Simultaneously Producing H2 and H2O2 by Photocatalytic Water Splitting: Recent Progress and Future.

The solar-driven overall water splitting (2H2O→2H2 + O2) is considered as one of the most promising strategies for reducing carbon emissions and meeting energy demands. However, due to the sluggish performance and high H2 cost, there is still a big gap for the current photocatalytic systems to meet the requirements for practical sustainable H2 production. Economic feasibility can be attained through simultaneously generating products of greater value than O2, such as hydrogen peroxide (H2O2, 2H2O→H2 + H2O2). Compared with overall water splitting, this approach is more kinetically feasible and generates more high-value products of H2 and H2O2. In several years, there has been an increasing surge in exploring the possibility and substantial progress has been achieved. In this review, a concise overview of the importance and underlying principles of PIWS is first provided. Next, the reported typical photocatalysts for PIWS are discussed, including commonly used semiconductors and cocatalysts, essential design features of these photocatalysts, and connections between their structures and activities, as well as the selected approaches for enhancing their stability. Then, the techniques used to quantify H2O2 and the operando characterization techniques that can be employed to gain a thorough understanding of the reaction mechanisms are summarized. Finally, the current existing challenges and the direction needing improvement are presented. This review aims to provide a thorough summary of the most recent research developments in PIWS and sets the stage for future advancements and discoveries in this emerging area.

Integrated Bismuth Oxide Ultrathin Nanosheets/Carbon Foam Electrode for Highly Selective and Energy-Efficient Electrocatalytic Conversion of CO2 to HCOOH.

Electroreduction of CO2 into formic acid (HCOOH) is of particular interest as a hydrogen carrier and chemical feedstock. However, its conversion is limited by a high overpotential and low stability due to undesirable catalysts and electrode design. Herein, an integrated 3D bismuth oxide ultrathin nanosheets/carbon foam electrode is designed by a sponge effect and N-atom anchor for energy-efficient and selective electrocatalytic conversion of CO2 to HCOOH for the first time. Benefitting from the unique 3D array foam architecture for highly efficient mass transfer, and optimized exposed active sites, as confirmed by density functional theory calculations, the integrated electrode achieves high electrocatalytic performance, including superior partial current density and faradaic efficiency (up to 94.1 %) at a moderate overpotential as well as a high energy conversion efficiency of 60.3 % and long-term durability.

Generating Defect-Rich Bismuth for Enhancing the Rate of Nitrogen Electroreduction to Ammonia.

The electrochemical N2 fixation, which is far from practical application in aqueous solution under ambient conditions, is extremely challenging and requires a rational design of electrocatalytic centers. We observed that bismuth (Bi) might be a promising candidate for this task because of its weak binding with H adatoms, which increases the selectivity and production rate. Furthermore, we successfully synthesized defect-rich Bi nanoplates as an efficient noble-metal-free N2 reduction electrocatalyst via a low-temperature plasma bombardment approach. When exclusively using 1 H NMR measurements with N2 gas as a quantitative testing method, the defect-rich Bi(110) nanoplates achieved a 15 NH3 production rate of 5.453 µg mgBi -1 h-1 and a Faradaic efficiency of 11.68 % at -0.6 V vs. RHE in aqueous solution at ambient conditions.

Recent Advances toward the Rational Design of Efficient Bifunctional Air Electrodes for Rechargeable Zn-Air Batteries.

Large-scale application of renewable energy and rapid development of electric vehicles have brought unprecedented demand for advanced energy-storage/conversion technologies and equipment. Rechargeable zinc (Zn)-air batteries represent one of the most promising candidates because of their high energy density, safety, environmental friendliness, and low cost. The air electrode plays a key role in managing the many complex physical and chemical processes occurring on it to achieve high performance of Zn-air batteries. Herein, recent advances of air electrodes from bifunctional catalysts to architectures are summarized, and their advantages and disadvantages are discussed to underline the importance of progress in the evolution of bifunctional air electrodes. Finally, some challenges and the direction of future research are provided for the optimized design of bifunctional air electrodes to achieve high performance of rechargeable Zn-air batteries.

A Biodegradable Polydopamine-Derived Electrode Material for High-Capacity and Long-Life Lithium-Ion and Sodium-Ion Batteries.

Polydopamine (PDA), which is biodegradable and is derived from naturally occurring products, can be employed as an electrode material, wherein controllable partial oxidization plays a key role in balancing the proportion of redox-active carbonyl groups and the structural stability and conductivity. Unexpectedly, the optimized PDA derivative endows lithium-ion batteries (LIBs) or sodium-ion batteries (SIBs) with superior electrochemical performances, including high capacities (1818 mAh g(-1) for LIBs and 500 mAh g(-1) for SIBs) and good stable cyclabilities (93 % capacity retention after 580 cycles for LIBs; 100 % capacity retention after 1024 cycles for SIBs), which are much better than those of their counterparts with conventional binders.

C and N Hybrid Coordination Derived Co-C-N Complex as a Highly Efficient Electrocatalyst for Hydrogen Evolution Reaction.

Development of an efficient hydrogen evolution reaction (HER) catalyst composed of earth-abundant elements is scientifically and technologically important for the water splitting associated with the conversion and storage of renewable energy. Herein we report a new class of Co-C-N complex bonded carbon (only 0.22 at% Co) for HER with a self-supported and three-dimensional porous structure that shows an unexpected catalytic activity with low overpotential (212 mV at 100 mA cm(-2)) and long-term stability, better than that of most traditional-metal catalysts. Experimental observations in combination with density functional theory calculations reveal that C and N hybrid coordination optimizes the charge distribution and enhances the electron transfer, which synergistically promotes the proton adsorption and reduction kinetics.

Photothermal Membrane Distillation toward Solar Water Production.

Freshwater production is one of the biggest global challenges today. Though desalination can provide a climate-independent source of clean water, the process requires a high energy consumption. Emerging advancement of photothermal nanomaterials and the urgent demand for a green technology transition have reinvigorated the established solar distillation technology. The current development of photothermal vaporization focuses on material innovation and interfacial heating, which largely emphasizes vapor generation efficiency, without considering pragmatic water collection. Moreover, salt accumulation is another critical issue of seawater solar-driven vaporization. The incorporation of photothermal materials into a photothermal membrane distillation (PMD) solar evaporator design harmoniously resolves these issues through combination of renewable energy and efficient interfacial distillation, to achieve the ultimate goal of practical saline water into freshwater conversion. At this juncture, it is imperative to review the recent opportunities and progresses of the PMD system. Here, the fundamental photothermal processes, strategies for efficient evaporator design, evaluation of various criteria for photothermal material incorporation with desired properties, discussions on desalination, water treatment, and energy generation applications are covered. Guidelines in material and system designs to further advance the PMD system that is highly promising in delivering portable water for both large-scale and decentralized systems are provided.

A Hybrid Solar Absorber-Electrocatalytic N-Doped Carbon/Alloy/Semiconductor Electrode for Localized Photothermic Electrocatalysis.

Converting and storing intermittent solar energy into stable chemical fuels of high efficiency depend crucially on harvesting excess energy beyond the conventional ultraviolet light spectrum. The means of applying highly efficient solar-thermal conversion on practical electricity-driven water splitting could be a significant stride toward this goal, while some bottlenecks remain unresolved. Herein, photothermic electrocatalytic oxygen and hydrogen evolution reactions are proposed, which bestow a distinctive exothermic activation and electrochemical reactivity in a reconstructed electrolyzer system, and which are poised for efficient renewable energy production. Attributed to the synergistic in situ coupling of the N-doped carbon, metallic alloy and oxides, in view of their broadband light absorption, high electrochemical surface area, and efficient charge transfer attributes, the hybrid photothermal electrocatalytic electrode simultaneously satisfies efficient photon-to-heat conversion and augmented electrochemical catalytic activity. Finally, a system level design of an appropriate photothermally mediated electrolytic cell with close-proximity light-illumination window along with a low-thermal-emittance electrolyte separator that preserve an overall large localized thermal gradient and efficient mass transport is devised. Such a photothermally mediated electrocatalytic system presented here may open up new avenues for the development of solar-thermal energy utilization in other forms.

Prevention of dendrite growth and volume expansion to give high-performance aprotic bimetallic Li-Na alloy-O2 batteries.

Rechargeable aprotic alkali metal (Li or Na)-O2 batteries are the subject of great interest because of their high theoretical specific energy. However, the growth of dendrites and cracks at the Li or Na anode, as well as their corrosive oxidation lead to poor cycling stability and safety issues. Understanding the mechanism and improving Li/Na-ion plating and stripping electrochemistry are therefore essential to realizing their technological potential. Here, we report how the use of a Li-Na alloy anode and an electrolyte additive realizes an aprotic bimetal Li-Na alloy-O2 battery with improved cycling stability. Electrochemical investigations show that stripping and plating of Li and Na and the robust and flexible passivation film formed in situ (by 1,3-dioxolane additive reacting with the Li-Na alloy) suppress dendrite and buffer alloy anode volume expansion and thus prevent cracking, avoiding electrolyte consumption and ensuring high electron transport efficiency and continued electrochemical reactions.

Amorphizing of Cu Nanoparticles toward Highly Efficient and Robust Electrocatalyst for CO2 Reduction to Liquid Fuels with High Faradaic Efficiencies.

Conversion of carbon dioxide (CO2 ) into valuable chemicals, especially liquid fuels, through electrochemical reduction driven by sustainable energy sources, is a promising way to get rid of dependence on fossil fuels, wherein developing of highly efficient catalyst is still of paramount importance. In this study, as a proof-of-concept experiment, first a facile while very effective protocol is proposed to synthesize amorphous Cu NPs. Unexpectedly, superior electrochemical performances, including high catalytic activity and selectivity of CO2 reduction to liquid fuels are achieved, that is, a total Faradaic efficiency of liquid fuels can sum up to the maximum value of 59% at -1.4 V, with formic acid (HCOOH) and ethanol (C2 H6 O) account for 37% and 22%, respectively, as well as a desirable long-term stability even up to 12 h. More importantly, this work opens a new avenue for improved electroreduction of CO2 based on amorphous metal catalysts.

Electrochemical Reduction of N2 under Ambient Conditions for Artificial N2 Fixation and Renewable Energy Storage Using N2 /NH3 Cycle.

Using tetrahexahedral gold nanorods as a heterogeneous electrocatalyst, an electrocatalytic N2 reduction reaction is shown to be possible at room temperature and atmospheric pressure, with a high Faradic efficiency up to 4.02% at -0.2 V vs reversible hydrogen electrode (1.648 µg h-1 cm-2 and 0.102 µg h-1 cm-2 for NH3 and N2 H4 ·H2 O, respectively).

Integrated Three-Dimensional Carbon Paper/Carbon Tubes/Cobalt-Sulfide Sheets as an Efficient Electrode for Overall Water Splitting.

The development of an efficient catalytic electrode toward both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is of great significance for overall water splitting associated with the conversion and storage of clean and renewable energy. In this study, carbon paper/carbon tubes/cobalt-sulfide is introduced as an integrated three-dimensional (3D) array electrode for cost-effective and energy-efficient HER and OER in alkaline medium. Impressively, this electrode displays superior performance compared to non-noble metal catalysts reported previously, benefiting from the unique 3D array architecture with increased exposure and accessibility of active sites, improved vectorial electron transport capability, and enhanced release of gaseous products. Such an integrated and versatile electrode makes the overall water splitting proceed in a more direct and smooth manner, reducing the production cost of practical technological devices.

Reactive Multifunctional Template-Induced Preparation of Fe-N-Doped Mesoporous Carbon Microspheres Towards Highly Efficient Electrocatalysts for Oxygen Reduction.

A novel in situ replication and polymerization strategy is developed for the synthesis of Fe-N-doped mesoporous carbon microspheres (Fe-NMCSs). This material benefits from the synergy between the high catalytic activity of Fe-N-C and the fast mass transport of the mesoporous microsphere structure. Compared to commercial Pt/C catalysts, the Fe-NMCSs show a much better electrocatalytic performance in terms of higher catalytic activity, selectivity, and durability for the oxygen reduction reaction.

Gelatin-derived sustainable carbon-based functional materials for energy conversion and storage with controllability of structure and component.

Nonprecious carbon catalysts and electrodes are vital components in energy conversion and storage systems. Despite recent progress, controllable synthesis of carbon functional materials is still a great challenge. We report a novel strategy to prepare simultaneously Fe-N-C catalysts and Fe3O4/N-doped carbon hybrids based on the sol-gel chemistry of gelatin and iron with controllability of structure and component. The catalysts demonstrate higher catalytic activity and better durability for oxygen reduction than precious Pt/C catalysts. The active sites of FeN4/C (D1) and N-FeN2+2/C (D3) are identified by Mössbauer spectroscopy, and most of the Fe ions are converted into D1 or D3 species. The oxygen reduction reaction (ORR) activity correlates well with the surface area, porosity, and the content of active Fe-N x /C (D1 + D3) species. As an anode material for lithium storage, Fe3O4/carbon hybrids exhibit superior rate capability and excellent cycling performance. The synthetic approach and the proposed mechanism open new avenues for the development of sustainable carbon-based functional materials.

[Ecological characteristics of preferred habitat of reindeer of Daxing'an Mountain forest area Northeast China in summer].

In July and August of 2012 and 2013, habitat selection and use patterns of reindeer were studied using both line and strip-transect surveys. Twenty-three habitat factors were measured and compared in known reindeer range areas in northwestern China. A total of 72 sampling sites were designated as being used by reindeer, and 162 sites were designated as unused control plots. The results indicated that, compared to the non-used habitat plots, reindeer selected summer habitats with higher values in altitude (26.9 ± 0.8 m), arbor canopy (17.9% ± 2.4%), arbor DBH (35.5 ± 2.1 cm), arbor height (8.2 ± 0.5 m), arbor density (6.9 ± 0.5 ind · 400 m(-2)) and stump quan- tity (1.3 ± 0.2 ind · 400 m(-2)), and with a lower shrub height (54.2 ± 2.0 cm). Moreover, reindeer also selected habitats at intermediate positions of intermediate slope gradient, which provided good water accessibility, more distance from human disturbance and herder influence, but bad concealment and lee condition. Results of the principal component analysis showed that the disturbance intensity (i. e. residential dispersion, anthropogenic-disturbance dispersion), arbor characteristics (arbor height and arbor density, arbor DBH and arbor canopy), geography characteristics (i. e. slope position, slope aspect and soil moisture), food abundance (ground-plant cover and shrub cover), openness (concealment and lee condition) and slope gradient were the most important factors influencing the habitat selection of reindeer in summer. In summary, the summer habitat selection of reindeer is a multidimensional process, through which reindeer adapt according to their ecological needs of food resources, safety and anti-predation. Furthermore, the pattern of habitat selection of reindeer showed that reindeer in China has not yet been domesticated, and reindeer populations and their core habitats should be conserved from intensive disturbance.

Nitrogen-doped porous carbon nanosheets as low-cost, high-performance anode material for sodium-ion batteries.

Between the sheets: Sodium-ion batteries are an attractive, low-cost alternative to lithium-ion batteries. Nitrogen-doped porous carbon sheets are prepared by chemical activation of polypyrrole-functionalized graphene sheets. When using the sheets as anode material in sodium-ion batteries, their unique compositional and structural features result in high reversible capacity, good cycling stability, and high rate capability.