Highly Conjugated Graphitic Carbon Nitride Nanofoam for Photocatalytic Hydrogen Evolution.

As a metal-free photocatalyst, graphitic carbon nitride (g-CN) shows great potential for photocatalytic water splitting, although its performance is significantly limited by structural defects due to incomplete polymerization. In the present work, we successfully synthesize highly conjugated g-CN nanofoam through an iodide substitution technique. The product possesses a high polymerization degree, low defect density, and large specific surface area; as a result, it achieves a hydrogen evolution rate of 9.06 mmol h-1 g-1 under visible light irradiation, with an apparent quantum efficiency (AQE) of 18.9% at 420 nm. Experimental analysis and theoretical calculations demonstrate that the recombination of photogenerated carriers at C-NHx defects was effectively depressed in the nanofoam, giving rise to the high photocatalytic activity.

The influence of adjacent Al atoms on the hydrothermal stability of H-SSZ-13: a first-principles study.

The Al concentration and distribution have a great influence on the hydrothermal stability of the H-SSZ-13 zeolites in experiments. In this work, first-principles calculations are performed to clarify the decomposition mechanism of an H-SSZ-13 framework with adjacent Al atom pair distribution under hydrothermal conditions. It is found that the adjacent Al atoms have a tendency to occupy the para-sites of the 4-membered rings (4MRs) in the framework. Water molecules are chemisorbed onto the Al atom one by one, and the hydroxylation of the neighboring O atoms induces the breaking of the Al-O bonds, which causes the first dealumination in 4MRs. The other Al atom in the para-site can be easily removed from the framework once the first one is lost. The feasible subsequent dealumination of adjacent Al atoms would break the linker of 6MRs in the framework, which is responsible for the degraded hydrothermal stability. Moreover, the partial substitution of metal ions (such as Na+ and Cu+) for the protons in the framework will greatly stabilize the Al-O bonds and enlarge the energy barrier of para-site Al dealumination, which leads to the improved hydrothermal stability of H-SSZ-13.

Porous Cobalt-Nickel Hydroxide Nanosheets with Active Cobalt Ions for Overall Water Splitting.

Low-cost and high-performance catalysts are of great significance for electrochemical water splitting. Here, it is reported that a laser-synthesized catalyst, porous Co0.75 Ni0.25 (OH)2 nanosheets, is highly active for catalyzing overall water splitting. The porous nanosheets exhibit low overpotentials for hydrogen evolution reaction (95 mV@10 mA cm-2 ) and oxygen evolution reaction (235 mV@10 mA cm-2 ). As both anode and cathode catalysts, the porous nanosheets achieve a current density of 10 mA cm-2 at an external voltage of 1.56 V, which is much lower than that of commercial Ir/C-Pt/C couple (1.62 V). Experimental and theoretical investigations reveal that numerous Co3+ ions are generated on the pore wall of nanosheets, and the unique atomic structure around Co3+ ions leads to appropriate electronic structure and adsorption energy of intermediates, thus accelerating hydrogen and oxygen evolution.

Hierarchical Nanostructured WO3 with Biomimetic Proton Channels and Mixed Ionic-Electronic Conductivity for Electrochemical Energy Storage.

Protein channels in biologic systems can effectively transport ions such as proton (H(+)), sodium (Na(+)), and calcium (Ca(+)) ions. However, none of such channels is able to conduct electrons. Inspired by the biologic proton channels, we report a novel hierarchical nanostructured hydrous hexagonal WO3 (h-WO3) which can conduct both protons and electrons. This mixed protonic-electronic conductor (MPEC) can be synthesized by a facile single-step hydrothermal reaction at low temperature, which results in a three-dimensional nanostructure self-assembled from h-WO3 nanorods. Such a unique h-WO3 contains biomimetic proton channels where single-file water chains embedded within the electron-conducting matrix, which is critical for fast electrokinetics. The mixed conductivities, high redox capacitance, and structural robustness afford the h-WO3 with unprecedented electrochemical performance, including high capacitance, fast charge/discharge capability, and very long cycling life (>50,000 cycles without capacitance decay), thus providing a new platform for a broad range of applications.

Fine regulation of electron transfer in Ag@Co3O4 nanoparticles for boosting the oxygen evolution reaction.

In this study, a core-shell structure (Ag@Co3O4) was constructed to modify the valence state of cobalt cations precisely by continuously adjusting the shell thickness. There exists a volcano relationship between the valence state of Co sites and OER activity, and the lowest overpotential (212 mV@10 mA cm-2) has been obtained.

Multi-functional anodes boost the transient power and durability of proton exchange membrane fuel cells.

Proton exchange membrane fuel cells have been regarded as the most promising candidate for fuel cell vehicles and tools. Their broader adaption, however, has been impeded by cost and lifetime. By integrating a thin layer of tungsten oxide within the anode, which serves as a rapid-response hydrogen reservoir, oxygen scavenger, sensor for power demand, and regulator for hydrogen-disassociation reaction, we herein report proton exchange membrane fuel cells with significantly enhanced power performance for transient operation and low humidified conditions, as well as improved durability against adverse operating conditions. Meanwhile, the enhanced power performance minimizes the use of auxiliary energy-storage systems and reduces costs. Scale fabrication of such devices can be readily achieved based on the current fabrication techniques with negligible extra expense. This work provides proton exchange membrane fuel cells with enhanced power performance, improved durability, prolonged lifetime, and reduced cost for automotive and other applications.

Tuning the structure of bifunctional Pt/SmMn2O5 interfaces for promoted low-temperature CO oxidation activity.

The interfacial structure of metal-oxide composite catalysts plays a vital role in heterogeneous catalysis, which is crucial to the adsorption and activation of reactants. Herein, the interfacial effects of bare and Fe/Co/Ni doped SmMn2O5 mullite oxide supported Pt clusters on CO oxidation have been investigated by first-principles based microkinetics analysis. A robust formation of Pt/Mn2 trimer structures is demonstrated at the bifunctional interfaces irrespective of the Ptn cluster's size, which can provide spatially separated sites for CO adsorption and O2 dissociation. The binding strength of CO at the interfacial Pt sites is in the optimal range due to the charge transfer from Pt clusters to oxide, while the strong polarization of Mn2 dimers induced by Pt clusters with stable three-dimensional morphologies can lower the energy barrier of O2 dissociation. Based on the microkinetics analysis, the O2 dissociation is the rate-determining step in the full CO oxidation cycle, and the introduction of Mn-Fe hetero-dimers at the interface is predicted to further enhance the low temperature CO oxidation activity of Pt/SmMn2O5 catalysts.

High-quality mesoporous graphene particles as high-energy and fast-charging anodes for lithium-ion batteries.

The application of graphene for electrochemical energy storage has received tremendous attention; however, challenges remain in synthesis and other aspects. Here we report the synthesis of high-quality, nitrogen-doped, mesoporous graphene particles through chemical vapor deposition with magnesium-oxide particles as the catalyst and template. Such particles possess excellent structural and electrochemical stability, electronic and ionic conductivity, enabling their use as high-performance anodes with high reversible capacity, outstanding rate performance (e.g., 1,138 mA h g-1 at 0.2 C or 440 mA h g-1 at 60 C with a mass loading of 1 mg cm-2), and excellent cycling stability (e.g., >99% capacity retention for 500 cycles at 2 C with a mass loading of 1 mg cm-2). Interestingly, thick electrodes could be fabricated with high areal capacity and current density (e.g., 6.1 mA h cm-2 at 0.9 mA cm-2), providing an intriguing class of materials for lithium-ion batteries with high energy and power performance.

Iron-decorated nitrogen-rich carbons as efficient oxygen reduction electrocatalysts for Zn-air batteries.

A low-cost and scalable method has been developed to synthesize Fe-decorated N-rich carbon electrocatalysts for the oxygen reduction reaction (ORR) based on pyrolysis of metal carbonyls containing metal-organic frameworks (MOFs). Such a method simultaneously optimizes the Fe-related active sites and the porous structure of the catalysts. Accordingly, the best-performing Fe-NC-900-M catalyst shows excellent ORR activity with a half-wave potential of 0.91 V vs. RHE, exceeding that of the 40% Pt/C catalyst in alkaline media. Furthermore, the zinc-air batteries constructed with Fe-NC-900-M as the cathode catalyst exhibit high open-circuit voltage (1.5 V) and peak power density (271 mW cm-2), and outperform most zinc-air batteries with noble-metal free ORR catalysts.

Creating Lithium-Ion Electrolytes with Biomimetic Ionic Channels in Metal-Organic Frameworks.

Solid-state electrolytes are the key to the development of lithium-based batteries with dramatically improved energy density and safety. Inspired by ionic channels in biological systems, a novel class of pseudo solid-state electrolytes with biomimetic ionic channels is reported herein. This is achieved by complexing the anions of an electrolyte to the open metal sites of metal-organic frameworks (MOFs), which transforms the MOF scaffolds into ionic-channel analogs with lithium-ion conduction and low activation energy. This work suggests the emergence of a new class of pseudo solid-state lithium-ion conducting electrolytes.