Jingfu He

Vacancy-Induced Ferromagnetism of MoS2 Nanosheets

Outstanding magnetic properties are highly desired for two-dimensional ultrathin semiconductor nanosheets. Here, we propose a phase incorporation strategy to induce robust room-temperature ferromagnetism in a nonmagnetic MoS2 semiconductor. A two-step hydrothermal method was used to intentionally introduce sulfur vacancies in a 2H-MoS2 ultrathin nanosheet host, which prompts the transformation of the surrounding 2H-MoS2 local lattice into a trigonal (1T-MoS2) phase. 25% 1T-MoS2 phase incorporation in 2H-MoS2 nanosheets can enhance the electron carrier concentration by an order, introduce a Mo(4+) 4d energy state within the bandgap, and create a robust intrinsic ferromagnetic response of 0.25 μB/Mo by the exchange interactions between sulfur vacancy and the Mo(4+) 4d bandgap state at room temperature. This design opens up new possibility for effective manipulation of exchange interactions in two-dimensional nanostructures.

CoOOH Nanosheets with High Mass Activity for Water Oxidation.

Endowing transition-metal oxide electrocatalysts with high water oxidation activity is greatly desired for production of clean and sustainable chemical fuels. Here, we present an atomically thin cobalt oxyhydroxide (γ-CoOOH) nanosheet as an efficient electrocatalyst for water oxidation. The 1.4 nm thick γ-CoOOH nanosheet electrocatalyst can effectively oxidize water with extraordinarily large mass activities of 66.6 A g(-1), 20 times higher than that of γ-CoOOH bulk and 2.4 times higher than that of the benchmarking IrO2 electrocatalyst. Experimental characterizations and first-principles calculations provide solid evidence to the half-metallic nature of the as-prepared nanosheets with local structure distortion of the surface CoO(6-x) octahedron. This greatly enhances the electrophilicity of H2O and facilitates the interfacial electron transfer between Co ions and adsorbed -OOH species to form O2, resulting in the high electrocatalytic activity of layered CoOOH for water oxidation.

Aligned Fe2TiO5-containing nanotube arrays with low onset potential for visible-light water oxidation

There remains a pressing challenge in the efficient utilization of visible light in the photoelectrochemical applications of water splitting. Here, we design and fabricate pseudobrookite Fe2TiO5 ultrathin layers grown on vertically aligned TiO2 nanotube arrays that can enhance the conduction and utilization of photogenerated charge carriers. Our photoanodes are characterized by low onset potentials of ~0.2 V, high photon-to-current efficiencies of 40-50% under 400-600 nm irradiation and total energy conversion efficiencies of ~2.7%. The high performance of Fe2TiO5 nanotube arrays can be attributed to the anisotropic charge carrier transportation and elongated charge carrier diffusion length (compared with those of conventional TiO2 or Fe2O3 photoanodes) based on electrochemical impedance analysis and first-principles calculations. The Fe2TiO5 nanotube arrays may open up more opportunities in the design of efficient and low-cost photoanodes working in visible light for photoelectrochemical applications.

Curing BiVO4 Photoanodes with Ultraviolet Light Enhances Photoelectrocatalysis

Exposure of BiVO4 photoanodes to ultraviolet (UV) radiation for extended time periods (e.g., 20 h) produces a morphological change and concomitant improvement in photo-electrocatalytic (PEC) efficiency for driving water splitting directly by sunlight. The ∼230 mV cathodic shift in onset potential and doubling of the photocurrent at 1.23 V vs. RHE after UV curing are comparable to the effects engendered by the presence of a secondary catalyst layer. PEC measurements and absorption spectra indicate that the cathodic shift after UV curing corresponds to a suppression of charge recombination and a greater photovoltage generation caused by the shift of the flat-band potential, and not an improvement in electrocatalytic activity or light absorption. Spectroscopic surface analysis suggests that surface defect sites, which are eliminated by UV curing, for the differences in observed charge recombination.

High-Throughput Synthesis of Mixed-Metal Electrocatalysts for CO2 Reduction

The utilization of CO2 as a feedstock requires fundamental breakthroughs in catalyst design. The efficiencies and activities of pure metal electrodes towards the CO2 reduction reaction are established, but the corresponding data on mixed-metal systems are not as well developed. In this study we show that the near-infrared driven decomposition (NIRDD) of solution-deposited films of metal salts and subsequent electrochemical reduction offers the unique opportunity to form an array of mixed-metal electrocatalyst coatings with excellent control of the metal stoichiometries. This synthetic method enabled us to develop an empirical structure-property correlation to help inform the development of optimized CO2 catalyst compositions.

Cu and Co codoping effects on room-temperature ferromagnetism of (Co,Cu):ZnO dilute magnetic semiconductors

Homogeneous distribution of magnetic dopants in semiconductor hosts is highly desired for practical applications in spintronics. Herein, we show that codoping 2 at. % Cu with Zn0.98Co0.02O could change the magnetic behavior from paramagnetism to room temperature ferromagnetism. For Zn0.96Cu0.02Co0.02O nanocrystals prepared by a modified solid-state reaction method, the combination of x-ray absorption fine structure spectra at Co, Cu, and O K-edge reveals that the Cu and Co ions are substitutionally incorporated into the ZnO matrix and distribute randomly in the host. First-principles calculations further indicate strong hybridization between Co 3d states and Cu-induced donor impurity bands at the Fermi level, which effectively enhances the indirect ferromagnetic superexchange of Co ions and is responsible for the occurrence of ferromagnetism in (Co,Cu)-codoped ZnO.

Realizing Ferromagnetic Coupling in Diluted Magnetic Semiconductor Quantum Dots

Manipulating the ferromagnetic interactions in diluted magnetic semiconductor quantum dots (DMSQDs) is a central theme to the development of next-generation spin-based information technologies, but this remains a great challenge because of the intrinsic antiferromagnetic coupling between impurity ions therein. Here, we propose an effective approach capable of activating ferromagnetic exchange in ZnO-based DMSQDs, by virtue of a core/shell structure that engineers the energy level of the magnetic impurity 3d levels relative to the band edge. This idea has been successfully applied to Zn(0.96)Co(0.04)O DMSQDs covered by a shell of ZnS or Ag2S. First-principles calculations further indicate that covering a ZnS shell around the Co-doped ZnO core drives a transition of antiferromagnetic-to-ferromagnetic interaction, which occurs within an effective depth of 1.2 nm underneath the surface in the core. This design opens up new possibility for effective manipulation of exchange interactions in doped oxide nanostructures for future spintronics applications.

Mediating distribution of magnetic Co ions by Cr-codoping in (Co,Cr): ZnO thin films

The control over the distribution of magnetic ions in a host is crucial for the functionality of magnetically doped semiconductors. Herein, (Co,Cr)-codoped ZnO shows a possibility of Cr-codoping engineering in mediating the distribution of magnetic Co ions via manipulating the charge state of the Co ions. The x-ray absorption fine structure analyses at Co K-edge indicate that a secondary phase of metallic Co clusters is formed in the Zn0.92Co0.08O film. However, Cr-codoping suppresses the formation of Co clusters, so that all doped Co ions occupy the substitutional sites in ZnO. The ability of Cr in mediating Co distribution, as revealed by first-principles calculations, arises from the strong hybridization between the Co 3d states and the donor band induced by substitutional Cr ions, which facilitates the charge transfer from the donor band to the Co 3d states, changes the charge state of Co ions and modifies the electrostatic interactions among Co ions.

Exposure of WO3 Photoanodes to Ultraviolet Light Enhances Photoelectrochemical Water Oxidation

Exposure of WO3 photoanodes to sustained irradiation by ultraviolet (UV) light induces a morphology change that enhances the photoelectrochemical (PEC) activity towards the oxygen evolution reaction (OER). A 30% enhancement in photocurrent density at 1.23 V vs RHE was measured despite a nominal change in onset potential. A structural and electrochemical analysis of the films before and after exposure to UV irradiation indicates that a higher film porosity and correspondingly higher specific surface area is responsible for the enhancement in PEC activity. The effect of prolonged UV irradiation on the WO3 films is fundamentally different to that which was previously observed for BiVO4 films.

Electrocatalytic Alloys for CO2 Reduction

Electrochemically reducing CO2 using renewable energy is a contemporary global challenge that will only be met with electrocatalysts capable of efficiently converting CO2 into fuels and chemicals with high selectivity. Although many different metals and morphologies have been tested for CO2 electrocatalysis over the last several decades, relatively limited attention has been committed to the study of alloys for this application. Alloying is a promising method to tailor the geometric and electric environments of active sites. The parameter space for discovering new alloys for CO2 electrocatalysis is particularly large because of the myriad products that can be formed during CO2 reduction. In this Minireview, mixed-metal electrocatalyst compositions that have been evaluated for CO2 reduction are summarized. A distillation of the structure-property relationships gleaned from this survey are intended to help in the construction of guidelines for discovering new classes of alloys for the CO2 reduction reaction.