Anisotropic Charge Migration on Perovskite Oxysulfide for Boosting Photocatalytic Overall Water Splitting.

The synthesis of photocatalysts with both broad light absorption and efficient charge separation is significant for a high solar energy conversion, which still remains to be a challenge. Herein, a narrow-bandgap Y2Ti2O5S2 (YTOS) oxysulfide nanosheet coexposed with defined {101} and {001} facets synthesized by a flux-assisted solid-state reaction was revealed to display the character of an anisotropic charge migration. The selective photodeposition of cocatalysts demonstrated that the {101} and {001} surfaces of YTOS nanosheets were the reduction and oxidation regions during photocatalysis, respectively. Density functional theory (DFT) calculations indicated a band energy level difference between the {101} and {001} facets of YTOS, which contributes to the anisotropic charge migration between them. The exposed Ti atoms on the {101} surface and S atoms on the {001} surface were identified, respectively, as reducing and oxidizing centers of YTOS nanosheets. This anisotropic charge migration generated a built-in electric field between these two facets, quantified by spatially resolved surface photovoltage microscopy, the intensity of which was found to be highly correlated with photocatalytic H2 production activity of YTOS, especially exhibiting a high apparent quantum yield of 18.2% (420 nm) after on-site modification of a Pt@Au cocatalyst assisted by Na2S-Na2SO3 hole scavengers. In conjunction with an oxygen-production photocatalyst and a [Co(bpy)3]2+/3+ redox shuttle, the YTOS nanosheets achieved a solar-to-hydrogen conversion efficiency of 0.15% via a Z-scheme overall water splitting. Our work is the first to confirm anisotropic charge migration in a perovskite oxysulfide photocatalyst, which is crucial for enhancing charge separation and surface catalytic efficiency in this material.

Highly Selective Photoelectroreduction of Carbon Dioxide to Ethanol over Graphene/Silicon Carbide Composites.

Using sunlight to produce valuable chemicals and fuels from carbon dioxide (CO2 ), i.e., artificial photosynthesis (AP) is a promising strategy to achieve solar energy storage and a negative carbon cycle. However, selective synthesis of C2 compounds with a high CO2 conversion rate remains challenging for current AP technologies. We performed CO2 photoelectroreduction over a graphene/silicon carbide (SiC) catalyst under simulated solar irradiation with ethanol (C2 H5 OH) selectivity of>99 % and a CO2 conversion rate of up to 17.1 mmol gcat -1 h-1 with sustained performance. Experimental and theoretical investigations indicated an optimal interfacial layer to facilitate the transfer of photogenerated electrons from the SiC substrate to the few-layer graphene overlayer, which also favored an efficient CO2 to C2 H5 OH conversion pathway.

Facet Engineering on WO3 Mono-Particle-Layer Electrode for Photoelectrochemical Water Splitting.

Photoelectrochemical (PEC) performance of WO3 photoanodes for water splitting is heavily influenced by the orientation of crystal facets. In this work, mono-particle-layer electrodes, assembled by particulate WO3 square plates with highly uniform alignment along the (002) facet, improved PEC water oxidation kinetics and stability. Photo-deposition of Au along the cracks formed on the surface of the plates, which are the edges of {110} facets, was found to further enhance electron collection efficiency. Combination of these two strategies allowed the facet-engineered WO3 electrode to produce significantly higher efficiencies in charge separation and transfer than the electrode prepared without facet orientation. This work has provided a facile route for fabricating a structurally designed WO3 photoelectrode, which is also applicable to other regularly shaped semiconductor photocatalysts with anisotropic charge migration.

Enhancement of solar hydrogen evolution from water by surface modification with CdS and TiO2 on porous CuInS2 photocathodes prepared by an electrodeposition-sulfurization method.

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.

Probing Intra-Gap States Mediated Charge Dynamics of Rh-Doped Rutile TiO2 Photocatalyst by Light-Modulated Photocurrent Spectroscopies.

The intra-gap states that are introduced into a semiconducting photocatalyst via dopants and other defects have significant implications on the transport dynamics of photoexcited electrons and holes during an aqueous light-driven reaction. In this work, mechanistic understanding of Rh-doped rutile, a promising photocatalyst for hydrogen production from water, is gained by systematic assessment combining intensity-modulated photocurrent spectroscopy with sub-gap excitations and alternating-current photocurrent spectroscopy. These operando techniques not only help in discovering a new electronic transport path in Rh-rutile via surface Rh4+ species and elucidating complex interaction between electrolyte molecules and semiconductors, but also underscore the potential of utilizing multiple sub-gap excitations synergistically. This combination offers a powerful tool for acquiring insight into photo-physical and photo-chemical behaviors of photo(electro)catalysts with intra-gap states.

A Visible Light-Responsive TiO2 Photocathode Achieved by a Rh Dopant.

Developing an efficient and stable photocathode material for photoelectrochemical solar water splitting remains challenging. Herein, we demonstrate the potential of rutile TiO2 as a photocathode by Rh doping with visible light absorption up to 640 nm and an onset potential of 0.9 V versus the reversible hydrogen electrode. The dopant transforms the rutile host from an n-type semiconductor to a p-type one, as confirmed by the Mott-Schottky curve and kelvin probe force microscopy. Physical and photoelectrochemical analyses further suggest that the doping mechanism is dependent on concentration. Lower levels of dopants generate localized Rh3+, while higher levels favor Rh4+ that interacts more strongly with the O 2p orbitals. The latter is found not only to extend the visible light absorption range but also to facilitate charge transport. This work elucidates the role of the Rh dopant in adjusting the photoelectrochemical behavior of TiO2, and it provides a promising photocathode material for solar energy conversion.

Conformal and conductive biofilm-bridged artificial Z-scheme system for visible light-driven overall water splitting.

Semi-artificial Z-scheme systems offer promising potential toward efficient solar-to-chemical conversion, yet sustainable and stable designs are currently lacking. Here, we developed a sustainable hybrid Z-scheme system capable for visible light-driven overall water splitting by integrating the durability of inorganic photocatalysts with the interfacial adhesion and regenerative property of bacterial biofilms. The Z-scheme configuration is fabricated by drop casting a mixture of photocatalysts onto a glass plate, followed by the growth of biofilms for conformal conductive paste through oxidative polymerization of pyrrole molecules. Notably, the system exhibited scalability indicated by consistent catalytic efficiency across various sheet areas, resistance observed by remarkable maintaining of photocatalytic efficiency across a range of background pressures, and high stability as evidenced by minimal decay of photocatalytic efficiency after 100-hour reaction. Our work thus provides a promising avenue toward sustainable and high-efficiency artificial photosynthesis, contributing to the broader goal of sustainable energy solutions.

Rhodium-Doped Barium Titanate Perovskite as a Stable p-Type Photocathode in Solar Water Splitting.

Solar water splitting from a p-n-conjugated photoelectrochemical (PEC) system is a promising way to produce hydrogen sustainably. At present, finding a compatible p-type photocathode material for the p-n system remains a great challenge in consideration of the photocurrent and stability. This paper highlighted a promising candidate, Rh/BaTiO3, by switching BaTiO3 from an n-type photoanode to a p-type photocathode upon Rh doping. The dopant activated visible light absorption up to 550 nm and an onset potential as high as 1.0 V (vs RHE). Using surface photovoltage spectroscopy as a powerful characterization tool, the n- to p-type transition of the semiconductor was studied and explained microscopically by which we quantitatively isolated the cathodic contribution caused by the Rh dopant. Unbiased overall solar water splitting was accomplished by serially connecting the Pt/Rh/BaTiO3 photocathode to a CoOx/Mo/BiVO4 photoanode, which produced a solar to hydrogen conversion efficiency of 0.1% and an excellent stability over 100 h of operation at ambient pressure. This work revealed the key role that the Rh dopant played in the n- to p-type adjustment of titanate semiconductors and demonstrated its great potential for application in PEC water splitting.

Stille type P-C coupling polycondensation towards phosphorus-crosslinked polythiophenes with P-regulated photocatalytic hydrogen evolution.

Recently, exploring new type polymerization protocols has been a major driving force in advancing organic polymers into highly functional materials. Herein we report a new polycondensation protocol to implant the phosphorus (P) atom in the main backbone of crosslinked polythiophenes. The polycondensation harnesses a Stille phosphorus-carbon (P-C) coupling reaction between phosphorus halides and aryl stannanes that has not been reported previously. Mechanistic studies uncovered that the P-electrophile makes the reactivity of a catalytic Pd-center highly sensitive towards the chemical structures of aryl stannanes, which is distinct from the typical Stille carbon-carbon coupling reaction. The efficient P-C polycondensation afforded a series of P-crosslinked polythiophenes (PC-PTs). Leveraging on the direct P-crosslinking polymerization, solid-state 31P NMR studies revealed highly uniform crosslinking environments. Efficient post-polymerization P-chemistry was also applied to the PC-PTs, which readily yielded the polymers with various P-environments. As a proof of concept, new PC-PTs were applied as the photocatalysts for H2 evolution under visible light irradiation. PC-PTs with an ionic P(Me)-center exhibit a H2 evolution rate up to 2050 µmol h-1 g-1, which is much higher than those of PC-PTs with a P(O)-center (900 µmol h-1 g-1) and P(iii)-center (155 µmol h-1 g-1). For the first time, the studies reveal that regulating P-center environments can be an effective strategy for fine tuning the photocatalytic H2 evolution performance of organic polymers.

Photoelectrochemical conversion of toluene to methylcyclohexane as an organic hydride by Cu2ZnSnS4-based photoelectrode assemblies.

Direct photoelectrochemical conversion of toluene (TL) to methylcyclohexane (MC) with water has been examined as an organic hydride conversion using light irradiation. The production of MC from TL was observed on Pt/CdS/Cu(2)ZnSnS(4)/Mo photoelectrodes with anion-type ionomer membrane assemblies. A cathodic photocurrent was observed below 0.7 V vs RHE (V(RHE)) in 0.1 M Na(2)SO(4)/NaOH (pH 9.5) aqueous solution, and an apparent photocurrent density of 0.5 mA cm(-2) was obtained at 0 V(RHE) under the irradiation of a 300 W Xe lamp with a 420 nm cutoff filter. The yield of MC was measured by gas chromatography, and an 88% faradaic efficiency was estimated. This study suggests the possibility of direct energy conversion from solar energy to MC as an energy carrier of organic hydrides.

Insight into the Light-Driven Hydrogen Production over Pure and Rh-Doped Rutile in the Presence of Ascorbic Acid: Impact of Interfacial Chemistry on Photocatalysts.

The surface states of a semiconductor photocatalyst are essential for interfacial charge transfer in heterogeneous photocatalytic reactions. Here, we report that the light-driven hydrogen evolution reaction (HER) activity of 0.5 mol % Rh-doped rutile increases by more than 30 times compared with that of rutile when ascorbic acid is used as a sacrificial agent. Intensity-modulated photocurrent spectroscopy and surface photovoltage spectroscopy are employed to reveal the impact of surface states on the photo-oxidation reactions. It is found that the adsorption of ascorbic acid molecules dramatically reduces the activity of rutile due to coverage of the HER-active Ti sites. Nevertheless, for Rh-doped rutile, ascorbic acid neutralizes the Rh(IV) sites that would otherwise cause severe recombination of electron-hole pairs and resurrects its photocatalytic performance. This work demonstrates the key role of interfacial chemistry in photocatalytic reactions and provides a strategy for excavating the potential of various photocatalysts.

A Transfer Learning-Based Method for Personalized State of Health Estimation of Lithium-Ion Batteries.

State of health (SOH) estimation of lithium-ion batteries (LIBs) is of critical importance for battery management systems (BMSs) of electronic devices. An accurate SOH estimation is still a challenging problem limited by diverse usage conditions between training and testing LIBs. To tackle this problem, this article proposes a transfer learning-based method for personalized SOH estimation of a new battery. More specifically, a convolutional neural network (CNN) combined with an improved domain adaptation method is used to construct an SOH estimation model, where the CNN is used to automatically extract features from raw charging voltage trajectories, while the domain adaptation method named maximum mean discrepancy (MMD) is adopted to reduce the distribution difference between training and testing battery data. This article extends MMD from classification tasks to regression tasks, which can therefore be used for SOH estimation. Three different datasets with different charging policies, discharging policies, and ambient temperatures are used to validate the effectiveness and generalizability of the proposed method. The superiority of the proposed SOH estimation method is demonstrated through the comparison with direct model training using state-of-the-art machine learning methods and several other domain adaptation approaches. The results show that the proposed transfer learning-based method has wide generalizability as well as a positive precision improvement.

Enhanced visible-light activity of titania via confinement inside carbon nanotubes.

Titania confined inside carbon nanotubes (CNTs) was synthesized using a restrained hydrolysis method. Raman spectra and magnetic measurements using a SQUID magnetometer suggested the formation of remarkable oxygen vacancies over the encapsulated TiO(2) in comparison with nanoparticles dispersed on the outer surface of CNTs, extending the photoresponse of TiO(2) from the UV to the visible-light region. The CNT-confined TiO(2) exhibited improved visible-light activity in the degradation of methylene blue (MB) relative to the outside titania and commercial P25, which is attributed to the modification of the electronic structure of TiO(2) induced by the unique confinement inside CNTs. These results provide further insight into the effect of confinement within CNTs, and the composites are expected to be promising for applications in visible-light photocatalysis.

Iron(II) Spin Crossover Coordination Polymers Derived From a Redox Active Equatorial Tetrathiafulvalene Schiff-Base Ligand.

Two polymorphic FeII coordination polymers [FeIIL (TPPE)0.5] 1) and [(FeII 3L3 (TPPE)1.5)] 2), were obtained from a redox-active tetrathiafulvalene (TTF) functionalized ligand [H2L = 2,2'-(((2-(4,5-bis-(methylthio)-1,3-dithiol-2-ylidene)benzo(d) (1,3) dithiole-5,6-diyl)bis-(azanediyl))bis-(meth anylylidene)) (2E,2E')-bis(3-oxobutanoate)] and a highly luminescent connector {TPPE = 1,1,2,2-tetrakis[4-(pyridine-4-yl)phenyl]-ethene}. Complex 1 has a layered structure where the TPPE uses its four diverging pyridines from the TPPE ligand are coordinated by the trans positions to the flat TTF Schiff-base ligand, and complex 2 has an unprecedented catenation of layers within two interpenetrated frameworks. These coordination polymers reserved the redox activity of the TTF unit. Complex 1 shows gradual spin transition behavior without hysteresis. And the fluorescence intensity of TPPE in 1 changes in tandem with the spin crossover (SCO) transition indicating a possible interplay between fluorescence and SCO behavior.

Diatom-inspired multiscale mineralization of patterned protein-polysaccharide complex structures.

Marine diatoms construct their hierarchically ordered, three-dimensional (3D) external structures called frustules through precise biomineralization processes. Recapitulating the remarkable architectures and functions of diatom frustules in artificial materials is a major challenge that has important technological implications for hierarchically ordered composites. Here, we report the construction of highly ordered, mineralized composites based on fabrication of complex self-supporting porous structures-made of genetically engineered amyloid fusion proteins and the natural polysaccharide chitin-and performing in situ multiscale protein-mediated mineralization with diverse inorganic materials, including SiO2, TiO2 and Ga2O3. Subsequently, using sugar cubes as templates, we demonstrate that 3D fabricated porous structures can become colonized by engineered bacteria and can be functionalized with highly photoreactive minerals, thereby enabling co-localization of the photocatalytic units with a bacteria-based hydrogenase reaction for a successful semi-solid artificial photosynthesis system for hydrogen evolution. Our study thus highlights the power of coupling genetically engineered proteins and polysaccharides with biofabrication techniques to generate hierarchically organized mineralized porous structures inspired by nature.

A one-step synthesis of a Ta3N5 nanorod photoanode from Ta plates and NH4Cl powder for photoelectrochemical water oxidation.

A rod-like Ta3N5 thin film was synthesized by calcining a vacuum-sealed mixture of Ta metal plates and NH4Cl powder. Photoelectrochemical water oxidation results showed that an anodic photocurrent of 3.2 mA cm-2 at 1.23 V (vs. RHE) with a faradaic efficiency of unity for O2 evolution could be achieved by employing the as-prepared Ta3N5/Ta as a photoanode.

A general end-to-end diagnosis framework for manufacturing systems.

The manufacturing sector is envisioned to be heavily influenced by artificial-intelligence-based technologies with the extraordinary increases in computational power and data volumes. A central challenge in the manufacturing sector lies in the requirement of a general framework to ensure satisfied diagnosis and monitoring performances in different manufacturing applications. Here, we propose a general data-driven, end-to-end framework for the monitoring of manufacturing systems. This framework, derived from deep-learning techniques, evaluates fused sensory measurements to detect and even predict faults and wearing conditions. This work exploits the predictive power of deep learning to automatically extract hidden degradation features from noisy, time-course data. We have experimented the proposed framework on 10 representative data sets drawn from a wide variety of manufacturing applications. Results reveal that the framework performs well in examined benchmark applications and can be applied in diverse contexts, indicating its potential use as a critical cornerstone in smart manufacturing.

Visible-Light-Driven Photocatalytic Z-Scheme Overall Water Splitting in La5 Ti2 AgS5 O7 -based Powder-Suspension System.

La5 Ti2 Cux Ag1-x S5 O7 (x=0-1) is a type of long-wavelength-responsive oxysulfide photocatalysts for hydrogen evolution and has been demonstrated to enable the Z-scheme water-splitting coupling with oxygen evolution photocatalysts (OEPs) in the particulate sheet. Among La5 Ti2 Cux Ag1-x S5 O7 materials, La5 Ti2 AgS5 O7 was found to have the highest performance on Z-scheme overall water splitting in conjunction with PtOx -WO3 as an OEP and a triiodide/iodide (I3 - /I- ) redox couple as a shuttle electron mediator in a powder-suspension system. Loading Pt/NiS on La5 Ti2 AgS5 O7 benefitted the Z-scheme to achieve an apparent quantum yield of 0.12 % at 420 nm. The results for this powder-suspension system differ from earlier studies on photocatalyst sheet configurations, in which p-type doping and the formation of a solid solution could effectively enhance the water-splitting activity. This work not only demonstrates a La5 Ti2 AgS5 O7 -based Z-scheme water-splitting photocatalyst but also improves the understanding of the difference between particulate sheets and a powder-suspension system available in an optimal strategy for water splitting.

Efficient hydrogen evolution on (CuInS2)x(ZnS)1-x solid solution-based photocathodes under simulated sunlight.

A thin film of (CuInS2)x(ZnS)1-x has been developed as a photocathode for solar water splitting for the first time. A superior photoelectrochemical performance has been achieved, mainly attributed to the formation of a solid solution by CuInS2 and ZnS, which proved to be an effective strategy to improve the onset potential and efficiency of CuInS2 photocathodes.

Enhancement of photocatalytic H2 evolution on CdS by loading MoS2 as Cocatalyst under visible light irradiation.

This communication presents our recent results that the activity of photocatalytic H2 production can be significantly enhanced when a small amount of MoS2 is loaded on CdS as cocatalyst. The MoS2/CdS catalysts show high rate of H2 evolution from photocatalytic re-forming of lactic acid under visible light irradiation. The rate of H2 evolution on CdS is increased by up to 36 times when loaded with only 0.2 wt % of MoS2, and the activity of MoS2/CdS is even higher than those of the CdS photocatalysts loaded with different noble metals, such as Pt, Ru, Rh, Pd, and Au. The junction formed between MoS2 and CdS and the excellent H2 activation property of MoS2 are supposed to be responsible for the enhanced photocatalytic activity of MoS2/CdS.