Photocatalytic water splitting using particulate semiconductors is a potentially scalable and economically feasible technology for converting solar energy into hydrogen. Z-scheme systems based on two-step photoexcitation of a hydrogen evolution photocatalyst (HEP) and an oxygen evolution photocatalyst (OEP) are suited to harvesting of sunlight because semiconductors with either water reduction or oxidation activity can be applied to the water splitting reaction. However, it is challenging to achieve efficient transfer of electrons between HEP and OEP particles. Here, we present photocatalyst sheets based on La- and Rh-codoped SrTiO3 (SrTiO3:La, Rh; ref. ) and Mo-doped BiVO4 (BiVO4:Mo) powders embedded into a gold (Au) layer. Enhancement of the electron relay by annealing and suppression of undesirable reactions through surface modification allow pure water (pH 6.8) splitting with a solar-to-hydrogen energy conversion efficiency of 1.1% and an apparent quantum yield of over 30% at 419 nm. The photocatalyst sheet design enables efficient and scalable water splitting using particulate semiconductors.
Photoelectrochemical (PEC) devices that use semiconductors to absorb solar light for water splitting offer a promising way toward the future scalable production of renewable hydrogen fuels. However, the charge recombination in the photoanode/electrolyte (solid/liquid) junction is a major energy loss and hampers the PEC performance from being efficient. Here, we show that this problem is addressed by the conformal deposition of an ultrathin p-type NiO layer on the photoanode to create a buried p/n junction as well as to reduce the charge recombination at the surface trapping states for the enlarged surface band bending. Further, the in situ formed hydroxyl-rich and hydroxyl-ion-permeable NiOOH enables the dual catalysts of CoO(x) and NiOOH for the improved water oxidation activity. Compared to the CoO(x) loaded BiVO4 (CoO(x)/BiVO4) photoanode, the ∼6 nm NiO deposited NiO/CoO(x)/BiVO4 photoanode triples the photocurrent density at 0.6 V(RHE) under AM 1.5G illumination and enables a 1.5% half-cell solar-to-hydrogen efficiency. Stoichiometric oxygen and hydrogen are generated with Faraday efficiency of unity over 12 h. This strategy could be applied to other narrow band gap semiconducting photoanodes toward the low-cost solar fuel generation devices.
An increasing number of applications using ultraviolet radiation have renewed interest in ultraviolet photodetector research. Particularly, solar‐blind photodetectors sensitive to only deep UV (<280 nm), have attracted growing attention because of their wide applicability. Among recent advances in UV detection, nanowire (NW)‐based photodetectors seem promising, however, none of the reported devices possesses the required attributes for practical solar‐blind photodetection, namely, an efficient fabrication process, a high solar light rejection ratio, a low photocurrent noise, and a fast response. Herein, the assembly of β‐Ga2O3 NWs into high‐performance solar‐blind photodetectors by use of an efficient bridging method is reported. The device is made in a single‐step chemical vapor deposition process and has a high 250‐to‐280‐nm rejection ratio (∼2 × 103), low photocurrent fluctuation (<3%), and a fast decay time (<<20 ms). Further, variations in the synthesis parameters of the NWs induce drastic changes in the photoresponse properties, which suggest a possibility for tuning the performance of the photodetectors. The efficient fabrication method and high performance of the bridged β‐Ga2O3 NW photodetectors make them highly suitable for solar‐blind photodetection.
Porous films of p-type CuInS2, prepared by sulfurization of electrodeposited metals, are surface-modified with thin layers of CdS and TiO2. This specific porous electrode evolved H2 from photoelectrochemical water reduction under simulated sunlight. Modification with thin n-type CdS and TiO2 layers significantly increased the cathodic photocurrent and onset potential through the formation of a p-n junction on the surface. The modified photocathodes showed a relatively high efficiency and stable H2 production under the present reaction conditions.
Electrochemical reduction of CO2 (CO2R) to formic acid upgrades waste CO2; however, up to now, chemical and structural changes to the electrocatalyst have often led to the deterioration of performance over time. Here, we find that alloying p-block elements with differing electronegativities modulates the redox potential of active sites and stabilizes them throughout extended CO2R operation. Active Sn-Bi/SnO2 surfaces formed in situ on homogeneously alloyed Bi0.1Sn crystals stabilize the CO2R-to-formate pathway over 2400 h (100 days) of continuous operation at a current density of 100 mA cm−2. This performance is accompanied by a Faradaic efficiency of 95% and an overpotential of ~ −0.65 V. Operating experimental studies as well as computational investigations show that the stabilized active sites offer near-optimal binding energy to the key formate intermediate *OCHO. Using a cation-exchange membrane electrode assembly device, we demonstrate the stable production of concentrated HCOO– solution (3.4 molar, 15 wt%) over 100 h.
A highly efficient low-band-gap (1.2-0.8 eV) photoelectrode is critical for accomplishing efficient conversion of visible-near-infrared sunlight into storable hydrogen. Herein, we report an SbSe polycrystalline thin-film photocathode having a low band gap (1.2-1.1 eV) for efficient hydrogen evolution for wide solar-spectrum utilization. The photocathode was fabricated by a facile thermal evaporation of a single SbSe powder source onto the Mo-coated soda-lime glass substrate, followed by annealing under Se vapor and surface modification with an antiphotocorrosive CdS/TiO bilayer and Pt catalyst. The fabricated SbSe(Se-annealed)/CdS/TiO/Pt photocathode achieves a photocurrent density of ca. -8.6 mA cm at 0 V, an onset potential of ca. 0.43 V, a stable photocurrent for over 10 h, and a significant photoresponse up to the near-infrared region (ca. 1040 nm) in near-neutral pH buffered solution (pH 6.5) under AM 1.5G simulated sunlight. The obtained photoelectrochemical performance is attributed to the reliable synthesis of a micrometer-sized SbSe (Se-annealed) thin film as photoabsorber and the successful construction of an appropriate p-n heterojunction at the electrode-liquid interface for effective charge separation. The demonstration of a low-band-gap and high-performance SbSe photocathode with facile fabrication might facilitate the development of cost-effective PEC devices for wide solar-spectrum utilization.
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