Combined Analyses on Electronic Structure and Molecular Orbitals of d¹⁰ Bimetal Oxide In₂Ge₂O₇ and Photocatalytic Performances for Overall Water Splitting and CO₂ Reduction

Semiconducting photocatalytic overall water splitting and CO2 reduction are possible solutions to the emerging worldwide challenges of oil shortage and continual temperature increase, and the key is to develop an efficient photocatalyst. Most photocatalysts contain the d0, d10 or d10ns2 metals, and a guiding principle is desired to help to distinguish outstanding semiconductors. Here, the d10 bimetal oxide In2Ge2O7 was selected as the target. First, density functional theory (DFT) calculations point out that the nonbonding O 2p orbitals dominate the valence band maximum (VBM), and In 5s-O 2s and Ge 4s-O 2s antibonding orbitals are the major components of conduction band minimum (CBM). Moreover, the molecular orbitals were analyzed to consolidate the DFT calculations and make it more understandable for chemists. Due to the very small specific surface area (0.51 m2/g) and wide band gap (4.14 eV), as-prepared In2Ge2O7 did not exhibit any overall water splitting activity; nevertheless, when loading with 1 wt% cocatalyst (i.e., Pt, Pd), the surficial charge recombination can be greatly eliminated and the overall water splitting activity is significantly improved to 33.0(4) and 17.2(7) μmol/h for H2 and O2 generation, respectively. The apparent quantum yield (AQY) at 254 nm is 8.28%. This observation is proof that the inherent electronic structure of In2Ge2O7 is beneficial for the charge migration in bulk. Moreover, this catalyst also exhibits an observable CO2 reduction activity in pure water, which is a competition reaction with water splitting, anyway, the CH4 selectivity can be enhanced by loading Pd. This is a successful attempt to unravel the structure–property relationship by combining the analyses on electronic structure and molecular orbitals and is enlightening to further discover good candidates to photocatalysts

From Lewis Acid to Lewis Base by La³⁺-to‑Y³⁺ Substitution in α‑YB₅O₉: Local Structure Modification Induced Lewis Basicity

Different from the common perspective of average structure, we propose that the locally elongated metal–oxygen bonds induced by La3+-to-Y3+ substitution to a Lewis acid α-YB5O9 generate medium-strength basic sites. Experimentally, NH3- and CO2-TPD experiments prove that the La3+ doping of α-Y1–xLaxB5O9 (0 ≤ x ≤ 0.24) results in the emergence of new medium-strength basic sites and the increasing La3+ concentration modifies the number, not the strength, of the acidic and basic sites. The catalytic IPA conversion exhibits a reversal of the product selectivity, i.e., from 93% of propylene for α-YB5O9 to ∼90% of acetone for α-Y0.76La0.24B5O9, which means the La3+ doping gradually turns the solid from a Lewis acid to a Lewis base. Besides, α-Y0.76RE0.24B5O9 (RE = Ce, Eu, Gd, Tm) compounds were prepared to consolidate the above conjecture, where the acetone selectivity exhibits a linear dependence on the ionic radius (or electronegativity). This work suggests that the substitution-induced local structure change deserves more attention

From Lewis Acid to Lewis Base by La³⁺-to‑Y³⁺ Substitution in α‑YB₅O₉: Local Structure Modification Induced Lewis Basicity

Different from the common perspective of average structure, we propose that the locally elongated metal–oxygen bonds induced by La3+-to-Y3+ substitution to a Lewis acid α-YB5O9 generate medium-strength basic sites. Experimentally, NH3- and CO2-TPD experiments prove that the La3+ doping of α-Y1–xLaxB5O9 (0 ≤ x ≤ 0.24) results in the emergence of new medium-strength basic sites and the increasing La3+ concentration modifies the number, not the strength, of the acidic and basic sites. The catalytic IPA conversion exhibits a reversal of the product selectivity, i.e., from 93% of propylene for α-YB5O9 to ∼90% of acetone for α-Y0.76La0.24B5O9, which means the La3+ doping gradually turns the solid from a Lewis acid to a Lewis base. Besides, α-Y0.76RE0.24B5O9 (RE = Ce, Eu, Gd, Tm) compounds were prepared to consolidate the above conjecture, where the acetone selectivity exhibits a linear dependence on the ionic radius (or electronegativity). This work suggests that the substitution-induced local structure change deserves more attention

First-Principles Calculations on Narrow-Band Gap d¹⁰ Metal Oxides for Photocatalytic H₂ Production: Role of Unusual In²⁺ Cations in Band Engineering

The d10 metal oxides with low effective mass and high mobility of photoexcited electrons have received much attention in photocatalytic water splitting. However, there are still challenges in practical application due to insufficient visible light absorption. Here, an unusual phenomenon of the In2+ cation in PtIn6(GeO4)2O and PtIn6(Ga/InO4)2 with a narrow band gap is systematically investigated using density functional theory calculations. According to chemical bond analysis, the final band edge structure results from the interaction between the empty In-5p orbitals and the occupied antibonding state of the In 5s–O 2p orbitals as well as the further hybridization of adjacent In cations in PtIn6 octahedrons. The unique bonding characteristic of In2+ cations endows them with a narrow band gap and visible light response ability. Moreover, the occupied antibonding state could weaken the strength of the In–O covalent bond and strengthen the orbital hybridization of the In–In bond, causing the conduction band minimum to be located in the electroactive In6 cavity. This work reveals the origin of the narrow band gap of PtIn6(GeO4)2O and PtIn6(Ga/InO4)2 in view of bond theory and shows that they are promising semiconductors for the application of photocatalytic H2 generation

Transformation-Optics-Designed Plasmonic Singularities for Efficient Photocatalytic Hydrogen Evolution at Metal/Semiconductor Interfaces

Inspired by transformation optics, we propose a new concept for plasmonic photocatalysis by creating a novel hybrid nanostructure with a plasmonic singularity. Our geometry enables broad and strong spectral light harvesting at the active site of a nearby semiconductor where the chemical reaction occurs. A proof-of-concept nanostructure comprising Cu2ZnSnS4 (CZTS) and Au–Au dimer (t-CZTS@Au–Au) is fabricated via a colloidal strategy combining templating and seeded growth. On the basis of numerical and experimental results of different related hybrid nanostructures, we show that both the sharpness of the singular feature and the relative position to the reactive site play a pivotal role in optimizing photocatalytic activity. Compared with bare CZTS, the hybrid nanostructure (t-CZTS@Au–Au) exhibits an enhancement of the photocatalytic hydrogen evolution rate by up to ∼9 times. The insights gained from this work might be beneficial for designing efficient composite plasmonic photocatalysts for diverse photocatalytic reactions