Organic-inorganic Hybrid Systems Research Articles

Molecular Engineering for High-Performance X-ray Scintillators.

X-ray scintillators, materials that convert high-energy radiation into detectable light in the ultraviolet to visible spectrum, are widely used in industrial and medical applications. Organic and organic-inorganic hybrid systems have emerged as promising alternatives for X-ray detection and imaging due to their mechanical flexibility, lightweight, tunable excited states, and solution processability for large-scale fabrication. However, these systems often suffer from weak X-ray absorption and insufficient exciton utilization, which seriously affects their scintillation performance, limiting their potential for broader application and commercialization. This review highlights recent advances in molecular engineering for developing high-performance X-ray scintillators. Itfocuses on molecular design principles, such as the heavy atom effect, donor-acceptor/host-guest strategies, hydrogen/halogen bonding, molecular sensitization, and crystal packing, for enhancing scintillation performance. By leveraging these approaches, researchers have made significant strides in improving X-ray scintillation efficiency and advancing the potential of these materials for commercial applications.

Cyclic Oxothiomolybdates: Building Blocks for Cyclodextrin-Based Open Frameworks.

Desolvation processes, though common in self-assembled biological structures, are rarely evidenced and utilized in the design of crystalline architectures. In this study, we introduce a novel approach using the [Mo8S8O8(OH)8(guest)]2- complex, formed by the self-condensation of four [MoV 2O2S2]2- fragments around a guest unit (MoVIO6H4 or oxalate), as a chaotropic scaffold for crystallizing hybrid organic-inorganic systems with natural cyclodextrins. Our findings reveal that β-cyclodextrin (β-CD) facilitates the formation of host-guest complexes, while α-cyclodextrin (α-CD) induces the formation of a Kagome-type structure with significant voids. These new compounds were thoroughly characterized using X-ray diffraction (both powder and single-crystal), N2 adsorption, elemental and thermogravimetric analysis. Additionally, solution studies using 1H NMR titration and small-angle X-ray scattering (SAXS) demonstrated pre-association of the building units in solution. These results enhance our understanding of the design principles for supramolecular structures composed of inorganic polyanions and cyclodextrins.

The Configuration Identification of Guanine Molecules Adsorbed on the Si(100) Surface by Using XPS Shake-up Satellites and NEXAFS.

Bioelectronic devices can be manufactured by organic-inorganic hybrid systems based on biomolecules and silicon semiconductors. The performance of the hybrid systems is largely determined by the adsorption manners of biomolecules on the silicon surface. In this paper, we demonstrated that the X-ray photoelectron spectroscopy (XPS) shake-up satellites and near-edge X-ray absorption fine-structure (NEXAFS) spectra at the carbon K-edges can be used to distinguish the interface of guanine molecules anchored on Si(100) surface. There are only 9 possible stable guanine@Si(100) hybrid systems that have been found based on the density functional theory. According to the characteristic peaks, it is confirmed that NEXAFS spectra are more sensitive to the identification of adsorption configurations. While the first characteristic peak in the low energy region of NEXAFS spectra are capable of distinguishing chemical bonds at the interface of the adsorption configurations. These results may facilitate a better understanding of the interface formations between biomolecules and silicon surfaces, which could be further utilized for the new bioelectronic device design.

The Influence of TiO2-Lignin Hybrid Fillers in Low-Density Polyethylene Composites on Photocatalytic Performance and UV-Barrier Properties.

The main objective of this study was to discover new packaging materials that could integrate one of the most expected properties, such as UV protection, with a self-cleaning ability defined as photocatalytic performance. Accordingly, new hybrid additives were used to transform LDPE films into materials with complex performance properties. In this study, titanium dioxide-lignin (TL) hybrid systems with a weight ratio of inorganic to organic precursors of 5-1, 1-1, and 1-5 were prepared using a mechanical method. The obtained materials and pristine components were characterized using measurement techniques and research methods, such as Fourier-transform infrared spectroscopy (FTIR), thermal stability analysis (TGA/DTG), measurement of the electrokinetic potential as a function of pH, scanning electron microscopy (SEM), and particle size distribution measurement. It was found that hydrogen bonds were formed between the organic and inorganic components, based on which the obtained systems were classified as class I hybrid materials. In the next step, inorganic-organic hybrid systems and pristine components were used as fillers for a low-density polyethylene (LDPE) composite, 5 and 10% by weight, in order to determine their impact on parameters such as tensile elongation at break. Polymer composites containing titanium dioxide in their matrix were then subjected to a test of photocatalytic properties, based on which it was found that all materials with TiO2 in their structure exhibit photocatalytic properties, whereby the best results were obtained for samples containing the TiO2-lignin hybrid system (1-1). The mechanical tests showed that the thin sheet films had a strong anisotropy due to chill-roll extrusion, ranging from 1.98 to 3.32. UV-Vis spectroscopy revealed four times higher light absorption for composites in which lignin was present than for pure LDPE, in the 250-450 nm range. On the other hand, the temperature at 5% and 30% weight loss revealed by TGA testing increased the highest performance for LDPE/TiO2 materials (by 20.4 °C and 8.7 °C, respectively).

Hydroxyapatite Nanorods Based Drug Delivery Systems for Bumetanide and Meloxicam, Poorly Water Soluble Active Principles.

Poorly water-soluble drugs represent a challenge for the pharmaceutical industry because it is necessary to find properly tuned and efficient systems for their release. In this framework, organic-inorganic hybrid systems could represent a promising strategy. A largely diffused inorganic host is hydroxyapatite (HAP, Ca10(PO4)6(OH)2), which is easily synthesized with different external forms and can adsorb different kinds of molecules, thereby allowing rapid drug release. Hybrid nanocomposites of HAP nanorods, obtained through hydrothermal synthesis, were prepared with two model pharmaceutical molecules characterized by low and pH-dependent solubility: meloxicam, a non-steroidal anti-inflammatory drug, and bumetanide, a diuretic drug. Both hybrids were physically and chemically characterized through the combined use of X-ray powder diffraction, scanning electron microscopy with energy-dispersive spectroscopy, differential scanning calorimetry, and infrared spectroscopy measurements. Then, their dissolution profiles and hydrophilicity (contact angles) in different media as well as their solubility were determined and compared to the pure drugs. This hybrid system seems particularly suitable as a drug carrier for bumetanide, as it shows higher drug loading and good dissolution profiles, while is less suitable for meloxicam, an acid molecule.

Anomalous Charge Transfer from Organic Ligands to Metal Halides in Zero-Dimensional [(C6H5)4P]2SbCl5 Enabled by Pressure-Induced Lone Pair-πInteraction.

Low-dimensional (low-D) organic metal halide hybrids (OMHHs) have emerged as fascinating candidates for optoelectronics due to their integrated properties from both organic and inorganic components. However, for most of low-D OMHHs, especially the zero-D (0D) compounds, the inferior electronic coupling between organic ligands and inorganic metal halides prevents efficient charge transfer at the hybrid interfaces and thus limits their further tunability of optical and electronic properties. Here, using pressure to regulate the interfacial interactions, efficient charge transfer from organic ligands to metal halides is achieved, which leads to a near-unity photoluminescence quantum yield (PLQY) at around 6.0 GPa in a 0D OMHH, [(C6H5)4P]2SbCl5. In situ experimental characterizations and theoretical simulations reveal that the pressure-induced electronic coupling between the lone-pair electrons of Sb3+ and the π electrons of benzene ring (lp-π interaction) serves as an unexpected "bridge" for the charge transfer. Our work opens a versatile strategy for the new materials design by manipulating the lp-π interactions in organic-inorganic hybrid systems.

Anomalous Charge Transfer from Organic Ligands to Metal Halides in Zero‐Dimensional [(C6H5)4P]2SbCl5 Enabled by Pressure‐Induced Lone Pair‐π Interaction

AbstractLow‐dimensional (low‐D) organic metal halide hybrids (OMHHs) have emerged as fascinating candidates for optoelectronics due to their integrated properties from both organic and inorganic components. However, for most of low‐D OMHHs, especially the zero‐D (0D) compounds, the inferior electronic coupling between organic ligands and inorganic metal halides prevents efficient charge transfer at the hybrid interfaces and thus limits their further tunability of optical and electronic properties. Here, using pressure to regulate the interfacial interactions, efficient charge transfer from organic ligands to metal halides is achieved, which leads to a near‐unity photoluminescence quantum yield (PLQY) at around 6.0 GPa in a 0D OMHH, [(C6H5)4P]2SbCl5. In situ experimental characterizations and theoretical simulations reveal that the pressure‐induced electronic coupling between the lone‐pair electrons of Sb3+ and the π electrons of benzene ring (lp‐π interaction) serves as an unexpected “bridge” for the charge transfer. Our work opens a versatile strategy for the new materials design by manipulating the lp‐π interactions in organic–inorganic hybrid systems.

Interfacial Passivation Enormously Enhances Electroluminescence of Triphenylphosphine Cu4 I4 Cube.

Defect is one of the key factors limiting optoelectronic performances of organic-inorganic hybrid systems. Although high-efficiency bidentate ligands based electroluminescent (EL) clusters reported, until present, only few EL clusters based on monodentate ligands are realized since their structural instability induces more surface/interface defects. Herein, this bottleneck is first overcome in virtue of interfacial passivation by electron transporting layers (ETL). Through using TmPyPB with meta-linked pyridines as ETL, photoluminescent (PL) and EL quantum efficiencies of the simplest monophosphine Cu4 I4 cube [TPP]4 Cu4 I4 are greatly improved by ≈2 and 23 folds, respectively, as well as ≈200 folds increased luminance, corresponding to a huge leap from nearly unlighted (<20 nits) to highly bright (>3000 nits). The passivation effect of TmPyPB on surface defects of cluster layer is embodied as preventing interfacial charge trapping and suppressing exciton nonradiation.

Enabling the Operation of Highly Compatible LiI‐3‐Hydroxypropionitrile Small‐Molecule Solid‐State Electrolytes in Lithium Metal Batteries via Stepped‐Amorphization Strategy

AbstractIntegrating the advantages of both inorganic ceramic and organic polymer solid‐state electrolytes, small‐molecule solid‐state electrolytes represented by LiI‐3‐hydroxypropionitrile (LiI‐HPN) inorganic–organic hybrid systems possess good interfacial compatibility and high modulus. However, their lack of intrinsic Li+ conduction ability hinders potential application in lithium metal batteries until now, despite containing LiI phase composition. Herein, inspired by evolution tendency of ionic conduction behaviors together with first‐principles molecular dynamics simulations, we propose a stepped‐amorphization strategy to break the Li+ conduction bottleneck of LiI‐HPN. It involves three progressive steps of composition (LiI‐content increasing), time (long‐time standing), and temperature (high‐temperature melting) regulations, to essentially construct a small‐molecule‐based composite solid‐state electrolyte with intensified amorphous degree, which realizes efficient conversion from an I− to Li+ conductor and improved conductivity. As a proof, the stepped‐optimized LiI‐HPN is successfully operated in lithium metal batteries cooperated with Li4Ti5O12 cathode to deliver considerable compatibility and stability over 250 cycles. This work not only clarifies the ionic conduction mechanisms of LiI‐HPN inorganic–organic hybrid systems, but also provides a reasonable strategy to broaden the application scenarios of highly compatible small‐molecule solid‐state electrolytes.

Enabling the Operation of Highly Compatible LiI-3-Hydroxypropionitrile Small-Molecule Solid-State Electrolytes in Lithium Metal Batteries via Stepped-Amorphization Strategy.

Integrating the advantages of both inorganic ceramic and organic polymer solid-state electrolytes, small-molecule solid-state electrolytes represented by LiI-3-hydroxypropionitrile (LiI-HPN) inorganic-organic hybrid systems possess good interfacial compatibility and high modulus. However, their lack of intrinsic Li+ conduction ability hinders potential application in lithium metal batteries until now, despite containing LiI phase composition. Herein, inspired by evolution tendency of ionic conduction behaviors together with first-principles molecular dynamics simulations, we propose a stepped-amorphization strategy to break the Li+ conduction bottleneck of LiI-HPN. It involves three progressive steps of composition (LiI-content increasing), time (long-time standing), and temperature (high-temperature melting) regulations, to essentially construct a small-molecule-based composite solid-state electrolyte with intensified amorphous degree, which realizes efficient conversion from an I- to Li+ conductor and improved conductivity. As a proof, the stepped-optimized LiI-HPN is successfully operated in lithium metal batteries cooperated with Li4 Ti5 O12 cathode to deliver considerable compatibility and stability over 250 cycles. This work not only clarifies the ionic conduction mechanisms of LiI-HPN inorganic-organic hybrid systems, but also provides a reasonable strategy to broaden the application scenarios of highly compatible small-molecule solid-state electrolytes.

Spiking neural networks compensate for weight drift in organic neuromorphic device networks

Organic neuromorphic devices can accelerate neural networks and integrate with biological systems. Devices based on the biocompatible and conductive polymer PEDOT:PSS are fast, require low amounts of energy and perform well in crossbar simulations. However, parasitic electrochemical reactions lead to self-discharge and the fading of the learned conductance states over time. This limits a neural network’s operating time and requires complex compensation mechanisms. Spiking neural networks (SNNs) take inspiration from biology to implement local and always-on learning. We show that these SNNs can function on organic neuromorphic hardware and compensate for self-discharge by continuously relearning and reinforcing forgotten states. In this work, we use a high-resolution charge transport model to describe the behavior of organic neuromorphic devices and create a computationally efficient surrogate model. By integrating the surrogate model into a Brian 2 simulation, we can describe the behavior of SNNs on organic neuromorphic hardware. A biologically plausible two-layer network for recognizing pixel MNIST images is trained and observed during self-discharge. The network achieves, for its size, competitive recognition results of up to 82.5%. Building a network with forgetful devices yields superior accuracy during training with 84.5% compared to ideal devices. However, trained networks without active spike-timing-dependent plasticity quickly lose their predictive performance. We show that online learning can keep the performance at a steady level close to the initial accuracy, even for idle rates of up to 90%. This performance is maintained when the output neuron’s labels are not revalidated for up to 24 h. These findings reconfirm the potential of organic neuromorphic devices for brain-inspired computing. Their biocompatibility and the demonstrated adaptability to SNNs open the path towards close integration with multi-electrode arrays, drug-delivery devices, and other bio-interfacing systems as either fully organic or hybrid organic-inorganic systems.

Pillararenes as Promising Carriers for Drug Delivery.

Since their discovery in 2008 by N. Ogoshi and co-authors, pillararenes (PAs) have become popular hosts for molecular recognition and supramolecular chemistry, as well as other practical applications. The most useful property of these fascinating macrocycles is their ability to accommodate reversibly guest molecules of various kinds, including drugs or drug-like molecules, in their highly ordered rigid cavity. The last two features of pillararenes are widely used in various pillararene-based molecular devices and machines, stimuli-responsive supramolecular/host-guest systems, porous/nonporous materials, organic-inorganic hybrid systems, catalysis, and, finally, drug delivery systems. In this review, the most representative and important results on using pillararenes for drug delivery systems for the last decade are presented.

Electronic Structure and Photoactivity of Organoarsenic Hybrid Polyoxometalates

Organofunctionalization of polyoxometalates (POMs) allows the preparation of hybrid molecular systems with tunable electronic properties. Currently, there are only a handful of approaches that allow for the fine-tuning of POM frontier molecular orbitals in a predictable manner. Herein, we demonstrate a new functionalization method for the Wells-Dawson polyoxotungstate [P2W18O62]6- using arylarsonic acids which enables modulation of the redox and photochemical properties. Arylarsonic groups facilitate orbital mixing between the organic and inorganic moieties, and the nature of the organic substituents significantly impacts the redox potentials of the POM core. The photochemical response of the hybrid POMs correlates with their computed and experimentally estimated lowest unoccupied molecular orbital energies, and the arylarsonic hybrids are found to exhibit increased visible light photosensitivity comparable with that of arylphosphonic analogues. Arylarsonic hybridization offers a route to stable and tunable organic-inorganic hybrid systems for a range of redox and photochemical applications.

Nanocrystalline CaWO4 and ZnWO4 Tungstates for Hybrid Organic-Inorganic X-ray Detectors.

Hybrid materials combining an organic matrix and high-Z nanomaterials show potential for applications in radiation detection, allowing unprecedented device architectures and functionality. Herein, novel hybrid organic-inorganic systems were produced using a mixture of tungstate (CaWO4 or ZnWO4) nanoparticles with a P3HT:PCBM blend. The nano-tungstates with a crystallite size of 43 nm for CaWO4 and 30 nm for ZnWO4 were synthesized by the hydrothermal method. Their structure and morphology were characterized by X-ray diffraction and scanning electron microscopy. The hybrid systems were used to fabricate direct conversion X-ray detectors able to operate with zero bias voltage. The detector performance was tested in a wide energy range using monochromatic synchrotron radiation. The addition of nanoparticles with high-Z elements improved the detector response to X-ray radiation compared with that of a pure organic P3HT:PCBM bulk heterojunction cell. The high dynamic range of our detector allows for recording X-ray absorption spectra, including the fine X-ray absorption structure located beyond the absorption edge. The obtained results suggest that nanocrystalline tungstates are promising candidates for application in direct organic-inorganic X-ray detectors.

Stability of Metal Hydroxide Organic Frameworks for Oxygen Evolution

The oxygen evolution reaction (OER) is central to storing electrical energy via chemical bonds in energy carriers and fuels through reactions such as electrochemical water splitting to produce hydrogen, CO2 reduction for CO and liquid hydrocarbons, and nitrogen to ammonia. While there has been considerable work towards the engineering of inexpensive yet highly active OER catalysts, current state-of-the-art materials are still at least an order of magnitude less active than oxygen evolving complexes found in biological systems that intricately combine inorganic metal-oxo clusters with organic ligands.1 As a result, metal organic frameworks (MOFs) have drawn considerable attention as hybrid organic-inorganic systems that can potentially mimic the unique structure of biological oxygen evolving complexes. Recently, metal hydroxide organic frameworks (MHOFs),2 a new class of MOFs that combine layered hydroxides with aromatic carboxylate linkers that stabilize the structure via π-π interactions, have been shown to display three times the tunability of layered hydroxides, offering extensive opportunities for further engineering of its electrochemical properties for numerous applications. However, the long-term stability of these material during OER is still unclear, which would be paramount to understand for further rational design of this class of material.In this study, we investigated Ni-based MHOFs with carboxylate linkers of varying π-π interaction strengths to understand how these differences affect the electrochemical stability of these materials during OER. We observed that the MHOFs all undergo activation during OER leading to two orders of magnitude increase in OER activity, where the MHOFs with weaker π-π interaction strengths tend to transform at a faster rate than the MHOFs with stronger π-π interaction strengths. We further characterized the MHOFs using a wide range of analytical techniques, including scanning transmission electron microscopy, Raman spectroscopy, x-ray photoelectron spectroscopy, and hard x-ray absorption spectroscopy, before and after extended OER cycling and galvanostatic tests to understand the transformed phase, which suggested that while the bulk structure largely remains unchanged, the surface undergoes significant restructuring into a Ni(OH)2-like phase during OER. Using operando UV-vis and Raman spectroscopy measurements on the MHOFs during OER to understand the factors that induce the transformation process, we found that there was a clear link between the Ni2+/3+, 4+ redox couple observed around 1.4 VRHE and a loss in the carboxylate organic linkers for the linkers with weak π-π interactions. However, for the MHOFs synthesized with linkers exhibiting strong π-π interaction strengths, there were smaller changes to the overall material during OER, suggesting that the bulk stability of these materials is largely dictated by the linker interaction strength and activation are primarily only surface transformations. These results directly demonstrate that linker selection also plays a key role in the stability MOFs under electrochemical conditions and are pertinent for rational design and understanding of the stability and activity of hybrid organic-inorganic materials as electrocatalysts.

Drug-Inclusive Inorganic-Organic Hybrid Systems for the Controlled Release of the Osteoporosis Drug Zoledronate.

Bisphosphonates (BPs) are common pharmaceutical treatments used for calcium- and bone-related disorders, the principal one being osteoporosis. Their antiresorptive action is related to their high affinity for hydroxyapatite, the main inorganic substituent of bone. On the other hand, the phosphonate groups on their backbone make them excellent ligands for metal ions. The combination of these properties finds potential application in the utilization of such systems as controlled drug release systems (CRSs). In this work, the third generation BP drug zoledronate (ZOL) was combined with alkaline earth metal ions (e.g., Sr2+ and Ba2+) in an effort to synthesize new materials. These metal–ZOL compounds can operate as CRSs when exposed to appropriate experimental conditions, such as the low pH of the human stomach, thus releasing the active drug ZOL. CRS networks containing Sr2+ or Ba2 and ZOL were physicochemically and structurally characterized and were evaluated for their ability to release the free ZOL drug during an acid-driven hydrolysis process. Various release and kinetic parameters were determined, such as initial rates and release plateau values. Based on the drug release results of this study, there was an attempt to correlate the ZOL release efficiency with the structural features of these CRSs.

(Invited) Novel Acene-Based Molecules and Materials for Singlet Fission

Singlet fission (SF) is a multi-exciton generation process in two neighboring organic chromophores (S1 + S0) where two individual triplet excitons (T1 + T1) are generated from one-photon absorption through a correlated triplet pair (TT). Therefore, SF is highly promising for construction of next-generation light energy conversion systems and quantum information science. In addition to the close interaction of two neighboring chromophores, energy-level matching condition between a singlet and two triplet states: [E(S1) ≥ 2E(T1)] are required for efficient SF.Observation of SF was widely discussed under various condition such as solid-state films and covalently-linked molecular dimers in homogeneous solution. In contrast, inorganic nanomaterials such as quantum dots and metal nanoclusters demonstrated the characteristic optical and electrochemical properties as compared to organic molecules. However, the number of organic-inorganic hybrid systems for efficient SF is extremely limited.1-3 Furthermore, there are no reports regarding SF systems using liquid molecules.4 In this presentation, we present our recent research results regarding novel acene-based molecules and materials for SF. References Sakai, H.; Inaya, R.; Tkachenko, N. V.; Hasobe, T. Chem. Eur. J. 2018, 24, 17062-17071. Saegusa, T.; Sakai, H.; Nagashima, H.; Kobori, Y.; Tkachenko, N. V.; Hasobe, T. J. Am. Chem. Soc. 2019, 141, 14720-14727. Zhang, J.; Sakai, H.; Suzuki, K.; Hasobe, T.; Tkachenko, N. V.; Chang, I. Y.; Hyeon-Deuk, K.; Kaji, H.; Teranishi, T.; Sakamoto, M. J. Am. Chem. Soc. 2021, 143, 17388-17394. Yoshino, K.; Sakai, H.; Shoji, Y.; Kajitani, T.; Anetai, H.; Akutagawa, T.; Fukushima, T.; Tkachenko, N. V.; Hasobe, T. J. Phys. Chem. B 2020, 124, 11910-11918.

Structural Rationale towards Designing Coordination Polymer Based Metallogels Displaying Anti‐Cancer and Anti‐Bacterial Properties

AbstractA new series of organic‐inorganic‐hybrid‐systems (OIHS) was synthesized with the aim of developing metallogels that might display ‘drug‐like’ function. Reaction of two dicarboxylate ligands namely 3‐carboxycinnamic acid (3‐cca) and 4‐carboxycinnamic acid (4‐cca) with various bivalent metal ions (Cu(II), Zn(II), Co(II), Cd(II), Mn(II)) produced a new series of OIHS which were crystallographically characterized; five of which were coordination polymers (CP1‐CP5) and one metal‐organic polyhedra (MOP‐1). Reaction of 3‐cca with various metal ions in presence of DMSO/water produced five metallogels (MG1‐MG5) of which the Zn(II)‐metallogel namely MG1 was evaluated for both anti‐cancer and anti‐bacterial properties against murine tumor cell line B16‐F10 (human skin cancer model) and gram positive bacterium S. aureus. While MTT and cell migration assays established the anti‐cancer activity of MG1 against B16‐F10, flow cytometry and laser scanning confocal microscopy (LSCM) images under various staining conditions supported apoptotic pathway of cancer cell death. Anti‐bacterial ability of MG1 was also established against S. aureus by zone inhibition, and flow cytometry and LSCM studies under various staining conditions. MG1 was also demonstrated to be effective in killing the intracellular bacterial cells when B16‐F10 cells were infected with S. aureus thereby suggesting its potential in treating post‐operative cancer surgery model system.

A self-powered solar-blind photodetector based on polyaniline/α-Ga2O3 p–n heterojunction

In this work, we demonstrated the self-powered solar-blind photodetector based on a polyaniline/α-Ga2O3 hybrid heterojunction. The resultant device exhibited distinct self-power characteristics with a peak photoresponsivity (R) of 8.2 mA/W, a UVC (UV light of wavelength range at 200–280 nm)/UVA (UV light of wavelength range at 320–400 nm) rejection ratio (R220 nm/R400 nm) of 2.97 × 104, and a response decay time (τdec) of 176 μs at zero bias. With an elevated bias to 5 V, the dark current remained in an ultralow level of 0.21 pA, while the rejection ratio and τdec were improved to be 7.13 × 104 and 153 μs, respectively, together with the corresponding external quantum efficiency of 38.4% and a detectivity of 6.63 × 1013 Jones. Thanks to the dual functions of bandpass transmission in the deep-ultraviolet spectral region and the hole spreading transport of the polyaniline layer, the responsivity to the visible light is suppressed with the negligible internal photoemission effect, thus leading to the improved rejection ratio. Furthermore, weak interface interactions in such polyaniline/α-Ga2O3 organic–inorganic hybrid systems avoid the introduction of interfacial trapping centers by lattice mismatch and the stabilization of negatively charged anions (O2−) by (−NH2)-+species in polyaniline deactivate oxygen vacancies at the α-Ga2O3 surface, both of which lead to the negligible persistent photoconductivity effect. As a result, in the aid of the interfacial built-in field, the constructed hybrid heterojunction exhibited a self-powered detecting characteristic and a fast response speed. These findings verify the feasibility of delivering high performance photodetectors by implementing the inorganic/organic hybrid bipolar device design to overcome the difficulty in p-type Ga2O3.

A sustainable molybdenum oxysulphide-cobalt phosphate photocatalyst for effectual solar-driven water splitting

IntroductionHydrogen is considered as a clean alternative green energy future fuel. Since the Honda-Fujishima effect for photoelectrochemical water splitting is known, there has been a substantial boost in this field. Numerous photocatalysts based on metals, semiconductors, and organic-inorganic hybrid-systems have been proposed. Several factors limit their efficiency, e.g., a stable PEC-WS setup, absorbing visible light, well-aligned band energy for charge transfer, electrons and holes, and their separation to avoid recombination and limited water redox reactions. Metallic doping and impregnation of stable and efficient co-catalysts such as Pt, Ag, and Au showed enhanced PEC-WS. We used Cobalt-based co-catalyst with molybdenum oxysulfide photocatalyst for effectual solar-driven water splitting. ObjectivesTo develop photocatalysts for efficient PEC processes capable of absorbing sufficient visible light, good band energy for effective charge transfer, inexpensive, significant solar-to-chemical energy conversion efficiencies. Above all, it is developing such PEC-WS systems that will be commercially viable for renewable energy resources. MethodsWe prepared Molybdenum oxysulphide-cobalt phosphate photocatalyst for PEC-WS through a facile hydrothermal route using ammonium heptamolybdate, thiourea, and metallic Cobalt precursors. ResultsAn effectual photocatalyst is produced for solar-driven water splitting. The conformal morphology of MoOxSy-CoPi nanoflowers is a significant feature, as observed under FE-SEM and HR-TEM. XRD confirmed the degree of purity and orthorhombic crystal structure of MoOxSy-CoPi. EDX and XPS identify the elemental compositions and corresponding oxidation states of each atom. A 2.44 eV band-gap energy is calculated for MoOxSy-CoPi from the diffused reflectance spectrum. Photo- Electrochemical Studies (PEC) under 1-SUN solar irradiation revealed 7-8 folds enhanced photocurrent (∼ 3.5 mA/cm2) generated from MoOxSy-CoPi/FTO in comparison to Co-PI/FTO (∼ 0.5 mA/cm2) and MoOxSy-/FTO respectively, within 0.5 M Na2SO4 electrolyte (@pH=7) and standard three electrodes electrochemical cell. ConclusionOur results showed MoOxSy-CoPi as promising photocatalyst material for improved solar-driven photoelectrochemical water splitting system.