De-Pinning Fermi Level and Accelerating Surface Kinetics with an ALD Finish Boost the Fill Factor of BiVO4 Photoanodes to 44.

With the rapid development of performance and long-term stability, bismuth vanadate (BiVO4 ) has emerged as the preferred photoanode in photoelectrochemical tandem devices. Although state-of-the-art BiVO4 photoanodes realize a saturated photocurrent density approaching the theoretical maximum, the fill factor (FF) is still inferior, pulling down the half-cell applied bias photon-to-current efficiency (HC-ABPE). Among the major fundamental limitations are the Fermi level pinning and sluggish surface kinetics at the low applied potentials. This work demonstrates that the plasma-assisted atomic layer deposition technique is capable of addressing these issues by seamlessly installing an angstrom-scale FeNi-layer between BiVO4 and electrolyte. Not only this ultrathin FeNi layer serves as an efficient OER cocatalyst, more importantly, it also effectively passivates the surface states of BiVO4 , de-pins the surface Fermi level, and enlarges the built-in voltage, allowing the photoanode to make optimal use of the photogenerated holes for achieving high FF up to 44% and HC-ABPE to 2.2%. This study offers a new approach for enhancing the FF of photoanodes and provides guidelines for designing efficient unassisted solar fuel devices.

Prompt Hole Extraction Suppresses V5+ Dissolution and Sustains Large-Area BiVO4 Photoanodes for Over 2100 h Water Oxidation.

Nanostructured bismuth vanadate (BiVO4) is at the forefront of emerging photoanodes in photoelectrochemical tandem devices for solar water splitting owing to the suitable band edge position and efficient charge separation capability. However, the (photo)chemical corrosion involving V5+ dissolution limits the long-term stability of BiVO4. Herein, guided by DFT calculations, we introduce an ALD-derived NiOx catalyst layer on BiVO4 to stabilize the surface Bi-O bonds, facilitate hole extraction, and thus suppress the V5+ dissolution. At the same time, the ALD NiOx catalyst layer could efficiently suppress the surface recombination and accelerate the surface OER kinetics, boosting the half-cell applied bias photon-to-current efficiency of BiVO4 to 2.05%, as well as a fill factor of 47.1%. By adding trace NaVO3 to the electrolyte, the NiOx/BiVO4 photoanode with an illumination area of 10.5 cm2 shows a record operational stability of more than 2100 h.

Syntheses of η1 -Alkyl-η3 -Allyl-η5 -Cyclopentadienyl Cobalt(III) Complexes and Their Use in Low-temperature Atomic Layer Deposition of Cobalt-Containing Thin Films.

Herein, we report the design and scalable synthesis of three new Co(III) complexes, which have an unusual hydrocarbon η1 -alkyl-η3 -allyl-η5 -cyclopentadienyl ligation structure, from the reactions of readily available cobalt(II) compound CoCl2 (PPh3 )2 and biomass material ß-pinene via C-C bond activation. These Co(III) complexes are air-stable, fairly volatile, and thermally stable, so they are excellent candidates as the metal precursors for the vapor deposition of cobalt-containing thin films. As a demonstration, we show that the Co(III) complex of [(3'-5'-η,1-σ)-methylene(2,2,4-trimethyl-4-cyclohexene-1,3-diyl)](η5 -methylcyclopentadienyl)Co (i. e. (seco-pinene)(MeCp)Co) is well suited for the atomic layer deposition (ALD) of Co3 O4 and CoS2 thin films, and the deposited Co3 O4 and CoS2 films are able to conformally cover trench structures with a fairly high aspect ratio of 10 : 1.

Atomic layer deposited nickel sulfide for bifunctional oxygen evolution/reduction electrocatalysis and zinc-air batteries.

Rechargeable Zn-air batteries are a promising type of metal-air batteries for high-density energy storage. However, their practical use is limited by the use of costly noble-metal electrocatalysts for the sluggish kinetics of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) occurred at the air electrode of the Zn-air batteries. This work reports a new non-precious bifunctional OER/ORR electrocatalyst of NiSx/carbon nanotubes (CNTs), which is made by atomic layer deposition (ALD) of nickel sulfide (NiSx) on CNTs, for the applications for the air electrode of the Zn-air batteries. The NiSx/CNT electrocatalyst on a carbon cloth electrode exhibits a low OER overpotential of 288 mV to reach 10 mA cm-2in current density, and the electrocatalyst on a rotating disk electrode exhibits a half-wave ORR potential of 0.81 V in alkaline electrolyte. With the use of the NiSx/CNT electrocatalyst for the air electrode, the fabricated aqueous rechargeable Zn-air batteries show a fairly good maximum output power density of 110 mW cm-2, which highlights the great promise of the ALD NiSx/CNT electrocatalyst for Zn-air batteries.

Facet-Selective Deposition of Ultrathin Al2 O3 on Copper Nanocrystals for Highly Stable CO2 Electroreduction to Ethylene.

Catalysts based on Cu nanocrystals (NCs) for electrochemical CO2 -to-C2+ conversion with high activity have been a subject of considerable interest, but poor stability and low selectivity for a single C2+ product remain obstacles for realizing sustainable carbon-neutral cycles. Here, we used the facet-selective atomic layer deposition (FS-ALD) technique to selectively cover the (111) surface of Cu NCs with ultrathin Al2 O3 to increase the exposed facet ratio of (100)/(111), resulting in a faradaic efficiency ratio of C2 H4 /CH4 for overcoated Cu NCs 22 times higher than that for pure Cu NCs. Peak performance of the overcoated catalyst (Cu NCs/Al2 O3 -10C) reaches a C2 H4 faradaic efficiency of 60.4 % at a current density of 300 mA cm-2 in 5 M KOH electrolyte, when using a gas diffusion electrode flow cell. Moreover, the Al2 O3 overcoating effectively suppresses the dynamic mobility and the aggregation of Cu NCs, which explains the negligible activity loss and selectivity degradations of Cu NCs/Al2 O3 -10C shown in stability tests.

Bifunctional Ag/C3N4.5 composite nanobelts for photocatalysis and antibacterium.

Multiple functions can be achieved in carbon nitride-based composite nanomaterials by tuning their components and structures. Here, we report on a large-scale synthesis of novel bifunctional Ag/C3N4.5 composite nanobelts (CNBs) with efficient photocatalytic and antibacterial activity. The Ag/C3N4.5 CNBs were synthesized in high yield by a two-step route including a homogeneous precipitation process and a subsequent calcination treatment. The structural, morphological, compositional, and spectroscopic characterizations revealed that the Ag/C3N4.5 CNBs are composed of N-deficient melem ultrathin nanobelts and crystalline Ag nanoparticles attached to the surface of the nanobelts with good contact. The band gap of the Ag/C3N4.5 CNBs is determined to be about 3.04 eV. The efficient photocatalytic and antibacterial activities of the composite nanomaterials are verified by testing the degradation of Rhodamine B (RhB) and the inhibition zone to bacterium E. coli. The work provides a facile route to bifunctional carbon nitride-based composites with potential applications in the fields of the environment and biology.

Carbon dots/TiO2 enhanced visible light-assisted photocatalytic of leachate: Simultaneous effects and Mechanism insights.

The persistence and potential fouling risks associated with humic substances and bacteria present in leachate have gained increasing attention. Therefore, developing efficient and environmentally compatible technologies for their removal is essential. This study presented the hydrothermal synthesis of a photocatalyst by coupling carbon dots (CDs) and bulk TiO2 (P25). The incorporation of CDs increased the photocatalytic performance by enhancing visible light absorption and facilitating the separation of electrons/holes. Compared to P25, the CDs/P25 exhibited optimal photocatalytic activity for humic acid (HA), fulvic acid (FA), and leachate, with 1.64, 1.02, and 1.12 times higher activity, respectively. Remarkedly, the CDs/P25 accelerated the conversion of large HA molecules into small molecules at a faster rate and higher amount than the bulk P25, due to the increase of hydroxyl radicals, monoclinic oxygen radicals, and superoxide radicals. Additionally, the CDs/P25 demonstrated better bacterial-deactivation ability than the P25, with dead bacteria percentages of 83.3% and 34.6%, respectively. This study provides a promising strategy for efficiently applying CDs/P25 photocatalysis to leachate treatment.

Solvent engineering of MAPbI3 perovskite thick film for a direct X-ray detector.

The emergence of organic-inorganic hybrid perovskites with a high µτ product and a high absorption coefficient has made it possible to adopt an aerosol-liquid-solid technology for direct X-ray detectors. The film quality from the ALS process is often compromised, especially on the film surface, when deposited in ambient conditions with uncontrolled humidity. Herein we develop a solvent engineering strategy in the ALS process to obtain high-quality MAPbI3 thick films. The key is the introduction of a molecular additive to intervene and regulate the perovskite crystallization process so that the negative effect of the ALS ambience is minimized. This strategy allows us to prepare direct X-ray detectors with much reduced dark current, enhanced response speed and improved overall performance.