Visible-Light Harvesting SrTiO3 Solid Solutions for Photocatalytic Hydrogen Evolution from Water.

The fabrication of solid solutions represents a compelling approach to modulating the physicochemical properties of materials. In this study, we achieved the successful synthesis of solid solutions comprising SrTiO3 and SrTaO2N (denoted as (SrTiO3)1-x-(SrTaO2N)x, 0≤x≤1) using the magnesium powder-assisted nitridation method. The absorption edge of (SrTiO3)1-x-(SrTaO2N)x is tunable from 500 to 600 nm. The conduction band minimum (CBM) of (SrTiO3)1-x-(SrTaO2N)x comprises the Ti 3d orbitals and the Ta 5d orbitals, while the valence band maximum (VBM) consists of the O 2p and N 2p orbitals. The microstructure of the (SrTiO3)1-x-(SrTaO2N)x consists of small nanoparticles, exhibiting a larger specific surface area than the parent compounds of SrTiO3 and SrTaO2N. In the photocatalytic hydrogen evolution reaction (HER) with sacrificial reagents, the activity of solid solutions is notably superior to that of nitrogen-doped SrTiO3 and SrTaO2N. This superiority is mainly attributed to its broad light absorption range and high charge separation efficiency, which indicates its potential as a promising photocatalytic material. Moreover, the magnesium powder-assisted nitridation method exhibits obvious advantages for the synthesis of oxynitrides and bears instructional significance for the synthesis of other nitrogen-containing compounds and even sulfur-containing compounds.

Metallic Powder Promotes Nitridation Kinetics for Facile Synthesis of (Oxy)Nitride Photocatalysts.

Nitrogen-containing semiconductors (including metal nitrides, metal oxynitrides, and nitrogen-doped metal oxides) have been widely researched for their application in energy conversion and environmental purification because of their unique characteristics; however, their synthesis generally encounters significant challenges owing to sluggish nitridation kinetics. Herein, a metallic-powder-assisted nitridation method is developed that effectively promotes the kinetics of nitrogen insertion into oxide precursors and exhibits good generality. By employing metallic powders with low work functions as electronic modulators, a series of oxynitrides (i.e., LnTaON2 (Ln = La, Pr, Nd, Sm, and Gd), Zr2 ON2 , and LaTiO2 N) can be prepared at lower nitridation temperatures and shorter nitridation periods to obtain comparable or even lower defect concentrations compared to those of the conventional thermal nitridation method, leading to superior photocatalytic performance. Moreover, some novel nitrogen-doped oxides (i.e., SrTiO3- x Ny and Y2 Zr2 O7- x Ny ) with visible-light responses can be exploited. As revealed by density functional theory (DFT) calculations, the nitridation kinetics are enhanced via the effective electron transfer from the metallic powder to the oxide precursors, reducing the activation energy of nitrogen insertion. The modified nitridation route developed in this work is an alternative method for preparing (oxy)nitride-based materials for energy/environment-related heterogeneous catalysis.

Visible-light-responsive Photocatalyst Based on Nitrogen-doped Bulk Oxide YTaO4-x Ny for Z-scheme Overall Water Splitting.

Nitrogen doping into oxide has been proved to be an effective strategy to extend visible-light utilization of oxides with layered or channeled structure, but it is shortage for the bulk oxides free of layered or channeled structure. Here, we report a novel nitrogen-doped bulk oxide (denoted as YTaO4-x Ny ) with good visible light response. As benefited from the strong hybridization of N 2p and O 2p electronic state according to the density functional theory (DFT) calculations, the band gap (3.6 eV) of YTaO4 precursor was sharply narrowed to 2.4 eV on YTaO4-x Ny due to the obvious uplift of the valence band maximum (VBM). After decorated with the platinum cocatalyst, the Pt/YTaO4-x Ny was used as the H2 -evolving photocatalyst for assembly of Z-scheme overall water splitting system by coupling with the PtOx /WO3 as the oxygen evolution photocatalyst and using the I- /IO3- as the shuttle ions. This work enriches the material database of nitrogen-doped oxide with wide visible light absorption and shows its promising application in solar-to-chemical conversion.

Flux-assisted synthesis of tungsten-doped layered perovskite oxychloride with promoted visible-light-responsive O2 evolution performance.

Here, we successfully prepared Ba2Bi3Ta2O11Cl via a simple one-step molten salt method and adjusted its crystal morphology and structure, based on which the O2-evolving activity was significantly improved. In addition, W doping promotes the charge separation efficiency, lowers the energy barrier for water oxidation reaction, and thus improves the activity. Finally, the optimized W-doped sample after molten salt treatment shows the best O2 production activity (55 µmol h-1) without loading any cocatalyst, which is 6 times higher than that of pristine Ba2Bi3Ta2O11Cl and 2 times higher than that of the undoped Ba2Bi3Ta2O11Cl treated with molten salt, respectively.

Layered ß-ZrNBr Nitro-Halide as Multifunctional Photocatalyst for Water Splitting and CO2 Reduction.

Developing mixed-anion semiconductors for solar fuel production has inspired extensive interest, but the nitrohalide-based photocatalyst is still in shortage. Here we report a layered nitro-halide ß-ZrNBr with a narrow band gap of ca. 2.3 eV and low defect density to exhibit multifunctionalities for photocatalytic water reduction, water oxidation and CO2 reduction under visible-light irradiation. As confirmed by the results of electron paramagnetic resonance (EPR) and density functional theory (DFT) calculations, the formation of anion vacancies in the nitro-halide photocatalyst was inhibited due to its relatively high formation energy. Furthermore, performance of ß-ZrNBr can be effectively promoted by a simple exfoliation into nanosheets to shorten the carrier transfer distance as well as to promote charge separation. Our work extends the territory of functional photocatalysts into the nitro-halide, which opens a new avenue for fabricating efficient artificial photosynthesis.

Insight into the Crystal Facet Effect of {101} and {100} Facets of CeVO4 in the Photochemical Property and Photocatalysis.

To investigate the photochemical property of specific crystal facets, two well-defined CeVO4 dodecahedrons with exposed {101} and {100} facets are prepared, which have distinguishing appearances and unequal {101}/{100} area ratios (A{101}/A{100}), i.e., compressed dodecahedra (CeVO4 CD, A{101}/A{100} ≈ 1) and elongated dodecahedra (CeVO4 ED, A{101}/A{100} ≈ 0.3). During the visible-light-irradiated process, the {101} and {100} facets are certified to selectively deposit photogenerated holes (h+) and electrons (e-), thus exhibiting the photooxidability and photoreducibility, respectively. Meanwhile, a surface heterojunction could form at the adjacent facet interface and facilitate the spatial separation of carriers. Benefiting from the large exposure extent of the {101} facet and the rational A{101}/A{100} (∼1), the CeVO4 CD shows a superior photocatalytic performance for the degradation of tetracycline to the CeVO4 ED. Finally, simulation calculations reveal that the energy deviations of the valence band (VB) and conduction band (CB) between CeVO4{101} and CeVO4{100} impel the photogenerated h+ and e- to transfer in opposite directions, resulting in the facet-dependent photoactivity of the CeVO4 dodecahedron.

Pyrochlore-structural Nd2Ta2O5N2 photocatalyst with an absorption edge of over 600 nm for Z-scheme overall water splitting.

A pyrochlore-structural oxynitride Nd2Ta2O5N2 with a visible light absorption edge of ca. 620 nm was explored for photocatalytic water splitting. Dual functions of Nd2Ta2O5N2 were confirmed by proton reduction and water oxidation half-reactions through separately loading Pt or CoOx as a cocatalyst in the presence of the corresponding sacrificial reagent. Finally, the platinum modified sample (Pt/Nd2Ta2O5N2) was prepared and employed as the H2-evolving photocatalyst to fabricate an effective photocatalytic Z-scheme overall water splitting together with PtOx/WO3 as the O2-evolving photocatalyst and IO3-/I- as shuttle ions under visible light irradiation.

Direct Z-scheme MoSe2/TiO2 heterostructure with improved piezoelectric and piezo-photocatalytic performance.

Nano-semiconductor materials coupled with piezoelectric effect have received extensive attention due to their wide application in catalysis. In this work, few-layered MoSe2 nanosheets were grown vertically on TiO2 nanorods (TNr) to synthesize a direct Z-scheme heterojunction, exhibiting efficient piezocatalytic and piezo-photocatalytic performance. The MoSe2/TNr heterostructure exhibited superior piezoelectric degradation efficiency, successfully removing over 98% of RhB within 360 s under continuous magnetic stirring in dark. Compared with piezocatalysis, the piezo-photocatalytic system possessed higher degradation efficiency and cycle stability. Furthermore, a piezo-photoelectric synergistic effect of nanocomposites was observed by current outputs. Under stirring conditions, the current density of depleted MoSe2/TNr and MoSe2 nanosheets were respectively 6.3 µA/cm2 and 5.5 µA/cm2. When light and stirring were applied, the MoSe2/TNr current density increased twice to 13.2 µA/cm2, while the MoSe2 nanosheets didn't exhibit improvement. Through the direct Z-scheme heterojunction of MoSe2/TNr, photoexcitation and piezoelectric polarization work together to effectively replenish carriers under light irradiation, and then rapidly separate free charges through piezopotential. This work broadens the application prospects of piezocatalysis and piezo-photocatalysis in renewable energy harvesting and water purification.

Water-Stable Nickel Metal-Organic Framework Nanobelts for Cocatalyst-Free Photocatalytic Water Splitting to Produce Hydrogen.

Development of water-stable metal-organic frameworks (MOFs) for promising visible-light-driven photocatalytic water splitting is highly desirable but still challenging. Here we report a novel p-type nickel-based MOF single crystal (Ni-TBAPy-SC) and its exfoliated nanobelts (Ni-TBAPy-NB) that can bear a wide range of pH environment in aqueous solution. Both experimental and theoretical results indicate a feasible electron transfer from the H4TBAPy ligand (light-harvesting center) to the Ni-O cluster node (catalytic center), on which water splitting to produce hydrogen can be efficiently driven free of cocatalyst. Compared to the single crystal, the exfoliated two-dimensional (2D) nanobelts show more efficient charge separation due to its shortened charge transfer distance and remarkably enhanced active surface areas, resulting in 164 times of promoted water reduction activity. The optimal H2 evolution rate on the nanobelt reaches 98 µmol h-1 (ca. 5 mmol h-1 g-1) showing benchmarked apparent quantum efficiency (AQE) of 8.0% at 420 nm among water-stable MOFs photocatalysts.

Synthesis of a Visible-Light-Responsive Perovskite SmTiO2 N Bifunctional Photocatalyst via an Evaporation-Assisted Layered-Precursor Strategy.

Development of visible-light-responsive oxynitride photocatalysts has been highly inspired for promising solar-to-chemical conversion, but the number of Ti-based oxynitrides is scarce because of the relatively low thermal stability of Ti4+ ions under ammonia flow. Here, the feasible synthesis of a novel perovskite SmTiO2 N from the layered NaSmTiO4 precursor is demonstrated to exhibit wide visible-light response with a bandgap of ≈2.1 eV and to show effective water reduction and oxidation functionalities under visible-light irradiation. The successful preparation mainly results from the synergistic effect of the layered structure of NaSmTiO4 and the evaporation spillover of Na+ ions, both of which are favorable for ammonia diffusion to accelerate the substitution of nitrogen to oxygen atoms and to shorten the nitridation time. The thermodynamic and kinetic feasibility of SmTiO2 N for water splitting are investigated in detail, and its optimal apparent quantum efficiency (AQE) of water oxidation reaches 16.7% at 420 ± 10 nm, higher by far than that of most previous visible-light-responsive photocatalysts. Interestingly, a series of oxynitrides RTiO2 N (R = La, Pr, Nd) are similarly synthesized by the alkali-metal evaporation-assisted layered-precursor strategy, demonstrating its generality to prepare visible-light-responsive (oxy)nitride photocatalysts containing reducible metals for solar energy conversion.

Efficient visible-light photocatalytic H2 evolution with heterostructured Ag2S modified CdS nanowires.

The low separation efficiency of photogenerated charges and severe photocorrosion seriously impeded the application of CdS in photocatalytic water splitting. Here we report new routes to improve the photocatalytic performance of CdS nanowires (NWs) by decorating with Ag2S nanoparticles, so Ag2S/CdS heterojunction is constructed. The Ag2S/CdS heterojunction exhibited optimal photocatalytic H2 evolution rate of 777.3 µmol h-1 g-1, which is 12.1 times higher than that of pure CdS. The intrinsic characteristics of Ag2S/CdS nanocomposites, such as structure, optical properties, and surface chemical state are systematically studied by experimental characterizations and theoretical calculations. The comprehensive analysis demonstrates that the heterojunction between Ag2S and CdS accelerates photoinduced electrons transfer from CdS to Ag2S, enhancing their ability for water splitting. Meanwhile, the holes on the valence band of CdS react with the sacrificial agents, thus leading to the efficient separation of photogenerated electron-hole pairs. This work offers a simple route to synthesize one-dimensional CdS-based nanocomposites for efficient energy conversion driven by visible light.

NiSe2 as Co-Catalyst with CdS: Nanocomposites for High-Performance Photodriven Hydrogen Evolution under Visible-Light Irradiation.

One-dimensional NiSe2 /CdS nanocomposites (NCs), with NiSe2 nanoparticles (NPs) integrated onto the surface of CdS nanowires (NWs) were designed and fabricated through a two-step in situ solvothermal method. Density functional theory (DFT) calculations showed that NiSe2 plays an important role in enhancing photocatalystic hydrogen (H2 ) production when coupled with CdS catalyst, which arises from 1) the contribution of Ni 3d and Se 4p orbitals to the electronic structures and 2) the charge redistribution at the interface region of the heterostructure results in efficient promotion of the charge transfer and separation of the photogenerated electron-hole pairs. Under visible-light illumination (λ≥400 nm), the NCs showed improved photocatalytic H2 -generation activity in the presence of lactic acid. The peak value of 7610.1 µmol h-1 g-1 for H2 production was achieved with an apparent quantum efficiency (AQE) of 41.68 % when the Ni/Cd ratio was set to 10 %, which was approximately 48 times higher than that of bare CdS NWs. Photoelectrochemical measurements also confirmed the pivotal role of NiSe2 in the improvement of the H2 -evolution performance of NiSe2 /CdS NCs, which is consistent with the DFT investigations.