Shuangming Chen

Oxide Defect Engineering Enables to Couple Solar Energy into Oxygen Activation

Modern development of chemical manufacturing requires a substantial reduction in energy consumption and catalyst cost. Sunlight-driven chemical transformation by metal oxides holds great promise for this goal; however, it remains a grand challenge to efficiently couple solar energy into many catalytic reactions. Here we report that defect engineering on oxide catalyst can serve as a versatile approach to bridge light harvesting with surface reactions by ensuring species chemisorption. The chemisorption not only spatially enables the transfer of photoexcited electrons to reaction species, but also alters the form of active species to lower the photon energy requirement for reactions. In a proof of concept, oxygen molecules are activated into superoxide radicals on defect-rich tungsten oxide through visible-near-infrared illumination to trigger organic aerobic couplings of amines to corresponding imines. The excellent efficiency and durability for such a highly important process in chemical transformation can otherwise be virtually impossible to attain by counterpart materials.

Strain Dynamics of Ultrathin VO2 Film Grown on TiO2 (001) and the Associated Phase Transition Modulation

Tuning the metal insulator transition (MIT) behavior of VO2 film through the interfacial strain is effective for practical applications. However, the mechanism for strain-modulated MIT is still under debate. Here we directly record the strain dynamics of ultrathin VO2 film on TiO2 substrate and reveal the intrinsic modulation process by means of synchrotron radiation and first-principles calculations. It is observed that the MIT process of the obtained VO2 films can be modulated continuously via the interfacial strain. The relationship between the phase transition temperature and the strain evolution is established from the initial film growth. From the interfacial strain dynamics and theoretical calculations, we claim that the electronic orbital occupancy is strongly affected by the interfacial strain, which changes also the electron-electron correlation and controls the phase transition temperature. These findings open the possibility of an active tuning of phase transition for the thin VO2 film through the interfacial lattice engineering.

Growth and phase transition characteristics of pure M-phase VO2 epitaxial film prepared by oxide molecular beam epitaxy

VO2 epitaxial film with large size has been prepared by oxide-molecular beam epitaxy method on Al2O3 (0001) substrate. The VO2 film shows a perfect crystal orientation, uniformity, and distinct metal-insulator phase transition (MIT) characteristics. It is observed that the MIT character is closely associated with the crystal defects such as oxygen vacancies. By controlling the growth condition, the MIT temperature can be tuned through modifying the content of oxygen vacancies. The role of the oxygen vacancies on the phase transition behavior of this VO2 film is discussed in the framework of the hybridization theory and the valence state of vanadium.

Isolation of Cu Atoms in Pd Lattice: Forming Highly Selective Sites for Photocatalytic Conversion of CO2 to CH4

Photocatalytic conversion of CO2 to CH4, a carbon-neutral fuel, represents an appealing approach to remedy the current energy and environmental crisis; however, it suffers from the large production of CO and H2 by side reactions. The design of catalytic sites for CO2 adsorption and activation holds the key to address this grand challenge. In this Article, we develop highly selective sites for photocatalytic conversion of CO2 to CH4 by isolating Cu atoms in Pd lattice. According to our synchrotron-radiation characterizations and theoretical simulations, the isolation of Cu atoms in Pd lattice can play dual roles in the enhancement of CO2-to-CH4 conversion: (1) providing the paired Cu-Pd sites for the enhanced CO2 adsorption and the suppressed H2 evolution; and (2) elevating the d-band center of Cu sites for the improved CO2 activation. As a result, the Pd7Cu1-TiO2 photocatalyst achieves the high selectivity of 96% for CH4 production with a rate of 19.6 μmol gcat-1 h-1. This work provides fresh insights into the catalytic site design for selective photocatalytic CO2 conversion, and highlights the importance of catalyst lattice engineering at atomic precision to catalytic performance.

Amorphous nickel-cobalt complexes hybridized with 1T-phase molybdenum disulfide via hydrazine-induced phase transformation for water splitting

Highly active and robust eletcrocatalysts based on earth-abundant elements are desirable to generate hydrogen and oxygen as fuels from water sustainably to replace noble metal materials. Here we report an approach to synthesize porous hybrid nanostructures combining amorphous nickel-cobalt complexes with 1T phase molybdenum disulfide (MoS2) via hydrazine-induced phase transformation for water splitting. The hybrid nanostructures exhibit overpotentials of 70 mV for hydrogen evolution and 235 mV for oxygen evolution at 10 mA cm−2 with long-term stability, which have superior kinetics for hydrogen- and oxygen-evolution with Tafel slope values of 38.1 and 45.7 mV dec−1. Moreover, we achieve 10 mA cm−2 at a low voltage of 1.44 V for 48 h in basic media for overall water splitting. We propose that such performance is likely due to the complete transformation of MoS2 to metallic 1T phase, high porosity and stabilization effect of nickel-cobalt complexes on 1T phase MoS2.

Amorphous Metallic NiFeP: A Conductive Bulk Material Achieving High Activity for Oxygen Evolution Reaction in Both Alkaline and Acidic Media

The intrinsic catalytic activity at 10 mA cm-2 for oxygen evolution reaction (OER) is currently working out at overpotentials higher than 320 mV. A highly efficient electrocatalyst should possess both active sites and high conductivity; however, the loading of powder catalysts on electrodes may often suffer from the large resistance between catalysts and current collectors. This work reports a class of bulk amorphous NiFeP materials with metallic bonds from the viewpoint of electrode design. The materials reported here perfectly combine high macroscopic conductivity with surface active sites, and can be directly used as the electrodes with active sites toward high OER activity in both alkaline and acidic electrolytes. Specifically, a low overpotential of 219 mV is achieved at the geometric current density 10 mA cm-2 in an alkaline electrolyte, with the Tafel slope of 32 mV dec-1 and intrinsic overpotential of 280 mV. Meanwhile, an overpotential of 540 mV at 10 mA cm-2 is attained in an acidic electrolyte and stable for over 30 h, which is the best OER performance in both alkaline and acidic media. This work provides a different angle for the design of high-performance OER electrocatalysts and facilitates the device applications of electrocatalysts.

Control of the Metal-Insulator Transition in VO2 Epitaxial Film by Modifying Carrier Density

External controlling the phase transition behavior of vanadium dioxide is important to realize its practical applications as energy-efficient electronic devices. Because of its relatively high phase transition temperature of 68 °C, the central challenge for VO2-based electronics, lies in finding an energy efficient way, to modulate the phase transition in a reversible and reproducible manner. In this work, we report an experimental realization of p-n heterojunctions by growing VO2 film on p-type GaN substrate. By adding the bias voltage on the p-n junction, the metal-insulator transition behavior of VO2 film can be changed continuously. It is demonstrated that the phase transition of VO2 film is closely associated with the carrier distribution within the space charge region, which can be directly controlled by the bias voltage. Our findings offer novel opportunities for modulating the phase transition of VO2 film in a reversible way as well as extending the concept of electric-field modulation on other phase transition materials.

In situ Integration of a Metallic 1T-MoS2/CdS Heterostructure as a Means to Promote Visible-Light-Driven Photocatalytic Hydrogen Evolution

The replacement of expensive noble‐metals cocatalysts with inexpensive, earth‐abundant, metallic nonmetal materials in most semiconductor‐based photocatalytic systems is highly desirable. Herein, we report the fabrication of stable 1T‐MoS2 slabs in situ grown on CdS nanorods (namely, 1T‐MoS2@CdS) by using a solvothermal method. As demonstrated by ultrafast transient absorption spectroscopy, in combination with steady‐state and time‐resolved photoluminescence, the synergistic effects resulting from formation of the intimate nanojunction between the interfaces and effective electron transport in the metallic phase of 1T‐MoS2 largely contribute to boosting the photocatalytic activity of CdS. Notably, the heterostructure with an optimum loading of 0.2 wt % 1T‐MoS2 exhibits an almost 39‐fold enhancement in the photocatalytic activity relative to that exhibited by bare CdS. This work represents a step towards the in situ realization of a 1T‐phase MoS2‐based heterostructure as a promising cocatalyst with high performance and low cost.

Electronic Structure Reconfiguration toward Pyrite NiS2 via Engineered Heteroatom Defect Boosting Overall Water Splitting

Developing highly active and low-cost heterogeneous catalysts toward overall electrochemical water splitting is extremely desirable but still a challenge. Herein, we report pyrite NiS2 nanosheets doped with vanadium heteroatoms as bifunctional electrode materials for both hydrogen- and oxygen-evolution reaction (HER and OER). Notably, the electronic structure reconfiguration of pyrite NiS2 is observed from typical semiconductive characteristics to metallic characteristics by engineering vanadium (V) displacement defect, which is confirmed by both experimental temperature-dependent resistivity and theoretical density functional theory calculations. Furthermore, elaborate X-ray absorption spectroscopy measurements reveal that electronic structure reconfiguration of NiS2 is rooted in electron transfer from doped V to Ni sites, consequently enabling Ni sites to gain more electrons. The metallic V-doped NiS2 nanosheets exhibit extraordinary electrocatalytic performance with overpotentials of about 290 mV for OER and about 110 mV for HER at 10 mA cm-2 with long-term stability in 1 M KOH solutions, representing one of the best non-noble-metal bifunctional electrocatalysts to date. This work provides insights into electronic structure engineering from well-designed atomic defect metal sulfide.

Hydriding Pd cocatalysts: An approach to giant enhancement on photocatalytic CO2 reduction into CH4

Photocatalytic reduction of CO2 into high value-added CH4 is a promising solution for energy and environmental crises. Integrating semiconductors with cocatalysts can improve the activities for photocatalytic CO2 reduction; however, most metal cocatalysts mainly produce CO and H2. Herein, we report a cocatalyst hydridation approach for significantly enhancing the photocatalytic reduction of CO2 into CH4. Hydriding Pd cocatalysts into PdH0.43 played a dual role in performance enhancement. As revealed by our isotopic labeling experiments, the PdH0.43 hydride cocatalysts reduced H2 evolution, which suppressed the H2 production and facilitated the conversion of the CO intermediate into the final product: CH4. Meanwhile, hydridation promoted the electron trapping on the cocatalysts, improving the charge separation. This approach increased the photocatalytic selectivity in CH4 production from 3.2% to 63.6% on Pd{100} and from 15.6% to 73.4% on Pd{111}. The results provide insights into photocatalytic mechanism studies and introduce new opportunities for designing materials towards photocatalytic CO2 conversion.