Construction of H-Doped PdB Nanocrystals as Electrocatalysts to Modulate Formic Acid Oxidation.

The strong ligand effect in B-doped Pd-based (PdB) catalysts renders them a promising anode for constructing formic acid fuel cells (FAFCs) exhibiting high power density and outstanding stability. However, the enhancement of the oxidation barrier is unavoidable in this alloy system owing to the electron transfer (ET) from B to Pd. In this study, a hydrogen doping strategy is employed to open charge freedom in PdB compounds and boost their formic acid oxidation reaction (FAOR) activity by suppressing the ET process. The resulting hydrogen-doped PdB (PdBH) exhibits an ultrahigh mass activity of up to 1.2A mg-1 Pd, which is 3.23 times that of the PdB catalyst and 9.55 times that of Pd black. Detailed experimental and theoretical studies show that the interstitial hydrogen leads to enhanced orbital hybridization and reduced electron density around Pd. This optimized ligand effect weakens the carbon monoxide adsorption and increases the direct pathway preference of PdBH, resulting in its outstanding catalytic activity for the FAOR. The development of this high-performance hydrogen-doped PdB catalyst is an important step toward the construction of advanced light element co-doped metal catalysts.

Improving the Oxygen Evolution Reaction Kinetics in Zn-Air Battery by Iodide Oxidation Reaction.

Zinc-air batteries (ZABs) have garnered considerable attention as a highly promising contender in the field of energy storage and conversion. Nevertheless, their performance is considerably impeded by the proliferation of dendrites on the Zinc anode and the slow kinetics of the redox reaction on the air cathode. Herein, taking Ag30%@LaCoO3 (Ag30%@LCO) heterojunction catalyst as the cathode, it is demonstrated that adding KI additives to the alkaline electrolyte can not only enhance the oxygen electrocatalytic reaction but also inhibit the formation of zinc anode dendrites, thereby achieving a comprehensive improvement in the performance of ZABs. Under the action of the KI additive, the optimized Ag30%@LCO catalyst shows a decreased overpotential from 460 to 220 mV at j = 10 mA cm-2, while the assembled ZAB shows reduced charging potential (1.8 V), and long cycle stability (180 h). Furthermore, the morphology characterization results indicate a reduction in dendrites on the Zn anode. Both experimental and calculated results indicate that the presence of I- as a reaction modifier alters the trajectory of the conventional oxygen evolution reaction, resulting in a more thermodynamically favorable pathway. The introduction of KI additives as electrolytes provides a straightforward approach to developing comprehensively improved ZABs.

Covalent Organic Frameworks for Electrocatalysis：Design, Applications, and Perspectives.

Covalent organic frameworks (COFs) are an innovative class of crystalline porous polymers composed of light elements such as C, N, O, etc., linked by covalent bonds. The distinctive properties of COFs, including designable building blocks, large specific surface area, tunable pore size, abundant active sites, and remarkable stability, have led their widespread applications in electrocatalysis. In recent years, COF-based electrocatalysts have made remarkable progress in various electrocatalytic fields, including the hydrogen evolution reaction, oxygen evolution reaction, oxygen reduction reaction, nitrogen reduction reaction, nitrate reduction reaction, and carbon dioxide reduction reaction. This review begins with an introduction to the design and synthesis strategies employed for COF-based electrocatalysts. These strategies include heteroatom doping, metalation of COF and building monomers, encapsulation of active sites within COF pores, and the development of COF-based derived materials. Subsequently, a systematic overview of the recent advancements in the application of COF-based catalysts in electrocatalysis is presented. Finally, the review discusses the main challenges and outlines possible avenues for the future development of COF-based electrocatalysts.

Scalable Cathodic H2O2 Electrosynthesis using Cobalt-Coordinated Nanocellulose Electrocatalyst.

Converting hierarchical biomass structure into cutting-edge architecture of electrocatalysts can effectively relieve the extreme dependency of nonrenewable fossil-fuel-resources typically suffering from low cost-effectiveness, scarce supplies, and adverse environmental impacts. A cost-effective cobalt-coordinated nanocellulose (CNF) strategy is reported for realizing a high-performance 2e-ORR electrocatalysts through molecular engineering of hybrid ZIFs-CNF architecture. By a coordination and pyrolysis process, it generates substantial oxygen-capturing active sites within the typically oxygen-insulating cellulose, promoting O2 mass and electron transfer efficiency along the nanostructured Co3O4 anchored with CNF-based biochar. The Co-CNF electrocatalyst exhibits an exceptional H2O2 electrosynthesis efficiency of ≈510.58 mg L-1 cm-2 h-1 with an exceptional superiority over the existing biochar-, or fossil-fuel-derived electrocatalysts. The combination of the electrocatalysts with stainless steel mesh serving as a dual cathode can strongly decompose regular organic pollutants (up to 99.43% removal efficiency by 30 min), showing to be a desirable approach for clean environmental remediation with sustainability, ecological safety, and high-performance.

Flexible Hydrazone-Linked Metal-Covalent Organic Frameworks with Copper Clusters for Efficient Electrocatalytic Oxygen Evolution Reaction.

Despite the challenges associated with the synthesis of flexible metal-covalent organic frameworks (MCOFs), these offer the unique advantage of maximizing the atomic utilization efficiency. However, the construction of flexible MCOFs with flexible building units or linkages has rarely been reported. In this study, novel flexible MCOFs are constructed using flexible building blocks and copper clusters with hydrazone linkages. The heterometallic frameworks (Cu, Co) are prepared through the hydrazone linkage coordination method and evaluated as catalysts for the oxygen evolution reaction (OER). Owing to the spatial separation and functional cooperation of the heterometallic MCOF catalysts, the as-synthesized MCOFs exhibited outstanding catalytic activities with an overpotential of 268.8 mV at 10 mA cm-2 for the OER in 1 M KOH, which is superior to those of the reported covalent organic frameworks (COFs)-based OER catalysts. Theoretical calculations further elucidated the synergistic effect of heterometallic active sites within the linkages and frameworks, contributing to the enhanced OER activity. This study thus introduces a novel approach to the fundamental design of flexible MCOF catalysts for the OER, emphasizing their enhanced atomic utilization efficiency.

Polythiophene-coated carbon nano boxes for efficient platinum-based catalysts for methanol electrooxidation.

To improve the efficiency of the methanol oxidation reaction (MOR) in direct methanol fuel cells (DMFCs), it is essential to develop catalysts with high catalytic activity. However, constructing polyatomic doped carbon nanomaterials and understanding the interaction mechanisms between dopant elements remain significant challenges. In this study, we propose nitrogen-doped carbon nanobox (CNB) derived from Zeolitic Imidazolate Framework-67 (ZIF-67) crystals as precursors to serve as carriers for highly efficient platinum nanoparticles (Pt NPs). We synthesized platinum/poly(3,4-propylenedioxythiophene)/carbon nanobox (Pt/PProDOT/CNB) composites by wrapping CNB around PProDOT films via in situ oxidative polymerization. This unique structural design provides several advantages to the catalyst, including a large active surface area, numerous accessible electrocatalytic active centers, an optimized electronic structure, and good electronic conductivity. The Pt/PProDOT/CNB composites demonstrated excellent methanol oxidation performance, with a remarkable mass activity (MA) of 1639.9 mA mg-1Pt and a high electrochemical active surface area (ECSA) of 160.8 m2/g. Furthermore, the catalyst exhibited good CO resistance and outstanding durability.

Directional surface reconstruction of C and S Co-Doped Co2VO4/CoP for the cooperative enhancement of hydrogen production via seawater electrolysis.

The endeavor to architect bifunctional electrocatalysts that exhibit both exceptional activity and durability heralds an era of boundless potential for the comprehensive electrolysis of seawater, an aspiration that, nevertheless, poses a substantial challenge. Within this work, we describe the precise engineering of a three-dimensional interconnected nanoparticle system named SCdoped Co2VO4/CoP (SCCo2VO4), achieved through a meticulously arranged hydrothermal treatment sequence followed by gas-phase carbonization and phosphorization. The resulting SCCo2VO4 electrode exhibits outstanding bifunctional electrocatalytic stability, attributed to the strategic anionic doping and abundant heterogeneous interfaces. Doping not only adjusts the electronic structure, enhancing electron transfer efficiency but also optimizes the surface-active sites. This electrode prodigiously necessitated an extraordinarily minimal overpotential of merely 92 and 350 mV to attain current densities of 10 and 50 mA cm-2 for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively, in 1 M KOH solution. Noteworthily, when integrated into an electrolyzer for the exhaustive splitting of seawater, the SCP-Co2VO4 manifested an exceptionally low cell voltage of 2.08 V@50 mA cm-2 and showcased a durability that eclipses that of most hitherto documented nickel-based bifunctional materials. Further elucidation through Density Functional Theory (DFT) analyses underscored that anion doping and the inherent heterostructure adeptly optimize the Gibbs free energy of intermediates comprising hydrogen, chlorine, and oxygen (manifested as OH, O, OOH) within the HER and OER paradigms, thus propelling the electrochemical kinetics of seawater splitting to unprecedented velocities. These revelations unfurl a pioneering design philosophy for the creation of cost-effective yet superior catalysts aimed at the holistic division of water molecules, charting a course towards the realization of efficient and sustainable hydrogen production methodologies.

Trace Iron-Doped Nickel-Cobalt selenide with rich heterointerfaces for efficient overall water splitting at high current densities.

Developing bifunctional electrocatalysts based on non-precious metals for overall water splitting, while maintaining high catalytic activity and stability under high current densities, remains challenging. Herein, we successfully constructred trace iron-doped nickel-cobalt selenide with abundant CoSe2 (210)-Ni3Se4 (202) heterointerfaces via a simple one-step selenization reaction. The synthesized Fe-NiCoSex/NCFF (NCFF stands for nickel-cobalt-iron foam) exhibits outstanding hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) activity with low overpotentials of 328 mV for HER and 345 mV for OER at a high current density of 1000 mA cm-2, while maintaining stability for over 20 h. Additionally, the Fe-NiCoSex/NCFF exhibits the lowest Tafel slope values for both HER (33.7 mV dec-1) and OER (55.92 mV dec-1), indicating the fastest kinetics on its surface. The Fe-NiCoSex/NCFF features uniformly distributed micrometer-sized selenide particles with dense nanowires on their surface, providing a large reactive surface area and abundant active sites. Moreover, X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) analyses reveal that the catalyst is composed of nickel, cobalt, and iron, forming micrometer-sized particles with both crystalline and amorphous phases, thereby enhancing HER and OER performance under high current density. Density functional theory (DFT) calculations demonstrate that the heterostructure CoSe2 (210)-Ni3Se4 (202), with high electron density and suitable adsorption capacity for reaction intermediates, and low energy barriers for HER (-0.384 eV) and OER (ΔG1st: 0.243 eV, ΔG2nd: 0.376 eV), serves as an active center for both HER and OER.

High-Performance Bifunctional Electrocatalysts for Flexible and Rechargeable Zn-Air Batteries: Recent Advances.

Flexible rechargeable Zn-air batteries (FZABs) exhibit high energy density, ultra-thin, lightweight, green, and safe features, and are considered as one of the ideal power sources for flexible wearable electronics. However, the slow and high overpotential oxygen reaction at the air cathode has become one of the key factors restricting the development of FZABs. The improvement of activity and stability of bifunctional catalysts has become a top priority. At the same time, FZABs should maintain the battery performance under different bending and twisting conditions, and the design of the overall structure of FZABs is also important. Based on the understanding of the three typical configurations and working principles of FZABs, this work highlights two common strategies for applying bifunctional catalysts to FZABs: 1) powder-based flexible air cathode and 2) flexible self-supported air cathode. It summarizes the recent advances in bifunctional oxygen electrocatalysts and explores the various types of catalyst structures as well as the related mechanistic understanding. Based on the latest catalyst research advances, this paper introduces and discusses various structure modulation strategies and expects to guide the synthesis and preparation of efficient bifunctional catalysts. Finally, the current status and challenges of bifunctional catalyst research in FZABs are summarized.

Hybridization of bimetallic cobalt-molybdenum oxide multihole nanosheets with selenium adulteration as advanced bifunctional electrocatalysts for boosting overall water splitting.

Electrocatalytic water splitting produces green and pollution-free hydrogen as a clean energy carrier, which can effectively alleviate energy crisis. In this paper, bimetallic and selenium doped cobalt molybdate (Se-CoMoO4) nanosheets with rough surface are resoundingly prepared. The multihole Se-CoMoO4 nanosheets display ultrathin and rectangular architecture with the dimensions of âˆ¼ 3.5 µm and 700 nm for length and width, respectively. The Se-CoMoO4 electrocatalyst shows remarkable water electrolysis activity and stability. The overpotentials of oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) are 270 and 63.3 mV at 10 mA cm-2, along with low Tafel slopes of 51.6 and 62.0 mV dec-1. Furthermore, the Se-CoMoO4 couple electrolyzer merely requires a cell voltage of 1.48 V to achieve 10 mA cm-2 current density and presents no apparent attenuation for 30 h. This investigation declares that the hybridization of transition bimetallic oxide with nonmetallic adulteration can afford a tactic for the preparation of bifunctional non-precious metal-based electrocatalysts.

Electronic transfer and structural reconstruction in porous NF/FeNiP-CoP@NC heterostructure for robust overall water splitting in alkaline electrolytes.

Multimetal phosphides derived from metal-organic frameworks (MOFs) have garnered significant interest owing to their distinct electronic configurations and abundant active sites. However, developing robust and efficient catalysts based on metal phosphides for overall water splitting (OWS) remains challenging. Herein, we present an approach for synthesizing a self-supporting hollow porous cubic FeNiP-CoP@NC catalyst on a nickel foam (NF) substrate. Through ion exchange, the reconstruction chemistry transforms the FeNi-MOF nanospheres into intricate hollow porous FeNi-MOF-Co nanocubes. After phosphorization, numerous N, P co-doped carbon-coated FeNiP-CoP nanoparticles were tightly embedded within a two-dimensional (2D) carbon matrix. The NF/FeNiP-CoP@NC heterostructure retained a porous configuration, numerous heterogeneous interfaces, distinct defects, and a rich composition of active sites. Moreover, incorporating Co and the resulting structural evolution facilitated the electron transfer in FeNiP-CoP@NC, enhancing the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) processes. Consequently, the NF/FeNiP-CoP@NC catalyst demonstrated very low overpotentials of 78 mV for OER and 254 mV for HER in an alkaline medium. It also exhibited excellent long-term stability at various potentials (@10 mA cm-2, @20 mA cm-2, and @50 mA cm-2). As an overall water splitting cell, it required only 1.478 V to drive a current density of 50 mA cm-2 and demonstrated long-term stability. Density functional theory (DFT) calculations revealed a synergistic effect between multimetal phosphides, enhancing the intrinsic OER and HER activities of FeNiP-CoP@NC. This work not only elucidates the role of heteroatom induction in structural reconstruction but also highlights the importance of electronic structure modulation.

Concurrently boosted oxygen reduction/evolution electrocatalysis over highly loaded CoNi/onion-like carbon hybrid nanosheets.

Balancing the bicatalytic activities and stabilities between oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is a critical yet challenging task for exploring advanced rechargeable Zinc-air batteries (ZABs). Herein, a hybrid nanosheet catalyst with highly dispersed and densified metallic species is developed to boost the kinetics and stabilities of both ORR and OER concurrently. Through a progressive coordination and pyrolysis approach, we directly prepared highly conductive onion-like carbon (OLC) accommodating dense ORR-active CoNC species and enveloping high-loading OER-active CoNi-synergic structures within a porous lamellar architecture. The resultant CoNi/OLC nanosheet catalyst delivers better ORR and OER activities showcasing a smaller reversible oxygen electrode index (ΔE = Ej10 - E1/2) of 0.71 V, compared to state-of-the-art Pt/C-RuO2 catalysts (0.75 V), Co/amorphous carbon polyhedrons (0.80 V), NiO nanoparticles with higher Ni loading (1.00 V), and most CoNi-based bifunctional catalysts reported so far. The rechargeable ZAB assembled with the developed catalyst achieves a remarkable peak power density of 270.3 mW cm-2 (172 % of that achieved by Pt/C + RuO2) and ultrahigh cycling stability with a negligible increase in voltage gap after 800 h (110 mV increase after 200 h for a Pt/C + RuO2-based battery), standing the top level of those ever reported.

Vanadium Redox Flow Battery: Review and Perspective of 3D Electrodes.

Vanadium redox flow battery (VRFB) has garnered significant attention due to its potential for facilitating the cost-effective utilization of renewable energy and large-scale power storage. However, the limited electrochemical activity of the electrode in vanadium redox reactions poses a challenge in achieving a high-performance VRFB. Consequently, there is a pressing need to assess advancements in electrodes to inspire innovative approaches for enhancing electrode structure and composition. This work categorizes three-dimensional (3D) electrodes derived from materials such as foam, biomass, and electrospun fibers. By employing a flexible electrode design and compositional functionalization, high-speed mass transfer channels and abundant active sites for vanadium redox reactions can be created. Furthermore, the incorporation of 3D electrocatalysts into the electrodes is discussed, including metal-based, carbon-based, and composite materials. The strong interaction and ordered arrangement of these nanocomposites have an influence on the uniformity and stability of the surface charge distribution, thereby enhancing the electrochemical performance of the composite electrodes. Finally, the challenges and perspectives of VRFB are explored through advancements in 3D electrodes, 3D electrocatalysts, and mechanisms. It is hoped that this review will inspire the development of methodology and concept of 3D electrodes in VRFB, so as to promote the future development of scientific energy storage and conversion technology.

CuNi alloy anchored on dual-substrate TiOx/N-doped carbon nanofibers as a bifunctional electrocatalyst for rechargeable zinc-air batteries.

Development of non-noble metal-based electrocatalysts to enhance the performance of zinc-air batteries (ZABs) is of great significance, but it remains a formidable challenge due to their poor stability and activity. Herein, a bifunctional CuNi-TiOx/NCNFS electrocatalyst, featuring with electron-rich copper-nickel (CuNi) alloy nanoparticles anchored on titanium oxide/N-doped carbon nanofibers (TiOx/NCNFS), is constructed by a dual-substrate loading strategy. The introduction of TiOx has led to a significant increase in the stability of the dual-substrate. The strong electronic interaction between CuNi and TiOx strengthens the anchoring of active metal sites, thus accelerating the electron transfer. Theoretical calculations unclose that NCNFS can regulate the charge distribution of TiOx, inducing the charge transfer from NCNFS â†’ TiOx â†’ CuNi, thereby reducing the d-band center of Cu and Ni, which is beneficial to the desorption of intermediate oxide species of the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). Therefore, CuNi-TiOx/NCNFS delivers a remarkable bifunctional performance with a low OER overpotential of 258 mV at 10 mA cm-2 and an ORR half-wave potential of 0.85  V. When assembled into ZABs, CuNi-TiOx/NCNFS shows a low potential gap of 0.64 V, a higher power density of 149.6 mW cm-2 at 330 mA cm-2, and an outstanding stability for 250 h at 5mA cm-2. This study provides a novel approach by constructing dual-substrate to tune the electronic structure of active metal sites for efficient rechargeable ZABs.

Cr-doping promoted surface reconstruction of Ni3N electrocatalysts toward efficient overall water splitting.

Understanding and utilizing the dynamic changes of electrocatalysts under working conditions are important for advancing the sustainable hydrogen production. Here, we for the first time report that Cr-doping can promote the in situ reconstruction of a self-supported Ni3N electrocatalyst (Cr-Ni3N/NF) during oxygen and hydrogen evolution reactions (OER and HER), and therefore improve the electrocatalytic water splitting performance. As identified by in situ measurements and theoretical calculations, Cr-doping enhances OH- adsorption during OER at anode and thereby boosts the transformation of Ni3N pre-catalysts to defect-rich nickel oxyhydroxide (NiOOH) active species. Meanwhile, it facilitates the generation of Ni3N/Ni(OH)2 at cathodes due to effective H2O activation, leading to the fast HER kinetics on the Ni3N/Ni(OH)2 interfaces. Notably, the optimal Cr-Ni3N/NF displays good OER and HER performance in 1.0 M KOH electrolytes, with low overpotentials of 316 and 188 mV to achieve the current density of ± 100 mA cm-2, respectively. Benefiting from its bi-functionality and self-supporting property, an alkaline electrolyzer equipped with Cr-Ni3N/NF as both anode and cathode affords a small voltage of 1.72 V at 100 mA cm-2, along with 100 h operation stability. Elucidating that Cr-doping can boost in situ reconfiguration and consequently the electrocatalytic activity, this work would shed new light on the rational design and synthesis of electrocatalysts via directional reconstructions.

N, S co-doped carbon nanotubes loaded with Cu nanoclusters for efficient oxygen reduction reaction.

Developing highly superior precious-metal-free electrocatalysts for oxygen reduction reaction (ORR) are challenging and great significance. In this study, it is reported that an efficient ORR catalysts with N and S co-doped carbon nanotubes anchored to copper (Cu) nanoclusters by mechanical grinding and high temperature heat treatment. The obtained Cu-S1-N-C electrocatalysts exhibited a high ORR performance with an onset potential (Eonest) of 0.989 V and a half-wave potential (E1/2) of 0.905 V (vs. RHE) in alkaline electrolyte, which was superior to that of commercial Pt/C catalyst. In contrast to N doping alone, the defect structures and active species of the catalysts were optimized by precise modulation of S-atom doping, and moreover, the introduction of S-atoms provided more thiophene-sulfur active sites. This study provides an innovative idea for designing excellent ORR catalysts.

Atomic-Level Observation of Potential-Dependent Variations at the Surface of an Oxide Catalyst during Oxygen Evolution Reaction.

Understanding the intricate details of the surface atomic structure and composition of catalysts during the oxygen evolution reaction (OER) is crucial for developing catalysts with high stability in water electrolyzers. While many notable studies highlight surface amorphization and reconstruction, systematic analytical tracing of the catalyst surface as a function of overpotential remains elusive. Heteroepitaxial (001) films of chemically stable and lattice-oxygen-inactive LaCoO3 are thus utilized as a model catalyst to demonstrate a series of atomic-resolution observations of the film surface at different anodic potentials. The first key finding is that atoms at the surface are fairly dynamic even at lower overpotentials. Angstrom-scale atomic displacements within the perovskite framework are identified below a certain potential level. Another noteworthy feature is that amorphization (or paracrystallization) with no long-range order is finally induced at higher overpotentials. In particular, surface analyses consistently support that the oxidation of lattice oxygen is coupled with amorphous phase formation at the high potentials. Theoretical calculations also reveal an upward shift of oxygen 2p states toward the Fermi level, indicating enhanced lattice oxygen activation when atom displacement occurs more extensively. This study emphasizes that the degradation behavior of OER catalysts can distinctively vary depending on the overpotential level.

Electronic-Structure Transformation of Platinum-Rich Nanowires as Efficient Electrocatalyst for Overall Water Splitting.

Platinum (Pt) has been widely used as cathodic electrocatalysts for the hydrogen evolution reaction (HER) but unfortunately neglected as an anodic electrocatalyst for the oxygen evolution reaction (OER) due to excessively strong bonding with oxygen species in water splitting electrolyzers. Herein we report that fine control over the electronic-structure and local-coordination environment of Pt-rich PtPbCu nanowires (NWs) by doping of iridium (Ir) lowers the overpotential of the OER and simultaneously suppresses the overoxidation of Pt in IrPtPbCu NWs during water electrolysis. In light of the one-dimensional morphology featured with atomically dispersed IrOx species and electronically modulated Pt-sites, the IrPtPbCu NWs exhibit an enhanced OER (175 mV at 10 mA cm-2) and HER (25 mV at 10 mA cm-2) electrocatalytic performance in acidic media and yield a high turnover frequency. For OER at the overpotential of 250 mV, the IrPtPbCu NWs show an enhanced mass activity of 1.51 A mg-1Pt+Ir (about 19 times higher) than Ir/C. For HER at the overpotential of 50 mV, NWs exhibit a remarkable mass activity of 1.35 A mg-1Pt+Ir, which is 2.6-fold relative to Pt/C. Experimental results and theoretical calculations corroborate that the doping of Ir in NWs has the capacity to suppress the formation of Ptx>4 derivates and ameliorate the adsorption free energy of reaction intermediates during the water electrolysis. This approach enabled the realization of a previously unobserved mechanism for anodic electrocatalysts.

Facile and Scalable Colloidal Synthesis of Transition Metal Dichalcogenide Nanoparticles with High-Performance Hydrogen Production.

Transition metal dichalcogenides (TMDs) have garnered significant attention as efficient electrocatalysts for the hydrogen evolution reaction (HER) due to their high activity, stability, and cost-effectiveness. However, the development of a convenient and economical approach for large-scale HER applications remains a persistent challenge. In this study, we present the successful synthesis of TMD nanoparticles (including MoS2, RuS2, ReS2, MoSe2, RuSe2, and ReSe2) using a general colloidal method at room temperature. Notably, the ReSe2 nanoparticles synthesized in this study exhibit superior HER performance compared with previously reported nanostructured TMDs. Importantly, the synthesis of these TMD nanoparticles can readily be scaled up to gram quantities while preserving their exceptional HER performance. These findings highlight the potential of colloidal synthesis as a versatile and scalable approach for producing TMD nanomaterials with outstanding electrocatalytic properties for water splitting.

The Still Elusive Role of Lightweight Doping in Carbon-Based Electrocatalysts for the Selective Oxygen Reduction Reaction to Hydrogen Peroxide.

The two-electron electrocatalytic oxygen reduction reaction (ORR) to hydrogen peroxide (H2O2) is a valuable alternative to the more conventional and energy-intensive anthraquinone process. From a circularity viewpoint, metal-free catalysts constitute a sustainable alternative for the process. In particular, lightweight hetero-doped C-materials are cost-effective and easily scalable samples that replace - more and more frequently - the use of critical raw elements in the preparation of highly performing (electro)catalysts. Anyhow, their large-scale exploitation in industrial processes still suffers from technical limits of samples upscale and reproducibility other than a still moderate comprehension of their action mechanism in the process. This concept article offers a comprehensive and exhaustive "journey" through the most representative lightweight hetero-doped C-based electrocatalysts and their performance in the 2e- ORR process. It provides an interpretation of phenomena at the triple-phase interface of solid catalyst, liquid electrolyte and gaseous oxygen based on the doping-driven generation of ideal electronic microenvironments at the catalyst surface.