Sung-Fu Hung

Identification of catalytic sites for oxygen reduction and oxygen evolution in N-doped graphene materials: Development of highly efficient metal-free bifunctional electrocatalyst.

Doping of graphene with nitrogen imparted bifunctional electrocatalytic activities for efficient energy conversion and storage. Oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are critical to renewable energy conversion and storage technologies. Heteroatom-doped carbon nanomaterials have been reported to be efficient metal-free electrocatalysts for ORR in fuel cells for energy conversion, as well as ORR and OER in metal-air batteries for energy storage. We reported that metal-free three-dimensional (3D) graphene nanoribbon networks (N-GRW) doped with nitrogen exhibited superb bifunctional electrocatalytic activities for both ORR and OER, with an excellent stability in alkaline electrolytes (for example, KOH). For the first time, it was experimentally demonstrated that the electron-donating quaternary N sites were responsible for ORR, whereas the electron-withdrawing pyridinic N moieties in N-GRW served as active sites for OER. The unique 3D nanoarchitecture provided a high density of the ORR and OER active sites and facilitated the electrolyte and electron transports. As a result, the as-prepared N-GRW holds great potential as a low-cost, highly efficient air cathode in rechargeable metal-air batteries. Rechargeable zinc-air batteries with the N-GRW air electrode in a two-electrode configuration exhibited an open-circuit voltage of 1.46 V, a specific capacity of 873 mAh g−1, and a peak power density of 65 mW cm−2, which could be continuously charged and discharged with an excellent cycling stability. Our work should open up new avenues for the development of various carbon-based metal-free bifunctional electrocatalysts of practical significance.

In Operando Identification of Geometrical-Site-Dependent Water Oxidation Activity of Spinel Co3O4.

Spinel Co3O4, comprising two types of cobalt ions: one Co(2+) in the tetrahedral site (Co(2+)(Td)) and the other two Co(3+) in the octahedral site (Co(3+)(Oh)), has been widely explored as a promising oxygen evolution reaction (OER) catalyst for water electrolysis. However, the roles of two geometrical cobalt ions toward the OER have remained elusive. Here, we investigated the geometrical-site-dependent OER activity of Co3O4 catalyst by substituting Co(2+)(Td) and Co(3+)(Oh) with inactive Zn(2+) and Al(3+), respectively. Following a thorough in operando analysis by electrochemical impedance spectroscopy and X-ray absorption spectroscopy, it was revealed that Co(2+)Td site is responsible for the formation of cobalt oxyhydroxide (CoOOH), which acted as the active site for water oxidation.

Metal-cluster-decorated TiO2 nanotube arrays : a composite heterostructure toward versatile photocatalytic and photoelectrochemical applications

Recent years have witnessed increasing interest in the solution-phase synthesis of atomically precise thiolate-protected gold clusters (Aux ); nonetheless, research on the photocatalytic properties of Aux -semiconductor nanocomposites is still in its infancy. In this work, recently developed glutathione-capped gold clusters and highly ordered nanoporous layer-covered TiO2 nanotube arrays (NP-TNTAs) are employed as nanobuilding blocks for the construction of a well-defined Aux /NP-TNTA heterostructure via a facile electrostatic self-assembly strategy. Versatile photocatalytic performances of the Aux /NP-TNTA heterostructure which acts as a model catalyst, including photocatalytic oxidation of organic pollutant, photocatalytic reduction of aromatic nitro compounds and photoelectrochemical (PEC) water splitting under simulated solar light irradiation, are systematically exploited. It is found that synergistic interaction stemming from monodisperse coverage of Aux clusters on NP-TNTAs in combination with hierarchical nanostructure of NP-TNTAs reinforce light absorption of Aux /NP-TNTA heterostructure especially within visible region, hence contributing to the significantly enhanced photocatalytic and PEC water splitting performances. Moreover, photocatalytic and PEC mechanisms over Aux /NP-TNTA heterostructure are elucidated and corresponding reaction models were presented. It is anticipated that this work could boost new insight for photocatalytic properties of metal-cluster-sensitized semiconductor nanocomposites.

One-dimensional hybrid nanostructures for heterogeneous photocatalysis and photoelectrocatalysis

Semiconductor-based photocatalysis and photoelectrocatalysis have received considerable attention as alternative approaches for solar energy harvesting and storage. The photocatalytic or photoelectrocatalytic performance of a semiconductor is closely related to the design of the semiconductor at the nanoscale. Among various nanostructures, one-dimensional (1D) nanostructured photocatalysts and photoelectrodes have attracted increasing interest owing to their unique optical, structural, and electronic advantages. In this article, a comprehensive review of the current research efforts towards the development of 1D semiconductor nanomaterials for heterogeneous photocatalysis and photoelectrocatalysis is provided and, in particular, a discussion of how to overcome the challenges for achieving full potential of 1D nanostructures is presented. It is anticipated that this review will afford enriched information on the rational exploration of the structural and electronic properties of 1D semiconductor nanostructures for achieving more efficient 1D nanostructure-based photocatalysts and photoelectrodes for high-efficiency solar energy conversion.

Heterojunction of Zinc Blende/Wurtzite in Zn1-xCdxS Solid Solution for Efficient Solar Hydrogen Generation: X-ray Absorption/Diffraction Approaches.

In the past decade, inorganic semiconductors have been successfully demonstrated as light absorbers in efficient solar water splitting to generate chemical fuels. Pseudobinary semiconductors Zn1-xCdxS (0≤x≤1) have exhibited a superior photocatalytic reactivity of H2 production from splitting of water by artificial solar irradiation without any metal catalysts. However, most studies had revealed that the extremely high efficiency with an optimal content of Zn1-xCdxS solid solution was determined as a result of elevating the conduction band minimum (CBM) and the width of bandgap. In addition to corresponding band structure and bandgap, the local crystal structure should be taken into account as well to determine its photocatalytic performance. Herein, we demonstrated the correlations between the photocatalytic activity and structural properties that were first studied through synchrotron X-ray diffraction and X-ray absorption spectroscopy. The crystal structure transformed from zinc blende to coexisted phases of major zinc blende and minor wurtzite phases at a critical point. The heterojunction formed by coexistence of zinc blende and wurtzite phases in the Zn1-xCdxS solid solution can significantly improve the separation and migration of photoinduced electron-hole pairs. Besides, X-ray absorption spectra and UV-vis spectra revealed that the bandgap of the Zn0.45Cd0.55S sample extended into the region of visible light because of the incorporation of Cd element in the sample. These results provided a significant progress toward the realization of the photoelectrochemical mechanism in heterojunction between zinc blende and wurtzite phases, which can effectively separate the charge-carriers and further suppress their recombination to enhance the photocatalytic reactivity.

Light-Induced In Situ Transformation of Metal Clusters to Metal Nanocrystals for Photocatalysis.

In situ transformation of glutathione-capped gold (Aux) clusters to gold (Au) nanocrystals under simulated solar light irradiation was achieved and utilized as a facile synthetic approach to rationally fabricate Aux/Au/TiO2 ternary and Au/TiO2 binary heterostructures. Synergistic interaction of Aux clusters and Au nanocrystals contributes to enhanced visible-light-driven photocatalysis.

In situ morphological transformation and investigation of electrocatalytic properties of cobalt oxide nanostructures toward oxygen evolution

Morphologies of cobalt oxide nanostructures were tuned from nano-needles to nano-blanket, micro-plates, and nano-sheets by introducing nickel ions, copper ions, and zinc ions into the precursor solution. This structural transformation was able to generate several specific nanostructures with high surface area, which led to an enhanced performance toward the oxygen-evolution reaction.

An Earth-Abundant Catalyst-Based Seawater Photoelectrolysis System with 17.9% Solar-to-Hydrogen Efficiency

The implementation of water splitting systems, powered by sustainable energy resources, appears to be an attractive strategy for producing high-purity H2 in the absence of the release of carbon dioxide (CO2 ). However, the high cost, impractical operating conditions, and unsatisfactory efficiency and stability of conventional methods restrain their large-scale development. Seawater covers 70% of the Earths surface and is one of the most abundant natural resources on the planet. New research is looking into the possibility of using seawater to produce hydrogen through electrolysis and will provide remarkable insight into sustainable H2 production, if successful. Here, guided by density functional theory (DFT) calculations to predict the selectivity of gas-evolving catalysts, a seawater-splitting device equipped with affordable state-of-the-art electrocatalysts composed of earth-abundant elements (Fe, Co, Ni, and Mo) is demonstrated. This device shows excellent durability and specific selectivity toward the oxygen evolution reaction in seawater with near 100% Faradaic efficiency for the production of H2 and O2 . Powered by a single commercial III-V triple-junction photovoltaic cell, the integrated system achieves spontaneous and efficient generation of high-purity H2 and O2 from seawater at neutral pH with a remarkable 17.9% solar-to-hydrogen efficiency.