Recent advances in metal halide perovskite based photocatalysts for artificial photosynthesis and organic transformations.

Metal halide perovskites (MHP) emerged as highly promising materials for photocatalysis, offering significant advancements in the degradation of soluble and airborne pollutants, as well as the transformation of functional organic compounds. This comprehensive review focuses on recent developments in MHP-based photocatalysts, specifically examining two major categories: lead-based (such as CsPbBr3) and lead-free variants (e.g. Cs2AgBiX6, Cs3Bi2Br9 and others). While the review briefly discusses the contributions of MHPs to hydrogen (H2) production and carbon dioxide (CO2) reduction, the main emphasis is on the design principles that determine the effectiveness of perovskites in facilitating organic reactions and degrading hazardous chemicals through oxidative transformations. Furthermore, the review addresses the key factors that influence the catalytic efficiency of perovskites, including charge recombination, reaction mechanisms involving free radicals, hydroxyl ions, and other ions, as well as phase transformation and solvent compatibility. By offering a comprehensive overview, this review aims to serve as a guide for the design of MHP-based photocatalysis and shed light on the common challenges faced by the scientific community in the domain of organic transformations.

Pt1.8Pd0.2CuGa Intermetallic Nanocatalysts with Enhanced Methanol Oxidation Performance for Efficient Hybrid Seawater Electrolysis.

Seawater electrolysis is a potentially cost-effective approach to green hydrogen production, but it currently faces substantial challenges for its high energy consumption and the interference of chlorine evolution reaction (ClER). Replacing the energy-demanding oxygen evolution reaction with methanol oxidation reaction (MOR) represents a promising alternative, as MOR occurs at a significantly low anodic potential, which cannot only reduce the voltage needed for electrolysis but also completely circumvents ClER. To this end, developing high-performance MOR catalysts is a key. Herein, a novel quaternary Pt1.8Pd0.2CuGa/C intermetallic nanoparticle (i-NP) catalyst is reported, which shows a high mass activity (11.13 A mgPGM -1), a large specific activity (18.13 mA cmPGM -2), and outstanding stability toward alkaline MOR. Advanced characterization and density functional theory calculations reveal that the introduction of atomically distributed Pd in Pt2CuGa intermetallic markedly promotes the oxidation of key reaction intermediates by enriching electron concentration around Pt sites, resulting in weak adsorption of carbon-containing intermediates and favorable adsorption of synergistic OH- groups near Pd sites. MOR-assisted seawater electrolysis is demonstrated, which continuously operates under 1.23 V for 240 h in simulated seawater and 120 h in natural seawater without notable degradation.

Strategies for Semiconductor/Electrocatalyst Coupling toward Solar-Driven Water Splitting.

Hydrogen (H2) has a significant potential to enable the global energy transition from the current fossil-dominant system to a clean, sustainable, and low-carbon energy system. While presently global H2 production is predominated by fossil-fuel feedstocks, for future widespread utilization it is of paramount importance to produce H2 in a decarbonized manner. To this end, photoelectrochemical (PEC) water splitting has been proposed to be a highly desirable approach with minimal negative impact on the environment. Both semiconductor light-absorbers and hydrogen/oxygen evolution reaction (HER/OER) catalysts are essential components of an efficient PEC cell. It is well documented that loading electrocatalysts on semiconductor photoelectrodes plays significant roles in accelerating the HER/OER kinetics, suppressing surface recombination, reducing overpotentials needed to accomplish HER/OER, and extending the operational lifetime of semiconductors. Herein, how electrocatalyst coupling influences the PEC performance of semiconductor photoelectrodes is outlined. The focus is then placed on the major strategies developed so far for semiconductor/electrocatalyst coupling, including a variety of dry processes and wet chemical approaches. This Review provides a comprehensive account of advanced methodologies adopted for semiconductor/electrocatalyst coupling and can serve as a guideline for the design of efficient and stable semiconductor photoelectrodes for use in water splitting.

Vapor-solid synthesis of monolithic single-crystalline CoP nanowire electrodes for efficient and robust water electrolysis.

Electrochemical water splitting into hydrogen and oxygen is a promising technology for sustainable energy storage. The development of earth-abundant transition metal phosphides (TMPs) to catalyze the hydrogen evolution reaction (HER) and TMP-derived oxy-hydroxides to catalyze the oxygen evolution reaction (OER) has recently drawn considerable attention. However, most monolithically integrated metal phosphide electrodes are prepared by laborious multi-step methods and their operational stability at high current densities has been rarely studied. Herein, we report a novel vapor-solid synthesis of single-crystalline cobalt phosphide nanowires (CoP NWs) on a porous Co foam and demonstrate their use in overall water splitting. The CoP NWs grown on the entire surface of the porous Co foam ligaments have a large aspect ratio, and hence are able to provide a large catalytically accessible surface over a given geometrical area. Comprehensive investigation shows that under the OER conditions CoP NWs are progressively and conformally converted to CoOOH through electrochemical in situ oxidation/dephosphorization; the latter serving as an active species to catalyze the OER. The in situ oxidized electrode shows exceptional electrocatalytic performance for the OER in 1.0 M KOH, delivering 100 mA cm-2 at an overpotential (η) of merely 300 mV and a small Tafel slope of 78 mV dec-1 as well as excellent stability at various current densities. Meanwhile, the CoP NW electrode exhibits superior catalytic activity for the HER in the same electrolyte, affording -100 mA cm-2 at η = 244 mV and showing outstanding stability. An alkaline electrolyzer composed of two symmetrical CoP NW electrodes can deliver 10 and 100 mA cm-2 at low cell voltages of 1.56 and 1.78 V, respectively. The CoP NW electrolyzer demonstrates exceptional long-term stability for overall water splitting, capable of working at 20 and 100 mA cm-2 for 1000 h without obvious degradation.

One-Step Fabrication of Monolithic Electrodes Comprising Co9 S8 Particles Supported on Cobalt Foam for Efficient and Durable Oxygen Evolution Reaction.

A very easy and cost-effective approach to the fabrication of monolithic Co9 S8 water oxidation electrodes (Co@Co9 S8 ), fabricated by one-step hydrothermal treatment of commercially available cobalt foam in the presence of thiourea, is reported. The morphology, crystal structure, microstructure, and composition of as-fabricated Co@Co9 S8 electrodes were examined by using scanning electron microscopy (SEM), powder X-ray diffractometry (XRD), transmission electron microscope (TEM), and X-ray photoelectron spectroscopy (XPS), and their electrochemical properties were investigated by cyclic voltammetry (CV), chronopotentiometry (CP), chronoamperometry (CA), and electrochemical impedance spectroscopy (EIS). When used to catalyze the oxygen evolution reaction (OER) in alkaline solution, the Co@Co9 S8 electrode with an optimal Co9 S8 loading exhibits outstanding catalytic activity, requiring a low overpotential of 350 mV to deliver an anodic current density of 10 mA cm-2 and showing fast kinetics for OER with a small Tafel slope (55 mV dec-1 ) and charge-transfer resistance (0.44â€…Ω cm-2 ), which outperforms many sulfide-based OER catalysts and some state-of-the-art noble metal catalysts recently reported in the literature. Importantly, the electrodes show excellent long-term stability, and are capable of operating at both a low current density and a high current density relevant to industrial water electrolysis up to 100 hours.

Chemically induced porosity on BiVO4 films produced by double magnetron sputtering to enhance the photo-electrochemical response.

Double magnetron sputtering (DMS) is an efficient system that is well known because of its precise control of the thin film synthesizing process over any kind of substrate. Here, DMS has been adopted to synthesize BiVO4 films over a conducting substrate (FTO), using metallic vanadium and ceramic Bi2O3 targets simultaneously. The films were characterized using different techniques, such as X-ray diffraction (XRD), UV-Vis spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM) and profilometry. The photo-electrochemical analysis was performed using linear scan voltammetry, chronoamperometry and electrochemical impedance spectroscopy (EIS) under the illumination of simulated solar light at 1 Sun. The photocurrent density of the sputtered BiVO4 thin films could be improved from 0.01 mA cm(-2) to 1.19 mA cm(-2) at 1.23 V vs. RHE by chemical treatment using potassium hydroxide (KOH). The effect of KOH was the removal of impurities from the grain boundaries, leading to a more porous structure and more pure crystalline monoclinic BiVO4 particles. Such variations in the microstructure as well as the improvement of the charge transfer properties of the BiVO4 film after the KOH treatment were confirmed and studied in depth by EIS analysis.

Facile biofunctionalization of silver nanoparticles for enhanced antibacterial properties, endotoxin removal, and biofilm control.

Infectious diseases cause a huge burden on healthcare systems worldwide. Pathogenic bacteria establish infection by developing antibiotic resistance and modulating the host's immune system, whereas opportunistic pathogens like Pseudomonas aeruginosa adapt to adverse conditions owing to their ability to form biofilms. In the present study, silver nanoparticles were biofunctionalized with polymyxin B, an antibacterial peptide using a facile method. The biofunctionalized nanoparticles (polymyxin B-capped silver nanoparticles, PBSNPs) were assessed for antibacterial activity against multiple drug-resistant clinical strain Vibrio fluvialis and nosocomial pathogen P. aeruginosa. The results of antibacterial assay revealed that PBSNPs had an approximately 3-fold higher effect than the citrate-capped nanoparticles (CSNPs). Morphological damage to the cell membrane was followed by scanning electron microscopy, testifying PBSNPs to be more potent in controlling the bacterial growth as compared with CSNPs. The bactericidal effect of PBSNPs was further confirmed by Live/Dead staining assays. Apart from the antibacterial activity, the biofunctionalized nanoparticles were found to resist biofilm formation. Electroplating of PBSNPs onto stainless steel surgical blades retained the antibacterial activity against P. aeruginosa. Further, the affinity of polymyxin for endotoxin was exploited for its removal using PBSNPs. It was found that the prepared nanoparticles removed 97% of the endotoxin from the solution. Such multifarious uses of metal nanoparticles are an attractive means of enhancing the potency of antimicrobial agents to control infections.