Altering the CO2 Electroreduction Pathways Towards C1 or C2+ Products via Engineering the Strength of Interfacial Cu-O Bond.

Copper (Cu)-based catalysts have established their unique capability for yielding wide value-added products from CO2. Herein, we demonstrate that the pathways of the electrocatalytic CO2 reduction reaction (CO2RR) can be rationally altered toward C1 or C2+ products by simply optimizing the coordination of Cu with O-containing organic species (squaric acid (H2C4O4) and cyclohexanehexaone (C6O6)). It is revealed that the strength of Cu-O bonds can significantly affect the morphologies and electronic structures of derived Cu catalysts, resulting in the distinct behaviors during CO2RR. Specifically, the C6O6-Cu catalysts made up from organized nanodomains shows a dominant C1 pathway with a total Faradaic efficiency (FE) of 63.7 % at -0.6 V (versus reversible hydrogen electrode, RHE). In comparison, the C4O4-Cu with an about perfect crystalline structure results in uniformly dispersed Cu-atoms, showing a notable FE of 65.8 % for C2+ products with enhanced capability of C-C coupling. The latter system also shows stable operation over at least 10 h with a high current density of 205.1 mA cm-2 at -1.0 VRHE, i.e., is already at the boarder of practical relevance. This study sheds light on the rational design of Cu-based catalysts for directing the CO2RR reaction pathway.

Unraveling the Activity and Mechanism of TM@g-C4N3 Electrocatalysts in the Oxygen Reduction Reaction.

In this work, a high-throughput screening strategy and density functional theory (DFT) are jointly employed to identify high-performance TM@g-C4N3 (TM = 3d, 4d, 5d transition metals) single-atom catalysts (SACs) for the oxygen reduction reaction (ORR). Comprehensive studies demonstrated that Cu@, Zn@, and Ag@g-C4N3 show high ORR catalytic activities under both acidic and alkaline conditions with favorable overpotentials (ηORR) of 0.70, 0.89, and 0.89 V, respectively; among them, Cu@g-C4N3 is the best candidate. The ORR follows a four-electron mechanism with the final product H2O/OH-. Cu@, Zn@, and Ag@g-C4N3 catalysts also exhibit good thermal (500 K) and electrochemical (0.93-3.14 V) stabilities. Cu@, Zn@, and Ag@g-C4N3 demonstrate superior activities with low ηORR due to its moderate adsorption strength of *OH. The ηORR and the Gibbs free energy changes of *OH (ΔG4(acidic)/ΔG4(alkaline)) resemble a volcano-type relationship under acidic/alkaline conditions, respectively. Additionally, the O-O bond length in *OOH emerged as an effective structural descriptor for rapidly identifying the promising electrocatalysts. This research provides valuable insights into the origin of the ORR activity on TM@g-C4N3 and offers useful guidance for the efficient exploration of high-performance catalyst candidates.

Emerging Two-Dimensional Carbonaceous Materials for Electrocatalytic Energy Conversions: Rational Design of Active Structures through High-Temperature Chemistry.

Electrochemical energy conversion and storage technologies involving controlled catalysis provide a sustainable way to handle the intermittency of renewable energy sources, as well as to produce green chemicals/fuels in an ecofriendly manner. Core to such technology is the development of efficient electrocatalysts with high activity, selectivity, long-term stability, and low costs. Here, two-dimensional (2D) carbonaceous materials have emerged as promising contenders for advancing the chemistry in electrocatalysis. We review the emerging 2D carbonaceous materials for electrocatalysis, focusing primarily on the fine engineering of active structures through thermal condensation, where the design, fabrication, and mechanism investigations over different types of active moieties are summarized. Interestingly, all the recipes creating two-dimensionality on the carbon products also give specific electrocatalytic functionality, where the special mechanisms favoring 2D growth and their consequences on materials functionality are analyzed. Particularly, the structure-activity relationship between specific heteroatoms/defects and catalytic performance within 2D metal-free electrocatalysts is highlighted. Further, major challenges and opportunities for the practical implementation of 2D carbonaceous materials in electrocatalysis are summarized with the purpose to give future material design guidelines for attaining desirable catalytic structures.

Comprehensive identification and analysis of DUF640 genes associated with rice growth.

Protein domains with conserved amino acid sequences and uncharacterized functions are called domains of unknown function (DUF). The DUF640 gene family plays a crucial role in plant growth, particularly in light regulation, floral organ development, and fruit development. However, there exists a lack of systematic understanding of the evolutionary relationships and functional differentiation of DUF640 within the Oryza genus. In this study, 61 DUF640 genes were identified in the Oryza genus. The expression of DUF640s is induced by multiple hormonal stressors including abscisic acid (ABA), cytokinin (CK), ethylene (ETH), and indole-3-acetic acid (IAA). Specifically, OiDUF640-10 expression significantly increased after ETH treatment. Transgenic experiments showed that overexpressing OiDUF640-10 lines were sensitive to ETH, and seedling length was obstructed. Evolutionary analysis revealed differentiation of the OiDUF640-10 gene in O. sativa ssp. indica and japonica varieties, likely driven by natural selection during the domestication of cultivated rice. These results indicate that OiDUF640-10 plays a vital role in the regulation of rice seedling length.

Tin (II) Chloride Salt Melts as Non-Innocent Solvents for the Synthesis of Low-Temperature Nanoporous Oxo-Carbons for Nitrate Electrochemical Hydrogenation.

Carbonaceous electrocatalysts offer advantages over metal-based counterparts, being cost-effective, sustainable, and electrochemically stable. Their high surface area increases reaction kinetics, making them valuable for environmental applications involving contaminant removal. However, their rational synthesis is challenging due to the applied high temperatures and activation steps, leading to disordered materials with limited control over doping. Here, a new synthetic pathway using carbon oxide precursors and tin chloride as a p-block metal salt melt is presented. As a result, highly porous oxygen-rich carbon sheets (with a surface area of 1600 m2 g-1) are obtained at relatively low temperatures (400 °C). Mechanistic studies reveal that Sn(II) triggers reductive deoxygenation and concomitant condensation/cross-linking, facilitated by the Sn(II) → Sn(IV) transition. Due to their significant surface area and oxygen doping, these materials demonstrate exceptional electrocatalytic activity in the nitrate-to-ammonia conversion, with an ammonia yield rate of 221 mmol g-1 h-1 and a Faradic efficiency of 93%. These results surpass those of other carbon-based electrocatalysts. In situ Raman studies reveal that the reaction occurs through electrochemical hydrogenation, where active hydrogen is provided by water reduction. This work contributes to the development of carbonaceous electrocatalysts with enhanced performance for sustainable environmental applications.

Rapid Photothermal-Responsive Soft Hydrogel Actuator Contained Ti3C2Tx MXene and Laponite Clay with Enhanced Mechanical Properties.

Photothermal responsive hydrogels are widely used in bionic soft actuators due to their remote-controlled capabilities and flexibility. However, their weak mechanical properties and limited responsiveness hinder their potential applications. To overcome this, we developed an innovative laponite/MXene/PNIPAm (LxMyPN) nanocomposite hydrogel that is mechanically robust and exhibits excellent photothermally responsive properties based on abundant hydrogen bonds. Notably, laponite clay is used as a co-cross-linking agent to improve the mechanical properties of LxMyPN hydrogel, while MXene nanosheets are added to promote the photothermal responsiveness. The resulting L3M0.4PN nanocomposite hydrogel exhibits enhanced mechanical properties, with a compressive strength of 0.201 MPa, a tensile strength of 90 kPa, and a fracture toughness of 27.25 kJ m-2. In addition, the L3M0.4PN hydrogel displays a deswelling ratio of 73.6% within 60 s and experiences an excellent volume shrinkage of 82.4% under light irradiation. Furthermore, hydrogel actuators with fast response behaviors are constructed and employed as grippers capable of grasping and releasing target objects. Overall, this high-strength and fast-responsive hydrogel actuator is beneficial to paving the way for remote controlled soft robots.

Red Carbon Mediated Formation of Cu2O Clusters Dispersed on the Oxocarbon Framework by Fehling's Route and their Use for the Nitrate Electroreduction in Acidic Conditions.

The oligomers of carbon suboxide, known as red carbon, exhibit a highly conjugated structure and semiconducting properties. Upon mild heat treatment, it transforms into a carbonaceous framework rich in oxygen surface terminations, called oxocarbon. In this study, the abundant oxygen functionalities are harnessed as anchors to create oxocarbon-supported nanohybrid electrocatalysts. Starting with single atomic Cu (II) strongly coordinated to oxygen atoms on red carbon, the Fehling reaction leads to the formation of Cu2O clusters. Simultaneously, a covalent oxocarbon framework emerges via cross-linking, providing robust support for Cu2O clusters. Notably, the oxocarbon support effectively stabilizes Cu2O clusters of very small size, ensuring their high durability in acidic conditions and the presence of ammonia. The synthesized material exhibits a superior electrocatalytic activity for nitrate reduction under acidic electrolyte conditions, with a high yield rate of ammonium (NH4 +) at 3.31 mmol h-1 mgcat -1 and a Faradaic efficiency of 92.5% at a potential of -0.4 V (vs RHE).

Hollow Stair-Stepping Spherical High-Entropy Prussian Blue Analogue for High-Rate Sodium Ion Batteries.

Prussian blue analogues (PBAs) are considered to be one of the most suitable sodium storage materials, especially with the introduction of the high-entropy (HE) concept into their structure to further improve their various abilities. However, severe agglomeration of the HEPBA particles still limits the fast charging capabilities. Here, an HEPBA (Nax(FeMnCoNiCu)[Fe(CN)6]y□1-y·nH2O) with a hollow stair-stepping spherical structure has been prepared through the chemical etching process of the traditional cubic structure of HEPBA. Electrochemical characterization (sodium ion battery), kinetic analysis, and COMSOL Multiphysics simulations reveal that the nature of the high-entropy and the hollow stair-stepping spherical structure can greatly improve the diffusion behavior of Na+ ions. Moreover, the hollow structure effectively mitigates the volume change of HEPBA during SIBs operation, ultimately extending the lifespan. Consequently, the as-prepared HEPBA cathode exhibits excellent rate performance (126.5 and 76.4 mAh g-1 at 0.1 and 4.0 A g-1, respectively) and stable long-term capability (maintaining its 75.6% capacity after 1000 cycles) due to its unique structure. Furthermore, the waste of the etching process can easily be recycled to prepare more HEPBA product. This processing method holds great promise for designing nanostructures of advanced high-entropy Prussian blue analogues for sodium ion batteries.