Junkai He

The viability of photocatalysis for air purification.

Photocatalytic oxidation (PCO) air purification technology is reviewed based on the decades of research conducted by the United Technologies Research Center (UTRC) and their external colleagues. UTRC conducted basic research on the reaction rates of various volatile organic compounds (VOCs). The knowledge gained allowed validation of 1D and 3D prototype reactor models that guided further purifier development. Colleagues worldwide validated purifier prototypes in simulated realistic indoor environments. Prototype products were deployed in office environments both in the United States and France. As a result of these validation studies, it was discovered that both catalyst lifetime and byproduct formation are barriers to implementing this technology. Research is ongoing at the University of Connecticut that is applicable to extending catalyst lifetime, increasing catalyst efficiency and extending activation wavelength from the ultraviolet to the visible wavelengths. It is critical that catalyst lifetime is extended to realize cost effective implementation of PCO air purification.

Mesoporous Iron Sulfide for Highly Efficient Electrocatalytic Hydrogen Evolution

We report a facile synthetic protocol to prepare mesoporous FeS2 without the aid of hard template as an electrocatalyst for the hydrogen evolution reaction (HER). The mesoporous FeS2 materials with high surface area were successfully prepared by a sol-gel method following a sulfurization treatment in an H2S atmosphere. A remarkable HER catalytic performance was achieved with a low overpotential of 96 mV at a current density of 10 mA·cm-2 and a Tafel slope of 78 mV per decade under alkaline conditions (pH 13). The theoretical calculations indicate that the excellent catalytic activity of mesoporous FeS2 is attributed to the exposed (210) facets. The mesoporous FeS2 material might be a promising alternative to the Pt-based electrocatalysts for water splitting.

Highly Conductive In-SnO2/RGO Nano-Heterostructures with Improved Lithium-Ion Battery Performance.

The increasing demand of emerging technologies for high energy density electrochemical storage has led many researchers to look for alternative anode materials to graphite. The most promising conversion and alloying materials do not yet possess acceptable cycle life or rate capability. In this work, we use tin oxide, SnO2, as a representative anode material to explore the influence of graphene incorporation and In-doping to increase the electronic conductivity and concomitantly improve capacity retention and cycle life. It was found that the incorporation of In into SnO2 reduces the charge transfer resistance during cycling, prolonging life. It is also hypothesized that the increased conductivity allows the tin oxide conversion and alloying reactions to both be reversible, leading to very high capacity near 1200 mAh/g. Finally, the electrodes show excellent rate capability with a capacity of over 200 mAh/g at 10C.

High-rate and long-life of Li-ion batteries using reduced graphene oxide/Co3O4 as anode materials

Metal oxides as Li-ion battery anodes have received a great deal of attention because they offer a higher specific capacity than state-of-the-art commercial graphite. However, a large volume change and severe particle aggregation during battery operation have greatly impeded their practical application. Herein, we report a facile one-step microwave-assisted route for growing Co3O4 nanoparticles on reduced graphene oxide that results in a high performance anode material for Li-ion batteries. The lithium battery performances of several systems with varied reduced graphene oxide contents were studied. The optimized composites exhibit a high surface area of 222 m2 g−1, and a wide pore size distribution of 1.4 to 300 nm. More importantly, the Li-ion battery shows a high capacity of ∼1300 mA h g−1 at a high rate of 1C (1C = 890 mA g−1), long life of over 600 cycles, good capacity retention, and excellent rate capability. The synthesis process is simple, energy efficient, and time-saving, providing a new path in designing high-performance electrodes for Li-ion batteries.

Hierarchical Mesoporous NiO/MnO2@PANI Core–Shell Microspheres, Highly Efficient and Stable Bifunctional Electrocatalysts for Oxygen Evolution and Reduction Reactions

We report on the new facile synthesis of mesoporous NiO/MnO2 in one step by modifying inverse micelle templated UCT (University of Connecticut) methods. The catalyst shows excellent electrocatalytic activity and stability for both the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR) in alkaline media after further coating with polyaniline (PANI). For electrochemical performance, the optimized catalyst exhibits a potential gap, ΔE, of 0.75 V to achieve a current of 10 mA cm-2 for the OER and -3 mA cm-2 for the ORR in 0.1 M KOH solution. Extensive characterization methods were applied to investigate the structure-property of the catalyst for correlations with activity (e.g., XRD, BET, SEM, HRTEM, FIB-TEM, XPS, TGA, and Raman). The high electrocatalytic activity of the catalyst closely relates to the good electrical conductivity of PANI, accessible mesoporous structure, high surface area, as well as the synergistic effect of the specific core-shell structure. This work opens a new avenue for the rational design of core-shell structure catalysts for energy conversion and storage applications.

Copper manganese oxide enhanced nanoarray-based monolithic catalysts for hydrocarbon oxidation

Copper manganese oxide (CuMn2O4) was introduced into the nanoarray-based monolithic catalysts system for advanced exhaust after-treatment. Through scalable and cost-effective hydrothermal reactions, nanosheet layers of copper manganese oxide were uniformly coated onto the manganese oxide nanoarrays (HM-PCR), which were grown on the cordierite honeycomb monoliths. The core nanoarray support, HM-PCR, a well-defined array architecture for active material deposition, contributed to an increase of open surface area and thus enhanced catalytic oxidation performance. The CuMn2O4 coated nanoarray-based catalyst, NA-CuMn2O4, shows efficient 90% propane (C3H8) conversion at around 400 °C, which is 50 °C and 75 °C lower than CuMn2O4 wash-coated catalyst (WC-CuMn2O4) and Pd loaded catalyst (WC-Pd), respectively. Compared to monolithic catalysts with a traditional alumina support, the benefit of nanoarray morphology was demonstrated by correlating the variation of surface area to the reactivity. The incorporation of cobalt ions was found to increase the specific surface area and thus enhance C3H8 conversion of CuMn2O4. The CuMn2O4/MnO2 nanoarray-based monoliths are promising types of emission control devices.

Mesoporous cobalt/manganese oxide: a highly selective bifunctional catalyst for amine–imine transformations

Herein, we discuss a heterogeneous catalytic protocol using cobalt doped mesoporous manganese oxide for amine–alcohol cross-coupling to selectively produce symmetric or asymmetric imines. Thorough investigations on the surface chemistry and physical properties of the material revealed its outstanding oxidation–reduction properties and reaction mechanism which was supported by quantum mechanical calculations done by using density functional theory (DFT).

Enhanced Catalytic Properties of Molybdenum Promoted Mesoporous Cobalt Oxide: Structure-Surface-Dependent Activity for Selective Synthesis of 2-Substituted Benzimidazoles

High‐valent molybdenum ions were substituted into the cobalt oxide lattice through a one step, sol‐gel method and investigated for selective synthesis of 2‐substituted benzimidazoles. Catalyst synthesis involves surfactant assisted soft templating inverse micelle method, which forms mesopores by interconnected intraparticle voids. Substitutional doping of Mo6+ resulted in materials with modified structural, morphological, surface, and redox properties. The catalytic activity increased with Mo concentration until an optimum amount (3 % Mo incorporation). Modified material shows lattice expansion, increased surface oxygen vacancies, and high surface area, which are responsible for the higher catalytic activity in selective benzimidazole synthesis reaction. A strong correlation between surface properties of the catalyst and the product selectivity was observed and plausible mechanistic and kinetic data are proposed and collected, respectively.

Partial Oxidation of Methane to Synthesis Gas Using Supported Ga‐Containing Bimetallic Catalysts and a Ti‐Promoter

A series of bimetallic Ga‐containing materials using TiO2 and TiO2‐promoted SiO2 supports have been prepared. Rhodium, palladium, and platinum have been used as additional metals in this system. The materials are characterized and used as catalysts for the partial oxidation of methane into synthesis gas (H2 and CO). The presence of a low quantity of titanium in the form of anatase TiO2 was shown to improve the overall activity of catalytic methane oxidation and to strongly increase the selectivity of partial oxidation products over the total oxidation of methane to carbon dioxide and water. Particular attention is paid to the formation of gallium‐metal alloys on the surface of the catalyst supports. Rh‐Ga‐Ti‐SiO2 was found to be the most active and selective catalyst, giving 89 % conversion of methane and 99 % selectivity to synthesis gas at 750 °C, as well as exhibiting catalytic activity and preferential conversion to partial oxidation products at temperatures as low as 350 °C.