Arrayed metal phosphide heterostructure by Fe doping for robust overall water splitting.

Transition metal phosphides (TMPs) show promise in water electrolysis due to their electronic structures, which activate hydrogen/oxygen reaction intermediates. However, TMPs face limitations in catalytic efficiency due to insufficient active sites, poor conductivity, and multiple intermediate steps in water electrolysis. Here, we synthesize a highly efficient bifunctional self-supported electrocatalyst, which consists of an N-doped carbon shell anchored on Fe-doped CoP/Co2P arrays on nickel foam (NC@Fe-CoxP/NF) using hydrothermal and phosphorization techniques. Experimental and theoretical results indicate that the modified morphology, with increased active site density and a tunable electronic structure induced by Fe doping in the CoP/Co2P heterostructure, leads to superior water electrolysis performance. The resulting NC@Fe0.1-CoP/Co2P/NF catalyst exhibits overpotentials of 122 mV for the hydrogen evolution reaction (HER) and 270 mV for the oxygen evolution reaction (OER) at 100 mA cm-2. Furthermore, using NC@Fe0.1-CoP/Co2P/NF as both the cathode and anode in an alkaline electrolyzer enables the cell system to achieve 100 mA cm-2 at a voltage of 1.70 V, while maintaining long-term catalytic durability. This work may pave the way for designing self-supported, highly efficient electrocatalysts for practical water electrolysis applications.

Multifunctional Strategies of Advanced Electrocatalysts for Efficient Urea Synthesis.

The electrochemical reduction of nitrogenous species (such as N2, NO, NO2 -, and NO3 -) for urea synthesis under ambient conditions has been extensively studied due to their potential to realize carbon/nitrogen neutrality and mitigate environmental pollution, as well as provide a means to store renewable electricity generated from intermittent sources such as wind and solar power. However, the sluggish reaction kinetics and the scarcity of active sites on electrocatalysts have significantly hindered the advancement of their practical applications. Multifunctional engineering of electrocatalysts has been rationally designed and investigated to adjust their electronic structures, increase the density of active sites, and optimize the binding energies to enhance electrocatalytic performance. Here, surface engineering, defect engineering, doping engineering, and heterostructure engineering strategies for efficient nitrogen electro-reduction are comprehensively summarized. The role of each element in engineered electrocatalysts is elucidated at the atomic level, revealing the intrinsic active site, and understanding the relationship between atomic structure and catalytic performance. This review highlights the state-of-the-art progress of electrocatalytic reactions of waste nitrogenous species into urea. Moreover, this review outlines the challenges and opportunities for urea synthesis and aims to facilitate further research into the development of advanced electrocatalysts for a sustainable future.

Brusatol induces ferroptosis in oesophageal squamous cell carcinoma by repressing GSH synthesis and increasing the labile iron pool via inhibition of the NRF2 pathway.

Brusatol (Bru), a bioactive compound found in Brucea sumatrana, exerts antitumour effects on several malignancies. However, the role and molecular mechanism of Bru in squamous cell carcinoma of the oesophagus (ESCC) remain unclear. Here, we found that Bru decreased the survival of ESCC cells. Subsequently, the ferroptosis inhibitors, deferoxamine and liproxstatin-1, rescued Bru-induced cell death, indicating that ferroptosis plays a major role in Bru-induced cell death. Furthermore, Bru promoted lipid peroxidation, glutathione (GSH) depletion, and ferrous iron overload in vitro. Consistent with these in vitro results, Bru significantly inhibited tumour growth in KYSE150 xenograft nude mice by triggering ferroptosis. Mechanistically, nuclear factor E2-related factor 2 (NRF2) inactivation via increased ubiquitin-proteasome degradation was found to be a vital determinant of ferroptosis induced by Bru. Notably, Bru significantly decreases GSH synthesis, iron storage, and efflux by downregulating the expression of NRF2 target genes (glutamate-cysteine ligase catalytic subunit (GCLC), solute carrier family 7 member 11 (SLC7A11), ferritin heavy chain 1 (FTH1), and solute carrier family 40 member 1 (SLC40A1)), resulting in the accumulation of lethal lipid-based reactive oxygen species (ROS) and intracellular enrichment of chelated iron. Taken together, our findings indicate that ferroptosis is a novel mechanism underlying Bru-induced antitumour activity and will hopefully provide a valuable compound for ESCC treatment.

Epoxy-rich Fe Single Atom Sites Boost Oxygen Reduction Electrocatalysis.

Electrocatalysts for highly efficient oxygen reduction reaction (ORR) are crucial for energy conversion and storage devices. Single-atom catalysts with maximized metal utilization and altered electronic structure are the most promising alternatives to replace current benchmark precious metals. However, the atomic level understanding of the functional role for each species at the anchoring sites is still unclear and poorly elucidated. Herein, we report Fe single atom catalysts with the sulfur and oxygen functional groups near the atomically dispersed metal centers (Fe1/NSOC) for highly efficient ORR. The Fe1/NSOC delivers a half-wave potential of 0.92 V vs. RHE, which is much better than those of commercial Pt/C (0.88 V), Fe single atoms on N-doped carbon (Fe1/NC, 0.89 V) and most reported nonprecious metal catalysts. The spectroscopic measurements reveal that the presence of sulfur group induces the formation of epoxy groups near the FeN4S2 centers, which not only modulate the electronic structure of Fe single atoms but also participate the catalytic process to improve the kinetics. The density functional theory calculations demonstrate the existence of sulfur and epoxy group engineer the charges of Fe reactive center and facilitate the reductive release of OH* (rate-limiting step), thus boosting the overall oxygen reduction efficiency.

Atomically dispersed Mn atoms coordinated with N and O within an N-doped porous carbon framework for boosted oxygen reduction catalysis.

Developing efficient and robust catalysts to replace Pt group metals for the oxygen reduction reaction (ORR) is conducive to achieving highly efficient energy conversion. Here, we develop a general ion exchange strategy to construct highly efficient ORR catalysts consisting of various atomically dispersed metal atoms anchored on N-doped porous carbon (M-SAs/NC) to investigate the atomic structure-catalytic activity relationship. The structure characterization results demonstrated that the achieved atomic structure varied due to the presence of different metal centers. Mn-SAs/NC consists of MnN3O1 centers, in which the Mn single atoms are stabilized by 3 N and 1 O. In contrast, the center metals in Fe-/Co-/Cu single-atom catalysts are coordinated by merely N atoms. Mn-SAs/NC delivers superior performance for the ORR with a half-wave potential (E1/2) of 0.91 V vs. RHE in 0.1 M KOH solution, outperforming that of the commercial Pt/C catalyst and the control Fe-/Co-/Cu single-atom catalysts. Furthermore, Mn-SAs/NC also shows excellent methanol tolerance and stability up to 5000 cycles. Density functional theory (DFT) calculations reveal that Mn single atom catalysts with MnN3O1 centers contributed to the superior ORR performance with lower energy barriers and optimized adsorption capacity of intermediates. These findings provide insights into the design and development of specific coordinated structures of atomically dispersed catalysts to facilitate the practical applications of energy conversion.

Macro/Micro-Environment Regulating Carbon-Supported Single-Atom Catalysts for Hydrogen/Oxygen Conversion Reactions.

Single-atom catalysts (SACs) have attracted tremendous research interest due to their unique atomic structure, maximized atom utilization, and remarkable catalytic performance. Among the SACs, the carbon-supported SACs have been widely investigated due to their easily controlled properties of the carbon substrates, such as the tunable morphologies, ordered porosity, and abundant anchoring sites. The electrochemical performance of carbon-supported SACs is highly related to the morphological structure of carbon substrates (macro-environment) and the local coordination environments of center metals (micro-environment). This review aims to provide a comprehensive summary on the macro/micro-environment regulating carbon-supported SACs for highly efficient hydrogen/oxygen conversion reactions. The authors first summarize the macro-environment engineering strategies of carbon-supported SACs with altered specific surface areas and porous properties of the carbon substrates, facilitating the mass diffusion kinetics and structural stability. Then the micro-environment engineering strategies of carbon-supported SACs are discussed with the regulated atomic structure and electronic structure of metal centers, boosting the catalytic performance. Insights into the correlation between the co-boosted effect from the macro/micro-environments and catalytic activity for hydrogen/oxygen conversion reactions are summarized and discussed. Finally, the challenges and perspectives are addressed in building highly efficient carbon-supported SACs for practical applications.

Surface and Interface Engineering: Molybdenum Carbide-Based Nanomaterials for Electrochemical Energy Conversion.

Molybdenum carbide (Mox C)-based nanomaterials have shown competitive performances for energy conversion applications based on their unique physicochemical properties. A large surface area and proper surface atomic configuration are essential to explore potentiality of Mox C in electrochemical applications. Although considerable efforts are made on the development of advanced Mox C-based catalysts for energy conversion with high efficiency and stability, some urgent issues, such as low electronic conductivity, low catalytic efficiency, and structural instability, have to be resolved in accordance with their application environments. Surface and interface engineering have shown bright prospects to construct highly efficient Mox C-based electrocatalysts for energy conversion including the hydrogen evolution reaction, oxygen evolution reaction, nitrogen reduction reaction, and carbon dioxide reduction reaction. In this Review, the recent progresses in terms of surface and interface engineering of Mox C-based electrocatalytic materials are summarized, including the increased number of active sites by decreasing the particle size or introducing porous or hierarchical structures and surface modification by introducing heteroatom(s), defects, carbon materials, and others electronic conductive species. Finally, the challenges and prospects for energy conversion on Mox C-based nanomaterials are discussed in terms of key performance parameters for the catalytic performance.

Hierarchical Porous Molybdenum Carbide Based Nanomaterials for Electrocatalytic Hydrogen Production.

The electrocatalytic hydrogen evolution reaction (HER) for the preparation of hydrogen fuel is a very promising technology to solve the shortage of hydrogen storage. However, in practical applications, HER catalysts with excellent performance and moderate price are very rare. Molybdenum carbide (MoxC) has attracted extensive attention due to its electronic structure and natural abundance. Here, a comprehensive review of the preparation and performance control of hierarchical porous molybdenum carbide (HP-MoxC) based catalysts is summarized. The methods for preparing hierarchical porous materials and the regulation of their HER performance are mainly described. Briefly, the HP-MoxC based catalysts were prepared by template method, morphology-conserved transformations method, and secondary conversion method of an organic-inorganic hybrid material. The intrinsic HER kinetics are enhanced by the introduction of a carbon-based support, heteroatom doping, and the construction of a heterostructure. Finally, the future development of HP-MoxC based catalysts is prospected in this review.