Phthalocyanine Grafting Strategy Induces Strong Intrinsic Electric Fields and Molecule-Edge Carrier Transport Pathways for Photoelectrochemical Water Splitting.

Limited charge separation, slow charge mobility, and high electron-hole recombination rates remain critical challenges impeding the efficiency of photoelectrochemical (PEC) water splitting. More regrettably, the charge transfer pathways within bulk charge transport are not yet fully understood, and the development of effective strategies to design these pathways remains a significant challenge. Herein, by optimizing the anchoring sites of small molecular ligands, we developed a molecularly functionalized layer, 4-ethyl-carbazole copper phthalocyanine (4EtCz-Pc), which is characterized by a strong dipole moment, a large internal electric field, and surprisingly positive electrostatic potential at the edge.

Tailoring the special hole transfer layer between BiVO and oxygen evolution co-catalysts interfaces for boosting photoelectrochemical water splitting.

Tailoring the hole transport layer (HTL) between BiVO (BVO) and oxygen evolution co-catalysts (OECs) interfaces is a leading strategy to improve the performance of photoelectrochemical (PEC) water splitting. Nevertheless, the limited driving force at the BVO/OECs interfaces severely hinders the transport of charge carriers. In this study, we designed a specialized defective transition metal oxide (Vo-MnO) as the HTL.

Infrared Electrochemiluminescence from A Water-Soluble Anion-π Emitter for Sensitive Perfluorooctanoic Acid Sensing.

Electrochemiluminescence (ECL) analysis stands out among various analytical methods due to its exceptional sensitivity and accuracy. However, the poor solubility of most ECL probes limits their effectiveness in aqueous environments. To address this challenge, we developed a water-soluble anion-π ECL luminophore, DPBC-OTS.

Insight into the charge transfer behavior of an electrochemiluminescence sensor based on porphyrin-coumarin derivatives with a donor-acceptor configuration.

The excellent photophysical and electrochemical properties of porphyrins have inspired widespread interest in the realm of electrochemiluminescence (ECL). The aggregation-caused deficiency of ECL emission in aqueous solution, however, still severely impedes further applications. Herein, a molecule with a donor-acceptor (D-A) configuration, ATPP-Cou, consisting of monoaminoporphyrin as an electron donor and coumarin as an electron acceptor, was designed as an ECL luminophore to address the susceptibility of the porphyrin to aggregation-caused quenching (ACQ) in aqueous solution.

Synthesis and symmetry of perovskite oxynitride CaW(O,N).

Perovskite oxynitrides, in addition to being promising electrocatalysts and photoabsorbers, present an interesting case study in crystal symmetry. Full or partial ordering of the O and N anions affects global symmetry and influences material performance and functionality; however, anion ordering is challenging to detect experimentally. In this work, we synthesize a novel perovskite oxynitride CaW(O,N) and characterize its crystal structure using both X-ray and neutron diffraction.

Unveiling the Influence of Sulfur Doping on Photoelectrochemical Performance in BiVO/FeOOH Heterostructures.

BiVO is a promising photoanode for photoelectrochemical (PEC) water splitting but suffers from high charge carrier recombination and sluggish surface water oxidation kinetics that limit its efficiency. In this work, a model of sulfur-incorporated FeOOH cocatalyst-loaded BiVO was constructed. The composite photoanode (BiVO/S-FeOOH) demonstrates an enhanced photocurrent density of 3.

Fast Interfacial Carrier Dynamics Modulated by Bidirectional Charge Transport Channels in ZnIn S -based Composite Photoanodes Probed by Scanning Photoelectrochemical Microscopy.

Limited charge separation/transport efficiency remains the primary obstacle of achieving satisfying photoelectrochemical (PEC) water splitting performance. Therefore, it is essential to develop diverse interfacial engineering strategies to mitigate charge recombination. Despite obvious progress having been made, most works only considered a single-side modulation in either the electrons of conduction band or the holes of valence band in a semiconductor photoanode, leading to a limited PEC performance enhancement.

Iridium-Incorporated Strontium Tungsten Oxynitride Perovskite for Efficient Acidic Hydrogen Evolution.

Heteroanionic materials exhibit great structural diversity with adjustable electronic, magnetic, and optical properties that provide immense opportunities for materials design. Within this material family, perovskite oxynitrides incorporate earth-abundant nitrogen with differing size, electronegativity, and charge into oxide, enabling a unique approach to tuning metal-anion covalency and energy of metal cation electronic states, thereby achieving functionality that may be inaccessible from their perovskite oxide counterparts, which have been widely studied as electrocatalysts. However, it is very challenging to directly obtain such materials due to the poor thermal stability of late transition metals coordinated with N and/or at high valence states.

Ultrafast Preparation of Nonequilibrium FeNi Spinels by Magnetic Induction Heating for Unprecedented Oxygen Evolution Electrocatalysis.

Carbon-supported nanocomposites are attracting particular attention as high-performance, low-cost electrocatalysts for electrochemical water splitting. These are mostly prepared by pyrolysis and hydrothermal procedures that are time-consuming (from hours to days) and typically difficult to produce a nonequilibrium phase. Herein, for the first time ever, we exploit magnetic induction heating-quenching for ultrafast production of carbon-FeNi spinel oxide nanocomposites (within seconds), which exhibit an unprecedentedly high performance towards oxygen evolution reaction (OER), with an ultralow overpotential of only +260 mV to reach the high current density of 100 mA cm.

Theory-Guided Regulation of FeN Spin State by Neighboring Cu Atoms for Enhanced Oxygen Reduction Electrocatalysis in Flexible Metal-Air Batteries.

Iron, nitrogen-codoped carbon (Fe-N-C) nanocomposites have emerged as viable electrocatalysts for the oxygen reduction reaction (ORR) due to the formation of FeN C coordination moieties. In this study, results from first-principles calculations show a nearly linear correlation of the energy barriers of key reaction steps with the Fe magnetic moment. Experimentally, when single Cu sites are incorporated into Fe-N-C aerogels (denoted as NCAG/Fe-Cu), the Fe centers exhibit a reduced magnetic moment and markedly enhanced ORR activity within a wide pH range of 0-14.

Oxygen Reduction Reaction Catalyzed by Carbon-Supported Platinum Few-Atom Clusters: Significant Enhancement by Doping of Atomic Cobalt.

Oxygen reduction reaction (ORR) plays an important role in dictating the performance of various electrochemical energy technologies. As platinum nanoparticles have served as the catalysts of choice towards ORR, minimizing the cost of the catalysts by diminishing the platinum nanoparticle size has become a critical route to advancing the technological development. Herein, first-principle calculations show that carbon-supported Pt clusters represent the threshold domain size, and the ORR activity can be significantly improved by doping of adjacent cobalt atoms.

Nanowrinkled Carbon Aerogels Embedded with FeN Sites as Effective Oxygen Electrodes for Rechargeable Zinc-Air Battery.

Rational design of single-metal atom sites in carbon substrates by a flexible strategy is highly desired for the preparation of high-performance catalysts for metal-air batteries. In this study, biomass hydrogel reactors are utilized as structural templates to prepare carbon aerogels embedded with single iron atoms by controlled pyrolysis. The tortuous and interlaced hydrogel chains lead to the formation of abundant nanowrinkles in the porous carbon aerogels, and single iron atoms are dispersed and stabilized within the defective carbon skeletons.

An Efficient Strategy for Boosting Photogenerated Charge Separation by Using Porphyrins as Interfacial Charge Mediators.

Surface recombination at the photoanode/electrolyte junction seriously impedes photoelectrochemical (PEC) performance. Through coating of photoanodes with oxygen evolution catalysts, the photocurrent can be enhanced; however, current systems for water splitting still suffer from high recombination. We describe herein a novel charge transfer system designed with BiVO as a prototype.

Oxygen Reduction Reaction Catalyzed by Black-Phosphorus-Supported Metal Nanoparticles: Impacts of Interfacial Charge Transfer.

Development of effective catalysts for oxygen reduction reaction (ORR) plays a critical role in the applications of a range of electrochemical energy technologies. In this study, thin-layered black phosphorus (TLBP) was used as a unique supporting substrate for the deposition of metal nanoparticles (MNPs, M = Pt, Ag, Au), and the resulting M-TLBP nanocomposites were found to exhibit apparent ORR activity that was readily manipulated by interfacial charge transfer from TLBP to MNPs. This was confirmed by results from X-ray photoelectron spectroscopic measurements and density functional theory calculations.

Ruthenium atomically dispersed in carbon outperforms platinum toward hydrogen evolution in alkaline media.

Hydrogen evolution reaction is an important process in electrochemical energy technologies. Herein, ruthenium and nitrogen codoped carbon nanowires are prepared as effective hydrogen evolution catalysts. The catalytic performance is markedly better than that of commercial platinum catalyst, with an overpotential of only -12 mV to reach the current density of 10 mV cm in 1 M KOH and -47 mV in 0.

Point of Anchor: Impacts on Interfacial Charge Transfer of Metal Oxide Nanoparticles.

Photoinduced charge transfer across the metal oxide-organic ligand interface plays a key role in the diverse applications of metal oxide nanomaterials/nanostructures, such as photovoltaics, photocatalysis, and optoelectronics. Thus far, most studies are focused on molecular engineering of the organic chromophores, where the charge-transfer properties have been found to dictate the photo absorption efficiency and eventual device performance. Yet, as the chromophores are mostly bound onto the metal oxide surfaces by hydroxyl or carboxyl anchors, the impacts of the bonding interactions at the metal oxide-ligand interface on interfacial charge transfer have remained largely unexplored.

Carbon-Supported Single Atom Catalysts for Electrochemical Energy Conversion and Storage.

Single atoms of select transition metals supported on carbon substrates have emerged as a unique system for electrocatalysis because of maximal atom utilization (≈100%) and high efficiency for a range of reactions involved in electrochemical energy conversion and storage, such as the oxygen reduction, oxygen evolution, hydrogen evolution, and CO reduction reactions. Herein, the leading strategies for the preparation of single atom catalysts are summarized, and the electrocatalytic performance of the resulting samples for the various reactions is discussed. In general, the carbon substrate not only provides a stabilizing matrix for the metal atoms, but also impacts the electronic density of the metal atoms due to strong interfacial interactions, which may lead to the formation of additional active sites by the adjacent carbon atoms and hence enhanced electrocatalytic activity.

Impacts of interfacial charge transfer on nanoparticle electrocatalytic activity towards oxygen reduction.

Polymer electrolyte membrane fuel cells represent a next-generation power supply technology that may be used in a diverse range of applications. Towards this end, the rational design and engineering of functional nanomaterials as low-cost, high-performance catalysts is of critical significance in the wide-spread commercialization of fuel cell technology. One major bottleneck is the oxygen reduction reaction (ORR) at the cathode.

Recycling nanowire templates for multiplex templating synthesis: a green and sustainable strategy.

Template-directed synthesis of nanostructures has been emerging as one of the most important synthetic methodologies. A pristine nanotemplate is usually chemically transformed into other compounds and sacrificed after templating or only acts as an inert physical template to support the new components. If a nanotemplate is costly or toxic as waste, to recycle such a nanotemplate becomes highly desirable.

Effects of surface charges of graphene oxide on neuronal outgrowth and branching.

Graphene oxides with different surface charges were fabricated from carboxylated graphene oxide by chemical modification with amino- (-NH2), poly-m-aminobenzene sulfonic acid- (-NH2/-SO3H), or methoxyl- (-OCH3) terminated functional groups. The chemically functionalized graphene oxides and the carboxylated graphene oxide were characterized by infrared spectroscopy, X-ray photoelectron spectroscopy, UV-Vis spectrometry, ζ potential measurements, field emission scanning electron microscopy, and contact angle analyses. Subsequently, the resulting graphene oxides were used as substrates for culturing primary rat hippocampal neurons to investigate neurite outgrowth and branching.

A valuable visual colorimetric and electrochemical biosensor for porphyrin.

Porphyrin is able to specifically combine with phosphorus, thus a novel bifunctional sensing platform for determination of porphyrin by visual colorimetry and electrochemistry was demonstrated. A pretreated gold sheet (or electrode) with 2-mercatpoethanol (2-ME) was chemically modified by POCl(3) to obtain the surface phosphate active sites. The different stages of modified electrode were characterized by electrochemical impedance spectroscopy (EIS).