Efficient biological funneling of lignin into 2-pyrone-4,6-dicarboxylic acid via electrocatalytic depolymerization and genetically engineered Pseudomonas putida KT2440.

Lignin has been an abundant biomass resource with remarkable potential to produce value-added chemicals. The comprehensive process from lignin degradation to the biological conversion of its monomers remains a challenge for demonstrating the industrial applicability of lignin refinery. Herein, Pseudomonas putida KT-PDCV overexpressing homologous vanillate-O-methylase (VanAB) could efficiently produce 2-pyrone-4,6-dicarboxylic acid (PDC) from lignin-derived compounds (LDC), including S-unit monomers (e.

A hole-selective hybrid TiO layer for stable and low-cost photoanodes in solar water oxidation.

The use of conductive and corrosion-resistant protective layers represents a key strategy for improving the durability of light absorber materials in photoelectrochemical water splitting. For high performance photoanodes such as Si, GaAs, and GaP, amorphous TiO protective overlayers, deposited by atomic layer deposition, are conductive for holes via a defect band in the TiO. However, when coated on simply prepared, low-cost photoanodes such as metal oxides, no charge transfer is observed through amorphous TiO.

Specific interaction between the DSPHTELP peptide and various functional groups.

M13 bacteriophages serve as a versatile foundation for nanobiotechnology due to their unique biological and chemical properties. The polypeptides that comprise their coat proteins, specifically pVIII, can be precisely tailored through genetic engineering. This enables the customized integration of various functional elements through specific interactions, leading to the development of innovative hybrid materials for applications such as energy storage, biosensing, and catalysis.

Identifying a key spot for electron mediator-interaction to tailor CO dehydrogenase's affinity.

Fe‒S cluster-harboring enzymes, such as carbon monoxide dehydrogenases (CODH), employ sophisticated artificial electron mediators like viologens to serve as potent biocatalysts capable of cleaning-up industrial off-gases at stunning reaction rates. Unraveling the interplay between these enzymes and their associated mediators is essential for improving the efficiency of CODHs. Here we show the electron mediator-interaction site on ChCODHs (Ch, Carboxydothermus hydrogenoformans) using a systematic approach that leverages the viologen-reactive characteristics of superficial aromatic residues.

High-Valence W Ions Boost Cr Activity in CrWO for Ideal Water Oxidation.

Electrocatalytic activity of multi-valence metal oxides for oxygen evolution reaction (OER) arises from various interactions among the constituent metal elements. Although the high-valence metal ions attract recent attentions due to the interactions with their neighboring 3d transition metal catalytic center, atomic-scale explanations for the catalytic efficiencies are still lacking. Here, by employing density functional theory predictions and experimental verifications, unprecedented electronic isolation of the catalytic 3d center (M) induced by the surrounding high-valence ions such as W is discovered in multivalent oxides MWO (M = Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn).

Amine-Rich Hydrogels for Molecular Nanoarchitectonics of Photosystem II and Inverse Opal TiO toward Solar Water Oxidation.

Solar water oxidation is a crucial process in light-driven reductive synthesis, providing electrons and protons for various chemical reductions. Despite advances in light-harvesting materials and cocatalysts, achieving high efficiency and stability remains challenging. In this study, we present a simple yet effective strategy for immobilizing natural photosystems (PS) made of abundant and inexpensive elements, using amine-rich polyethylenimine (PEI) hydrogels, to fabricate organic/inorganic hybrid photoanodes.

Electrochemical Evolution of Ru-Based Polyoxometalates into Si,W-Codoped RuO for Acidic Overall Water Splitting.

Despite intensive studies over decades, the development of electrocatalysts for acidic water splitting still relies on platinum group metals, especially Pt and Ir, which are scarce, expensive, and poorly sustainable. Because such problems can be alleviated, Ru-based bifunctional catalysts such as rutile RuO have recently emerged. However, RuO has a relatively low activity for hydrogen evolution reactions (HER) and low stability for oxygen evolution reactions (OER) under acidic conditions.

Electrifying HO synthesis with g-CN-based single atom catalysts.

This article highlights the recent work of Zhang, Peng (, 2023, , 695, https://doi.org/10.1039/D2NH00564F) on transition metal single atom embedded graphitic carbon nitride nanosheets for the neutral electrosynthesis of hydrogen peroxide.

Solar Biomass Reforming and Hydrogen Production with Earth-Abundant Si-Based Photocatalysts.

Efficient electrochemical hydrogen production and biomass refinery are crucial for the decarbonization of various sectors. However, their energy-intensive nature and low efficiency have hindered their practical application. In this study, earth-abundant and non-toxic photocatalysts that can produce hydrogen and reform biomass efficiently, utilizing unlimited solar energy, are presented.

Modular Flow Reactors for Valorization of Kraft Lignin and Low-Voltage Hydrogen Production.

Recent studies have found that green hydrogen production and biomass utilization technologies can be combined to efficiently produce both hydrogen and value-added chemicals using biomass as an electron and proton source. However, the majority of them have been limited to proof-of-concept demonstrations based on batch systems. Here the authors report the design of modular flow systems for the continuous depolymerization and valorization of lignin and low-voltage hydrogen production.

Bias-free solar hydrogen production at 19.8 mA cm using perovskite photocathode and lignocellulosic biomass.

Solar hydrogen production is one of the ultimate technologies needed to realize a carbon-neutral, sustainable society. However, an energy-intensive water oxidation half-reaction together with the poor performance of conventional inorganic photocatalysts have been big hurdles for practical solar hydrogen production. Here we present a photoelectrochemical cell with a record high photocurrent density of 19.

Molecular design of heterogeneous electrocatalysts using tannic acid-derived metal-phenolic networks.

Electrochemistry could play a critical role in the transition to a more sustainable society by enabling the carbon-neutral production and use of various chemicals as well as efficient use of renewable energy resources. A prerequisite for the practical application of various electrochemical energy conversion and storage technologies is the development of efficient and robust electrocatalysts. Recently, molecularly designed heterogeneous catalysts have drawn great attention because they combine the advantages of both heterogeneous solid and homogeneous molecular catalysts.

Synthesis of hexagonal rosettes of g-CN with boosted charge transfer for the enhanced visible-light photocatalytic hydrogen evolution and hydrogen peroxide production.

Photocatalytic sustainable fuel production attracted extensive attention because of the urgent need of the society to shift from fossil fuels to solar fuels. Herein, the synthesis of hexagonal rosettes of g-CN with an efficient performance toward hydrogen evolution and hydrogen peroxide production as the two kinds of solar fuels were reported. The hexagonal rosettes of g-CN were simply fabricated via controlled solid-state polymerization of three-dimensional hexagonal rosettes of cyanuric acid-melamine adduct at 500 °C.

Selective photocatalytic production of CH using Zn-based polyoxometalate as a nonconventional CO reduction catalyst.

Efficient and selective production of CH through the CO reduction reaction (CO2RR) is a challenging task due to the high amount of energy consumption and various reaction pathways. Here, we report the synthesis of Zn-based polyoxometalate (ZnPOM) and its application in the photocatalytic CO2RR. Unlike conventional Zn-based catalysts that produce CO, ZnPOM can selectively catalyze the production of CH in the presence of an Ir-based photosensitizer (TIr3) through the photocatalytic CO2RR.

Tetraruthenium Polyoxometalate as an Atom-Efficient Bifunctional Oxygen Evolution Reaction/Oxygen Reduction Reaction Catalyst and Its Application in Seawater Batteries.

Although development and utilization of efficient catalysts with earth-abundant and cheap elements are desired, precious noble metal-based catalysts are still widely used and studied due to the urgent need to address energy and environmental issues. Polyoxometalates (POMs) can be excellent candidates in this context. In this study, we found that oxo-bridged tetraruthenium polyoxometalate (RuPOM) exhibits excellent electrocatalytic activity for both oxygen evolution and reduction reactions (OER and ORR) with minimal use of noble metal elements and can be used for the development of efficient seawater batteries (SWBs).

Superaerophobic hydrogels for enhanced electrochemical and photoelectrochemical hydrogen production.

The efficient removal of gas bubbles in (photo)electrochemical gas evolution reactions is an important but underexplored issue. Conventionally, researchers have attempted to impart bubble-repellent properties (so-called superaerophobicity) to electrodes by controlling their microstructures. However, conventional approaches have limitations, as they are material specific, difficult to scale up, possibly detrimental to the electrodes' catalytic activity and stability, and incompatible with photoelectrochemical applications.

Zwitterionic Conjugated Surfactant Functionalization of Graphene with pH-Independent Dispersibility: An Efficient Electron Mediator for the Oxygen Evolution Reaction in Acidic Media.

The functionalization of graphene has been extensively used as an effective route for modulating the surface property of graphene, and enhancing the dispersion stability of graphene in aqueous solutions via functionalization has been widely investigated to expand its use for various applications across a range of fields. Herein, an effective approach is described for enhancing the dispersibility of graphene in aqueous solutions at different pH levels via non-covalent zwitterion functionalization. The results show that a surfactant with electron-deficient carbon atoms in its backbone structure and large π-π interactive area enables strong interactions with graphene, and the zwitterionic side terminal groups of the molecule support the dispersibility of graphene in various pH conditions.

Unassisted solar lignin valorisation using a compartmented photo-electro-biochemical cell.

Lignin is a major component of lignocellulosic biomass. Although it is highly recalcitrant to break down, it is a very abundant natural source of valuable aromatic carbons. Thus, the effective valorisation of lignin is crucial for realising a sustainable biorefinery chain.

Native Void Space for Maximum Volumetric Capacity in Silicon-Based Anodes.

Volumetric energy density is considered a primary factor in developing high-energy batteries. Despite its significance, less efforts have been devoted to its improvement. Silicon-based materials have emerged as next-generation anodes for lithium-ion batteries due to their high specific capacity.

Catalytic Multilayers for Efficient Solar Water Oxidation through Catalyst Loading and Surface-State Passivation of BiVO Photoanodes.

We studied the kinetics of photoelectrochemical (PEC) water oxidation using a model photoanode BiVO modified with various water oxidation catalysts (WOCs) by electrochemical impedance spectroscopy. In particular, we prepared BiVO photoanodes with catalytic multilayers (CMs), where cationic polyelectrolytes and anionic polyoxometalate (POM) WOCs were assembled in a desired amount at a nanoscale precision, and compared their performance with those with well-known WOCs such as cobalt phosphate (CoPi) and NiOOH. Our comparative kinetics analysis suggested that the deposition of the CMs improved the kinetics of both the photogenerated charge carrier separation/transport in bulk BiVO due to passivation of surface recombination centers and water oxidation at the electrode/electrolyte interface due to deposition of efficient molecular WOCs.

Interface Engineering of Hematite with Nacre-like Catalytic Multilayers for Solar Water Oxidation.

An efficient water oxidation photoanode based on hematite has been designed and fabricated by tailored assembly of graphene oxide (GO) nanosheets and cobalt polyoxometalate (Co-POM) water oxidation catalysts into a nacre-like multilayer architecture on a hematite photoanode. The deposition of catalytic multilayers provides a high photocatalytic efficiency and photoelectrochemical stability to underlying hematite photoanodes. Compared to the bare counterpart, the catalytic multilayer electrode exhibits a significantly higher photocurrent density and large cathodic shift in onset potential (∼369 mV) even at neutral pH conditions due to the improved charge transport and catalytic efficiency from the rational and precise assembly of GO and Co-POM.

Semiconducting Synthetic Melanin-Based Organic/Inorganic Hybrid Photoanodes for Solar Water Oxidation.

We report the development of semiconducting melanin-based organic/inorganic hybrid photoanodes for solar water oxidation. Synthetic melanin thin-film incorporating polyoxometalate (POM) water oxidation catalysts (WOCs) are readily deposited on the surface of various n-type inorganic semiconductors (e.g.

Self-Assembled Supramolecular Hybrid of Carbon Nanodots and Polyoxometalates for Visible-Light-Driven Water Oxidation.

Water splitting is considered the most attractive pursuit in the field of solar energy conversion. In this study, we report the synthesis and application of a supramolecular hybrid of carbon nanodot (CD) and cobalt polyoxometalate (Co-POM) to solar water oxidation. The self-assembly of the alginate-based CD and Co-POM led to the formation of a spherical hybrid of CD/Co-POM.