Efficient Bifunctional Photoelectric Integrated Cathode for Solar Energy Conversion and Storage.

The integrated photoelectric battery serves as a compact and energy-efficient form for direct conversion and storage of solar energy compared to the traditional isolated PV-battery systems. However, combining efficient light harvesting and electrochemical energy storage into a single material is a great challenge. Here, a bifunctional lead phytate-cesium lead bromide (PbPA-CsPbBr3) cathode is explored for the solid-state batteries in terms of CsPbBr3 in situ grown on the PbPA framework. Specifically, CsPbBr3 nanocrystals generate electron-hole pairs under sunlight, the holes contribute to the lithium desorption of the discharged PbPA, and the electrons participate in the formation of the cathode interfacial film through oxygen reduction. The obtained solid-state photoelectric lithium-metal battery achieved a photoconversion efficiency of 0.72%, outperforming other systems under the same lighting conditions. The reasonable cathode design and its application in integrated solid-state batteries provide an efficient way for solar energy utilization.

Enhanced oxygen evolution over dual corner-shared cobalt tetrahedra.

Developing efficient catalysts is of paramount importance to oxygen evolution, a sluggish anodic reaction that provides essential electrons and protons for various electrochemical processes, such as hydrogen generation. Here, we report that the oxygen evolution reaction (OER) can be efficiently catalyzed by cobalt tetrahedra, which are stabilized over the surface of a Swedenborgite-type YBCo4O7 material. We reveal that the surface of YBaCo4O7 possesses strong resilience towards structural amorphization during OER, which originates from its distinctive structural evolution toward electrochemical oxidation. The bulk of YBaCo4O7 composes of corner-sharing only CoO4 tetrahedra, which can flexibly alter their positions to accommodate the insertion of interstitial oxygen ions and mediate the stress during the electrochemical oxidation. The density functional theory calculations demonstrate that the OER is efficiently catalyzed by a binuclear active site of dual corner-shared cobalt tetrahedra, which have a coordination number switching between 3 and 4 during the reaction. We expect that the reported active structural motif of dual corner-shared cobalt tetrahedra in this study could enable further development of compounds for catalyzing the OER.

K0.36(H2O) y WS2: a new layered compound for reversible hydrated potassium ion intercalation in aqueous electrolyte.

This work reports the synthesis of a new quasi two-dimensional layered compound, K0.36(H2O) y WS2, for aqueous potassium ion storage. Its crystal structure determined by single crystal X-ray diffraction is composed of WS2 layers and disordered hydrated K+ stacking along the c direction alternately. Due to the large interlayer spacing and high conductivity, K0.36(H2O) y WS2 is demonstrated to be a stable host for reversible intercalation and de-intercalation of hydrated K+ in K2SO4 aqueous solution.

Catalytic Intermediates of CO2 Hydrogenation on Cu(111) Probed by In Operando Near-Ambient Pressure Technique.

The in operando monitoring of catalytic intermediates is crucial for understanding the reaction mechanism and for optimizing the reaction conditions to improve the efficiency of the catalytic protocol; however, until now, this has remained a daunting challenge. Herein, we investigated the interaction of CO2 and H2 with the Cu(111) surface in a CO2 hydrogenation model system by using the in operando technique of near-ambient pressure X-ray photoelectron spectroscopy, which is further assisted by ultraviolet photoemission spectroscopy and low-energy electron diffraction (LEED) measurements. These techniques allowed the direct observation of CO2 dissociation into CO+O on the Cu(111) surface and the adsorption of O on the surface at room temperature. The intermediate HCOO- was unambiguously detected in the CO2 +H2 environment, which corroborated the formate pathway for methanol formation on the Cu(111) surface. We further found that O coverage can prevent the build up of graphitic carbon on the Cu surface. By taking advantage of the competitive interplay between Cu-O and graphitic carbon, we have proposed a feasible strategy for inhibition of the formation of graphitic carbon by tuning the CO2 and H2 partial pressures, which may contribute to sustaining the active Cu catalyst under the reaction conditions.

Unraveling Charge State of Supported Au Single-Atoms during CO Oxidation.

Thermally stable Au single-atoms supported by monolayered CuO grown at Cu(110) have been successfully prepared. The charge transfer from the CuO support to single Au atoms is confirmed to play a key role in tuning the activity for CO oxidation. Initially, the negatively charged Au single-atom is active for CO oxidation with its adjacent lattice O atom depleted to generate an O vacancy in the CuO monolayer. Afterward, the Au single-atom is neutralized, preventing further CO reaction. The produced O vacancy can be healed by exposure to O2 at 400 K and accordingly the reaction activity is restored.

Growth of Quasi-Free-Standing Single-Layer Blue Phosphorus on Tellurium Monolayer Functionalized Au(111).

Blue phosphorus, a newly proposed allotrope of phosphorus, represents a promising 2D material with predicted large tunable band gap and high charge-carrier mobility. Here, we report a simple method for the growth of quasi-free-standing single layer blue phosphorus on tellurium functionalized Au(111) by using black phosphorus as the precursor. In situ low-temperature scanning tunneling microscopy (LT-STM) measurements were used to monitor the growth of the single-layer blue phosphorus, which forms triangular structures arranged hexagonally on the tellurium layer. As revealed by in situ X-ray photoelectron spectroscopy, LT-STM measurements, and density functional theory calculation, the blue phosphorus layer weakly interacts with the underlying tellurium layer.

Probing the effect of the Pt-Ni-Pt(111) bimetallic surface electronic structures on the ammonia decomposition reaction.

We report a detailed investigation of elementary catalytic decomposition of ammonia on the Pt-Ni-Pt(111) bimetallic surface using in situ near ambient pressure X-ray photoelectron spectroscopy. Under the near ambient pressure (0.6 mbar) reaction conditions, a different dehydrogenation pathway with a reduced activation energy barrier for recombinative nitrogen desorption on the Pt-Ni-Pt(111) bimetallic surface is observed. The unique surface catalytic activity is correlated with the downward shift of the Pt 5d band states induced by the Ni subsurface atoms via charge redistribution of the topmost Pt layer. Our results provide a practical understanding of the unique chemistry of bimetallic catalysts for facile ammonia decomposition under realistic reaction conditions.

Reversible Tuning of Interfacial and Intramolecular Charge Transfer in Individual MnPc Molecules.

The reversible selective hydrogenation and dehydrogenation of individual manganese phthalocyanine (MnPc) molecules has been investigated using photoelectron spectroscopy (PES), low-temperature scanning tunneling microscopy (LT-STM), synchrotron-based near edge X-ray absorption fine structure (NEXAFS) measurements, and supported by density functional theory (DFT) calculations. It is shown conclusively that interfacial and intramolecular charge transfer arises during the hydrogenation process. The electronic energetics upon hydrogenation is identified, enabling a greater understanding of interfacial and intramolecular charge transportation in the field of single-molecule electronics.

Synthesis of hierarchical porous δ-MnO2 nanoboxes as an efficient catalyst for rechargeable Li-O2 batteries.

A rechargeable lithium-oxygen (Li-O2) battery with a remarkably high theoretical energy storage capacity has attracted enormous research attention. However, the poor oxygen reduction and oxygen evolution reaction (ORR and OER) activities in discharge and charge processes cause low energy efficiency, poor electrolyte stability and short cycle life. This requires the development of efficient cathode catalysts to dramatically improve the Li-O2 battery performances. MnO2-based materials are recognized as efficient and low-cost catalysts for a Li-O2 battery cathode. Here, we report a controllable approach to synthesize hierarchical porous δ-MnO2 nanoboxes by using Prussian blue analogues as the precursors. The obtained products possess hierarchical pore size and an extremely large surface area (249.3 m(2) g(-1)), which would favour oxygen transportation and provide more catalytically active sites to promote ORR and OER as the Li-O2 battery cathode. The battery shows enhanced discharge capacity (4368 mA h g(-1)@0.08 mA cm(-2)), reduced overpotential (270 mV), improved rate performance and excellent cycle stability (248 cycles@500 mA h g(-1) and 112 cycles@1000 mA h g(-1)), in comparison with the battery with a VX-72 carbon cathode. The superb performance of the hierarchical porous δ-MnO2 nanoboxes, together with a convenient fabrication method, presents an alternative to develop advanced cathode catalysts for the Li-O2 battery.

Synthesis of Au-SiO2 asymmetric clusters and their application in ZnO nanosheet-based dye-sensitized solar cells.

A facile and novel process modified from the Stöber method has been developed to prepare Au-SiO2 asymmetric clusters with a number of Au nanoparticles off-center. The Au-SiO2 asymmetric clusters exhibit the wanted surface plasmons along with increases in the plasmonic near field and optical extinction efficiency. They are incorporated into dye-sensitized solar cells (DSSCs) consisting of ZnO nanosheets as the photoanode, where the surface plasmonic effect on DSSCs performance arising from the Au-SiO2 asymmetric clusters is investigated. An enhancement in both the photocurrent and overall energy conversion efficiency is observed, arising from the improvement in light harvesting.