanced functionalities for catalysis.

Aluminum trimesate-based MOF (MIL-96-(Al)) has attracted intense attention due to its high chemical stability and strong CO 2 adsorption capacity. In this study, CO 2 capture and selectivity of MIL-96-Al was further improved by the coordination of the second metal Ca. To this end, a series of MIL-96(Al)-Ca were hydrothermally synthesised by a one-pot method, varying the molar ratio of Ca 2+ /Al 3+ . It is shown that the variation of Ca 2+ /Al 3+ ratio results in significant changes in crystal shape and size. The shape varies from the hexagonal rods capped in the ends by a hexagonal pyramid in MIL-96(Al) without Ca to the thin hexagonal disks in MIL-96(Al)-Ca4 (the highest Ca content). Adsorption studies reveal that the CO 2 adsorption on MIL-96(Al)-Ca1 and MIL-96(Al)-Ca2 at pressures up to 950 kPa is vastly improved due to the enhanced pore volumes compared to MIL-96(Al). The CO 2 uptake on these materials measured in the above sequence is 10.22, 9.38 and 8.09 mmol g -1 , respectively. However, the CO 2 uptake reduces to 5.26 mmol g -1 on MIL-96(Al)-Ca4. Compared with MIL-96(Al)-Ca1, the N 2 adsorption in MIL-96(Al)-Ca4 is significantly reduced by 90% at similar operational conditions. At 100 and 28.8 kPa, the selectivity of MIL-96(Al)-Ca4 to CO 2 /N 2 reaches up to 67 and 841.42, respectively, which is equivalent to 5 and 26 times the selectivity of MIL-96(Al). The present findings highlight that MIL-96(Al) with second metal Ca coordination is a potential candidate as an alternative CO 2 adsorbent for practical applications., Competing Interests: The authors declare no conflict of interest., (This journal is © The Royal Society of Chemistry.)

A series of unsupported and supported vanadium phosphorus oxide catalysts were prepared by employing a new strategy, which significantly reduced the complexity of catalyst preparation. The greatly simplified catalyst fabrication benefits a greener and lower-cost process for practical applications. The currently fabricated systems showed ca. 90% target product(s) selectivity with a promising yield as well as catalyst durability.

Holey 2D metal oxides have shown great promise as functional materials for energy storage and catalysts. Despite impressive performance, their processing is challenged by the requirement of templates plus capping agents or high temperatures; these materials also exhibit excessive thicknesses and low yields. The present work reports a metal-based coordination polymer (MCP) strategy to synthesize polycrystalline, holey, metal oxide (MO) nanosheets with thicknesses as low as two-unit cells. The process involves rapid exfoliation of bulk-layered, MCPs (Ce-, Ti-, Zr-based) into atomically thin MCPs at room temperature, followed by transformation into holey 2D MOs upon the removal of organic linkers in aqueous solution. Further, this work represents an extra step for decorating the holey nanosheets using precursors of transition metals to engineer their band alignments, establishing a route to optimize their photocatalysis. The work introduces a simple, high-yield, room-temperature, and template-free approach to synthesize ultrathin holey nanosheets with high-level functionalities., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Pond water as surface water has certain environmental impacts on environmental media such as groundwater, lakes, atmosphere, and soil. Organic pollutants present in pond water may pose health risks to humans, but research on organic pollutants in pond water is rare. Here, taking pond water collected in rural areas of Hebei province as the sample, we analyzed and evaluated four categories of semi-volatile organic compounds (SVOCs), including 11 phenolic compounds, 7 aniline compounds, 16 parent polycyclic aromatic hydrocarbons (PAHs), 14 PAH derivatives, and 16 phthalate esters (PAEs). The results show that the 10 water samples contained 26.2-17034 ng/L of Σ phenols, 33.7-2612 ng/L of Σ anilines, 33.9-1651 ng/L of Σ PAHs, and 59.0-2800 ng/L of Σ PAEs. Furthermore, non-carcinogenic risk and carcinogenic risk caused by SVOCs through direct ingestion and dermal exposure were also assessed. The current levels of non-carcinogenic risks and carcinogenic risks through these two means of exposure are within acceptable limits, except for the site 1 and site 5 in Hebei province where a total cancer risk exceeds 10 -6 . It can be concluded that the pond water studied had a low risk of carcinogenicity to the human.

Despite the fact that its crystal state is thermodynamically stable, Cu 64 Zr 36 alloy is prone to form metastable glass at a high cooling rate. However, the confinement can induce nano-crystallization with a novel sandwich-like hierarchical structure consisting of pure Cu layers, pure Zr layers and mixed layers by conducting molecular dynamics simulations. The liquid-to-crystal transition temperature and interatomic repulsion softness display abnormal oscillations, instead of monotonous variation, as the wall-wall separation increases. When the confinement size is 10 Å and 12 Å, the transition temperature reaches a maximum, resulting from the pending new sandwich layer. The atomic movement and dynamical heterogeneity are demonstrated to play a vital role in the abnormal oscillation behavior of physical properties of the nano confined metallic glass. The sandwich-like structure can alter the Cu-Zr bond fraction, which eventually influences the liquid-to-crystal transition temperature and interatomic repulsion softness. Our findings provide a deep insight into the hierarchical nanostructures and its liquid-to-crystal transition characteristics under confinement at the atomic level.

A simple, practical and precise method for the simultaneous analysis of 32 different polycyclic aromatic hydrocarbon (PAHs) including 16 parent PAHs, 8 oxygenated-PAHs (oxy-PAHs), 4 chloro-PAHs, and 4 nitrogen-containing heterocyclic PACs (N-PACs), in groundwater was established via gas chromatography-mass spectrometry (GC-MS) combined with liquid-liquid extraction (LLE). The obtained detection method possesses instrument detection limits (at a signal to noise of 3:1) in the range of 0.05-10 ng/mL and method detection limits in the range of 1.7-13.2 ng/L. The average recoveries of the 32 analytes were in the range of 54.3%-127.0% with relative standard deviations (RSDs) < 20%, and the recoveries of 16 PAH derivatives ranged from 54.3 to 115.1% with RSDs < 17.9%. The method has been successfully applied to the screening of 64 groundwater samples from eastern China. The results revealed that 30 types of targets including 16 PAHs and 14 PAH derivatives were detected and that the groundwater in most areas is slightly polluted, while the pollution of Jiangsu Province and Shandong Province was more serious.

Quantum mechanics-based simulations have been undertaken to support the development and application of multi-functional nano-devices constructed from zigzag silicon carbide nanoribbons (zSiCNRs), boron phosphide (BP), nanoribbons (zBPNRs), and Pb-chalcogenide (PbS, PbSe) nanoribbons. We explore the effect of gate voltage on the electronic performance of the devices. Symmetric I - V characteristics, spin polarization properties, NDR effects, and high rectification ratios are observed among these devices. The effects of the angle, length and width of the constructed nanoribbon are also studied. The results show that the width of the nanoribbons can have a substantial influence on their electronic performance. These results provide a crucial simulation input to help guide the design of multi-functional nano-devices built from hybrid SiC-BP/PbS/PbSe nanostructures, and this research is essential for better understanding of their electronic transport properties., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Molecular dynamics (MD) simulation has been employed to study the wetting transitions of liquid gallium droplet on the graphene surfaces, which are decorated with three types of carbon nanopillars, and to explore the effect of the surface roughness and morphology on the wettability of liquid Ga. The simulation results showed that, at the beginning, the Ga film looks like an upside-down dish on the rough surface, different from that on the smooth graphene surface, and its size is crucial to the final state of liquid. Ga droplets exhibit a Cassie⁻Baxter (CB) state, a Wenzel state, a Mixed Wetting state, and a dewetting state on the patterned surfaces by changing distribution and the morphology of nanopillars. Top morphology of nanopillars has a direct impact on the wetting transition of liquid Ga. There are three transition states for the two types of carbon nanotube (CNT) substrates and two for the carbon nanocone (CNC) one. Furthermore, we have found that the substrates show high or low adhesion to the Ga droplet with the variation of their roughness and top morphology. With the roughness decreasing, the adhesion energy of the substrate decreases. With the same roughness, the CNC/graphene surface has the lowest adhesion energy, followed by CNT/graphene and capped CNT/graphene surfaces. Our findings provide not only valid support to previous works but also reveal new theories on the wetting model of the metal droplet on the rough substrates.

Mesoporous metals with high surface area hold promise for a variety of catalytic applications, especially for the reduction of CO 2 to value-added products. This study has used a novel mesoporous rhodium (Rh) nanoparticles, which were recently developed via a simple wet chemical reduction approach ( Nat. Commun. 2017, 8, 15581) as catalyst for CO 2 methanation. Highly efficient performance and selectivity for methane formation are achieved due to their controllable crystallinity, high porosity, high surface energy, and large number of atomic steps distributions. The mesoporous Rh nanoparticles, possessing the largest surface area (69 m 2 g -1 ), exhibit a substantially higher reaction rate (5.28 × 10 -5 mol CO 2 g Rh -1 s -1 ) than the nonporous Rh nanoparticles (1.28 × 10 -5 mol CO 2 g Rh -1 s -1 ). Our results indicate the extensive use of mesoporous metals in heterogeneous catalysis processes.

This feature article summarizes the recent progress in porous perovskite oxides as advanced catalysts for both energy conversion applications and various heterogeneous reactions. Recently, research has been focused on specifically designing porous perovskite materials so that large surface areas can be harnessed and surface properties can be improved. Numerous potential applications of porous perovskites have been investigated, including heterogeneous catalysis and air battery applications that rely on interactions and/or reactions of other components with porous perovskites. The main objective of this article is to examine the progress of recent research studies on porous perovskite nanomaterials, including the preparation methods and their applications in catalysis and batteries. The wide variety of the related knowledge on porous mixed oxides can provide guidance for researchers with interests ranging from the design of functionalized materials to the field of heterogeneous catalysis and electrochemical applications.

Unique CO 2 methanation catalysts comprising bimetallic Ni-Rh nanoalloy/3DOM LaAlO 3 have been successfully prepared via a poly(methyl methacrylate) microsphere colloidal crystal-templating route, followed by the in situ growth of Ni nanoparticles (NPs). Here, we show that unlike traditional Ni particles deposited on a perovskite support, the exsolution of Ni occurs on both the external and internal surface of the porous perovskite substrate, leading to a strong metal-support interaction. Owing to the exsolution of Ni and the formation of Ni-Rh nanoalloys, a 52% enhancement in the methanation turnover frequency was obtained over the Ni-Rh/3DOM LaAlO 3 [13.9 mol/(mol h)] compared to Rh/3DOM LaNi 0.08 Al 0.92 O 3 [9.16 mol/(mol h)] before reduction treatment. The results show that the low-temperature reducibility, rich surface adsorbed oxygen species, and basic sites of the catalyst greatly improve its activity toward CO 2 methanation. The hierarchically porous structure of the perovskite support provides a high dispersion of bimetallic Ni-Rh NPs.

A green, robust and eco-friendly procedure for the oxidation of aromatic organic sulfides to sulfones using H 2 O 2 catalyzed by NH 2 -coordinately immobilized tris(8-quinolinolato)iron onto the silica coated magnetite (Fe 3 SiO 6 ) has been developed. Physicochemical properties of the resulting nanoparticles were investigated by means of techniques including X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, vibrating sample magnetometer, atomic adsorption spectroscopy and FT-IR spectroscopy. The catalytic activity of sulfides oxidation showed that this atom-economical protocol provided great yields of various sulfones and allowed the sulfide function reaction conducting under the mild conditions thus to prevent the sulfide being over-oxidized to sulfoxides. The Fe 3 O 4 @SiO 2 -FeQ 3 catalysts are magnetically separable and kept stable after recycling for 7 consecutive runs without detectable activity loss., (Copyright © 2017 Elsevier Inc. All rights reserved.)

We report a scalable method to obtain a new material where large graphene sheets form webs linking carbon fibers. Film-fiber hybrid nonwoven mats are formed during fiber processing and converted to carbon structures after a simple thermal treatment. This contrasts with multistep methods that attempt to mix previously prepared graphene and fibers, or require complicated and costly processes for deposition of graphene over carbon fibers. The developed graphene-fiber hybrid structures have seamless connections between graphene and fibers, and in fact the graphene "veils" extend directly from one fiber into another forming a continuous surface. The graphene-fiber hybrid structures are produced in situ from aqueous poly(vinyl alcohol) solutions. The solutions were subjected to centrifugal spinning to produce fine nanofiber mats. The addition of salt to the polymer solution stimulated a capillarity effect that promoted the formation of thin veils, which become graphene sheets upon dehydration by sulfuric acid vapor followed by carbonization (at relatively low temperatures, below 800 °C). These veils extend over several micrometers within the pores of the fiber network, and consist of crystalline graphene layers that cross-link the fibers to form a highly interconnected hybrid network. The surface area and pore diameter of the hybrid structures were measured to be 521 m 2 g -1 and 10 nm, respectively. The resulting structure shows high electrical conductivity, 550 S/m, and promising shielding of electromagnetic interference, making it an attractive system for a broad range of electronic applications.

Versatile superstructures composed of nanoparticles have recently been prepared using various disassembly methods. However, little information is known on how the structural disassembly influences the catalytic performance of the materials. Here we show how the disassembly of an ordered porous La 0.6 Sr 0.4 MnO 3 perovskite array, to give hexapod mesostructured nanoparticles, exposes a new crystal facet which is more active for catalytic methane combustion. On fragmenting three-dimensionally ordered macroporous (3DOM) structures in a controlled manner, via a process that has been likened to retrosynthesis, hexapod-shaped building blocks can be harvested which possess a mesostructured architecture. The hexapod-shaped perovskite catalyst exhibits excellent low temperature methane oxidation activity (T 90% =438 °C; reaction rate=4.84 × 10 -7  mol m -2  s -1 ). First principle calculations suggest the fractures, which occur at weak joints within the 3DOM architecture, afford a large area of (001) surface that displays a reduced energy barrier for hydrogen abstraction, thereby facilitating methane oxidation.

To overcome deactivation of Pd-based catalysts at high temperatures, we herein design a novel pathway by introducing a certain amount of CoO to the supported Au-Pd alloy nanoparticles (NPs) to generate high-performance Au-Pd-xCoO/three-dimensionally ordered macroporous (3DOM) Co 3 O 4 (x is the Co/Pd molar ratio) catalysts. The doping of CoO induced the formation of PdO-CoO active sites, which was beneficial for the improvement in adsorption and activation of CH 4 and catalytic performance. The Au-Pd-0.40CoO/3DOM Co 3 O 4 sample performed the best (T 90% = 341 °C at a space velocity of 20 000 mL g -1 h -1 ). Deactivation of the 3DOM Co 3 O 4 -supported Au-Pd, Pd-CoO, and Au-Pd-xCoO nanocatalysts resulting from water vapor addition was due to the formation and accumulation of hydroxyl on the catalyst surface, whereas deactivation of the Pd-CoO/3DOM Co 3 O 4 catalyst at high temperatures (680-800 °C) might be due to decomposition of the PdO y active phase into aggregated Pd 0 NPs. The Au-Pd-xCoO/3DOM Co 3 O 4 nanocatalysts exhibited better thermal stability and water tolerance ability compared to the 3DOM Co 3 O 4 -supported Au-Pd and Pd-CoO nanocatalysts. We believe that the supported Au-Pd-xCoO nanomaterials are promising catalysts in practical applications for organic combustion.

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 (λ max = 635 nm, 0.7 mW cm(-2) ) and yellow (λ max = 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., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

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., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The development of drug delivery systems (DDSs) using near infrared (NIR) light and upconversion nanoparticles (UCNPs) has generated intensive interest over the past five years. These NIR-initiated DDSs not only offer a high degree of spatial and temporal determination of therapeutic release but also provide precise control over the released dosage. Furthermore, these nanoplatforms confer several advantages over conventional light-based DDSs-NIR offers better tissue penetration depth and a reduced risk of cellular photo-damage caused by exposure to light at high-energy wavelengths (e.g., ultraviolet light, <400 nm). The development of DDSs that can be activated by low intensity NIR illumination is highly desirable to avoid exposing living tissues to excessive heat that can limit the in vivo application of these DDSs. This encompasses research in three directions: (i) enhancing the quantum yield of the UCNPs; (ii) incorporation of photo-responsive materials with red-shifted absorptions into the UCNPs; and (iii) tuning the UCNPs excitation wavelength. This review focuses on recent advances in the development of NIR-initiated DDS, with emphasis on the use of photo-responsive compounds and polymeric materials conjugated onto UCNPs. The challenges that limit UCNPs clinical applications, alongside with the aforementioned techniques that have emerged to overcome these limitations, are highlighted.

Three-dimensional (3D) ordered mesoporous Ag/MnO2 catalyst was prepared by impregnation method based on 3D-MnO2 and used for catalytic oxidation of HCHO. Ag nanoparticles are uniformly distributed on the polycrystalline wall of 3D-MnO2. The addition of Ag does not change the 3D ordered mesoporous structure of the Ag/MnO2, but does reduce the pore size and surface area. Ag nanoparticles provide sufficient active site for the oxidation reaction of HCHO, and Ag (111) crystal facets in the Ag/MnO2 are active faces. The 8.9% Ag/MnO2 catalyst shows a higher normalized rate (10.1 nmol·s(-1)·m(-2) at 110 °C) and TOF (0.007 s(-1) at 110 °C) under 1300 ppm of HCHO and 150 000 h(-1) of GHSV, and its apparent activation energy of the reaction is the lowest (39.1 kJ/mol). More Ag active sites, higher low-temperature reducibility, more abundant surface lattice oxygen species, oxygen vacancies, and lattice defects generated from interaction Ag with MnO2 are responsible for the excellent catalytic performance of HCHO oxidation on the 8.9% Ag/MnO2 catalyst. The 8.9% Ag/MnO2 catalyst remained highly active and stable under space velocity increasing from 60 000 to 150 000 h(-1), under initial HCHO concentration increasing from 500 to 1300 ppm, and under the presence of humidity, respectively.

Newly designed 3D highly ordered macro/mesoporous multifunctional La1-xCexCoO3 nanohybrid frameworks with a 2D hexagonal mesostructure were fabricated via facile meso-molding in a three-dimensionally macroporous perovskite (MTMP) route. The nanohybrid framework exhibited excellent catalytic activity for methane combustion, which derived from the MTMP providing a larger surface area and pore volume, uniform pore sizes, higher accessible surface oxygen concentration, better low-temperature reducibility, and a unique nanovoid 3D structure.

Multicomponent nanoframes (NFs) with a hollow structural character have shown the potential to be applied in many fields. Here we report a novel strategy to synthesize Zn x Cd1-x S NFs via the synergistic actions of the graphene oxide (GO) confinement effect and oriented cation exchange. The obtained samples have been systematically characterized by x-ray diffractometry (XRD), field-emission scanning electron microscopy (SEM), transmission electron microscopy (TEM), x-ray photospectroscopy (XPS) and Raman spectrometry. The results show that the two dimensional space confinement effect induced by GO and the oriented cation exchange reaction are responsible for the formation of the multicomponent NFs. The high photoelectrochemical activity and the low cost of the starting materials will make the multicomponent NFs applicable in photoelectronic and photoelectrocatalytic fields.

Highly dispersed Pt nanoparticles supported on high-surface-area 3D ordered macroporous (3DOM) Ce0.6 Zr0.3 Y0.1 O2 (CZY) are synthesized via a bubbling cetyltrimethyl ammonium bromide/P123-assisted reduction route. The 1.1 wt% Pt/3DOM CZY catalyst shows supercatalytic activity for methane combustion, which is attributed to a higher oxygen adspecies amount, larger surface area, better low-temperature reducibility, and unique nanovoid-walled 3DOM structure., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A facile one-step solution reaction route for growth of novel MoS2 nanorose cross-linked by 3D rGO network, in which the MoS2 nanorose is constructed by single-layered or few-layered MoS2 nanosheets, is presented. Due to the 3D assembled hierarchical architecture of the ultrathin MoS2 nanosheets and the interconnection of 3D rGO network, as well as the synergetic effects of MoS2 and rGO, the as-prepared MoS2-NR/rGO nanohybrids delivered high specific capacity, excellent cycling and good rate performance when evaluated as an anode material for lithium-ion batteries. Moreover, the nanohybrids also show excellent hydrogen-evolution catalytic activity and durability in an acidic medium, which is superior to MoS2 nanorose and their nanoparticles counterparts.

Three-dimensionally ordered macroporous (3DOM) Mn2O3 and its supported gold (xAu/3DOM Mn2O3, x=1.9-7.5wt%) nanocatalysts were prepared using the polymethyl methacrylate-templating and polyvinyl alcohol-protected reduction methods, respectively. The 3DOM Mn2O3 and xAu/3DOM Mn2O3 samples exhibited a surface area of 34-38m(2)/g. The Au nanoparticles (NPs) with a size of 3.0-3.5nm were uniformly dispersed on the skeletons of 3DOM Mn2O3. The 5.8Au/3DOM Mn2O3 sample performed the best, giving the T90% (the temperature required for a conversion of 90%) of -15°C at space velocity (SV)=20,000mL/(gh) for CO oxidation and 244°C at SV=40,000mL/(gh) for toluene oxidation. The apparent activation energies (30 and 54kJ/mol) over 5.8Au/3DOM Mn2O3 were much lower than those (80 and 95kJ/mol) over 3DOM Mn2O3 for CO and toluene oxidation, respectively. The effects of SV, water vapor, CO2, and SO2 on catalytic activity were also examined. It is concluded that the excellent catalytic performance of 5.8Au/3DOM Mn2O3 was associated with its high oxygen adspecies concentration, good low-temperature reducibility, and strong interaction between Au NPs and 3DOM Mn2O3 as well as high-quality porous architecture., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Highly dispersed Ag nanoparticles supported on high-surface-area 3DOM La0.6Sr0.4MnO3 were successfully generated via the dimethoxytetraethylene glycol-assisted gas bubbling reduction route. The macroporous materials showed super catalytic performance for methane combustion.

A series of novel metal-oxide-supported CeO(2) catalysts were prepared via the wet impregnation method, and their NH(3)-SCR activities were investigated. The Ce/TiO(2)-SiO(2) catalyst with a Ti/Si mass ratio of 3/1 exhibited superior NH(3)-SCR activity and high N(2) selectivity in the temperature range of 250-450 °C. The characterization results revealed that the activity enhancement was correlated with the properties of the support material. Cerium was highly dispersed on the TiO(2)-SiO(2) binary metal oxide support, and the interaction of Ti and Si resulted in greater conversion of Ce(4+) to Ce(3+) on the surface of the catalyst compared to that on the single metal oxide supports. As a result of in the increased number of acid sites on Ce/TiO(2)-SiO(2) that resulted from the addition of SiO(2), the NH(3) adsorption capacity was significantly improved. All of these factors played significant roles in the high SCR activity. More importantly, Ce/TiO(2)-SiO(2) exhibited strong resistance to SO(2) and H(2)O poisoning. After the addition of SiO(2), the number of Lewis-acid sites was not decreased, but the number of Brønsted-acid sites on the TiO(2)-SiO(2) carrier was increased. The introduction of SiO(2) further weakened the alkalinity over the surface of the Ce/TiO(2)-SiO(2) catalyst, which resulted in sulfate not easily accumulating on the surface of the Ce/TiO(2)-SiO(2) catalyst in comparison with Ce/TiO(2).

Co(1-x)M(x)Cr(2)O(4) (M = Li, Zr; x = 0-0.2) catalysts were prepared via the citric acid method and investigated for catalytic combustion of methane. Substitution at tetrahedral (A) sites with monovalent (Li) or tetravalent (Zr) metal ions led to a decrease or increase of the catalytic activity, respectively. The Co(0.95)Zr(0.05)Cr(2)O(4) catalyst proved to be the most active and its catalytic activity reached 90% of methane conversion at 448 °C, which dropped by 66 °C compared with that of the undoped CoCr(2)O(4) catalyst. XRD and Raman results indicated that lithium or zirconium substitution could modify the spinel structure and electronic properties. For lithium-doped catalysts, oxygen deficiency and a strong surface enrichment in lithium and chromium were detected. Zirconium substitution enhanced the reducibility of zirconium-doped catalysts and decreased the strength constant of both the Co-O band and the Cr-O band, which may contribute to the catalytic activity toward methane combustion. In addition, the prevalent catalytic combustion activity of the zirconium-substituted catalysts could be explained by their higher concentration of suprafacial, weakly chemisorbed oxygen.