Yunxiang Lin

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.

Atomic Iridium Incorporated in Cobalt Hydroxide for Efficient Oxygen Evolution Catalysis in Neutral Electrolyte

Developing highly efficient catalysts for oxygen evolution reaction (OER) in neutral media is extremely crucial for microbial electrolysis cells and electrochemical CO2 reduction. Herein, a facile one-step approach is developed to synthesize a new type of well-dispersed iridium (Ir) incorporated cobalt-based hydroxide nanosheets (nominated as CoIr) for OER. The Ir species as clusters and single atoms are incorporated into the defect-rich hydroxide nanosheets through the formation of rich Co-Ir species, as revealed by systematic synchrotron radiation based X-ray spectroscopic characterizations combining with high-angle annular dark-field scanning transmission electron microscopy measurement. The optimized CoIr with 9.7 wt% Ir content displays highly efficient OER catalytic performance with an overpotential of 373 mV to achieve the current density of 10 mA cm-2 in 1.0 m phosphate buffer solution, significantly outperforming the commercial IrO2 catalysts. Further characterizations toward the catalyst after undergoing OER process indicate that unique Co oxyhydroxide and high valence Ir species with low-coordination structure are formed due to the high oxidation potentials, which authentically contributes to superior OER performance. This work not only provides a state-of-the-art OER catalyst in neutral media but also unravels the root of the excellent performance based on efficient structural identifications.

Well‐Defined Cobalt Catalyst with N‐Doped Carbon Layers Enwrapping: The Correlation between Surface Atomic Structure and Electrocatalytic Property

Admittedly, the surface atomic structure of heterogenous catalysts toward the electrochemical oxygen reduction reaction (ORR) are accepted as the important features that can tune catalytic activity and even catalytic pathway. Herein, a surface engineering strategy to controllably synthesize a carbon-layer-wrapped cobalt-catalyst from 2D cobalt-based metal-organic frameworks is elaborately demonstrated. Combined with synchrotron radiation X-ray photoelectron spectroscopy, the soft X-ray absorption near-edge structure results confirmed that rich covalent interfacial CoNC bonds are efficiently formed between cobalt nanoparticles and wrapped carbon-layers during the polydopamine-assisted pyrolysis process. The X-ray absorption fine structure and corresponding extended X-ray absorption fine structure spectra further reveal that the wrapped cobalt with Co-N coordinations shows distinct surface distortion and atomic environmental change of Co-based active sites. In contrast to the control sample without coating layers, the 800 °C-annealed cobalt catalyst with N-doped carbon layers enwrapping achieves significantly enhanced ORR activity with onset and half-wave potentials of 0.923 and 0.816 V (vs reversible hydrogen electrode), highlighting the important correlation between surface atomic structure and catalytic property.

Active {010} facet-exposed Cu2MoS4 nanotube as high-efficiency photocatalyst

Rational design and facet-engineering of nanocrystal is an effective strategy to optimize the catalytic performance of abundant and economic semiconductor-based photocatalysts. In this study, we demonstrate a novel ternary Cu2MoS4 nanotube with the {010} facet exposed, synthesized via a hydrothermal method. Compared with two-dimensional Cu2MoS4 nanosheet with the {001} facet exposed, this one-dimensional nanotube exhibits highly enhanced performance of photodegradation and water splitting. Both theoretical calculations and experimental results suggest that the conduction band minimum (CBM) of the {010} facet crystal shows lower potential than that of the {001} facet. In particular, the up-shifted CBM in Cu2MoS4 nanotube is significantly beneficial for the absorption of dye molecules and reduction of H+ to H2. These results may open a new route for realizing high-efficiency photocatalysts based on Cu2MX4 by facet engineering.