MoS2 Nanosheets Supported on 3D Graphene Aerogel as a Highly Efficient Catalyst for Hydrogen Evolution

The development of efficient catalysts for electrochemical hydrogen evolution is essential for energy conversion technologies. Molybdenum disulfide (MoS₂) has emerged as a promising electrocatalyst for hydrogen evolution reaction, and its performance greatly depends on its exposed edge sites and conductivity. Layered MoS₂ nanosheets supported on a 3D graphene aerogel network (GA‐MoS₂) exhibit significant catalytic activity in hydrogen evolution. The GA‐MoS₂ composite displays a unique 3D architecture with large active surface areas, leading to high catalytic performance with low overpotential, high current density, and good stability.     

Unlocking the Electrocatalytic Activity of Antimony for CO2 Reduction by Two‐Dimensional Engineering of the Bulk Material

Two‐dimensional (2D) materials are known to be useful in catalysis. Engineering 3D bulk materials into the 2D form can enhance the exposure of the active edge sites, which are believed to be the origin of the high catalytic activity. Reported herein is the production of 2D “few‐layer” antimony (Sb) nanosheets by cathodic exfoliation. Application of this 2D engineering method turns Sb, an inactive material for CO₂ reduction in its bulk form, into an active 2D electrocatalyst for reduction of CO₂ to formate with high efficiency. The high activity is attributed to the exposure of a large number of catalytically active edge sites. Moreover, this cathodic exfoliation process can be coupled with the anodic exfoliation of graphite in a single‐compartment cell for in situ production of a few‐layer Sb nanosheets and graphene composite. The observed increased activity of this composite is attributed to the strong electronic interaction between graphene and Sb.     

Atomic Layer Deposition of Hafnium(IV) Oxide on Graphene Oxide: Probing Interfacial Chemistry and Nucleation by using X‐ray Absorption and Photoelectron Spectroscopies

Interfacing graphene with metal oxides is of considerable technological importance for modulating carrier density through electrostatic gating as well as for the design of earth‐abundant electrocatalysts. Herein, we probe the early stages of the atomic layer deposition (ALD) of HfO₂ on graphene oxide using a combination of C and O K‐edge near‐edge X‐ray absorption fine structure spectroscopies and X‐ray photoelectron spectroscopy. Dosing with water is observed to promote defunctionalization of graphene oxide as a result of the reaction between water and hydroxyl/epoxide species, which yields carbonyl groups that further react with migratory epoxide species to release CO₂. The carboxylates formed by the reaction of carbonyl and epoxide species facilitate binding of Hf precursors to graphene oxide surfaces. The ALD process is accompanied by recovery of the π‐conjugated framework of graphene. The delineation of binding modes provides a means to rationally assemble 2D heterostructures.     

Scrutinizing Defects and Defect Density of Selenium‐Doped Graphene for High‐Efficiency Triiodide Reduction in Dye‐Sensitized Solar Cells

Understanding the impact of the defects/defect density of electrocatalysts on the activity in the triiodide (I₃^?) reduction reaction of dye‐sensitized solar cells (DSSCs) is indispensable for the design and construction of high‐efficiency counter electrodes (CEs). Active‐site‐enriched selenium‐doped graphene (SeG) was crafted by ball‐milling followed by high‐temperature annealing to yield abundant edge sites and fully activated basal planes. The density of defects within SeG can be tuned by adjusting the annealing temperature. The sample synthesized at an annealing temperature of 900 °C exhibited a superior response to the I₃^? reduction with a high conversion efficiency of 8.42 %, outperforming the Pt reference (7.88 %). Improved stability is also observed. DFT calculations showed the high catalytic activity of SeG over pure graphene is a result of the reduced ionization energy owing to incorporation of Se species, facilitating electron transfer at the electrode–electrolyte interface.     

Ultrasmall Cu7S4@MoS2 Hetero‐Nanoframes with Abundant Active Edge Sites for Ultrahigh‐Performance Hydrogen Evolution

Increasing the active edge sites of molybdenum disulfide (MoS₂) is an efficient strategy to improve the overall activity of MoS₂ for the hydrogen‐evolution reaction (HER). Herein, we report a strategy to synthesize the ultrasmall donut‐shaped Cu₇S₄@MoS₂ hetero‐nanoframes with abundant active MoS₂ edge sites as alternatives to platinum (Pt) as efficient HER electrocatalysts. These nanoframes demonstrate an ultrahigh activity with 200 mA cm^?2 current density at only 206 mV overpotential using a carbon‐rod counter electrode. The finding may provide guidelines for the design and synthesis of efficient and non‐precious chalcogenide nanoframe catalysts.     

Controllable growth of conical and cylindrical TiO2-carbon core-shell nanofiber arrays and morphologically dependent electrochemical properties

Quasi‐aligned cylindrical and conical core–shell nanofibers consisting of carbon shells and TiO₂ nanowire cores are produced in situ on Ti foils without using a foreign metallic catalyst and template. A cylindrical nanofiber has a TiO₂ nanowire core 30–50 nm in diameter and a 5–10 nm‐thick cylindrical carbon shell, while in the conical nanostructure the TiO₂ nanowire core has a diameter of 20–40 nm and the thickness of the carbon shell varies from about 200 nm at the bottom to about 5 nm at the tip. Electrochemical analysis reveals well‐defined redox peaks of the [Fe(CN)₆]^3?/4? redox couple and heterogeneous charge‐transfer rate constants of 0.010 and 0.062 cm s^?1 for the cylindrical and conical nanofibers, respectively. The coverage of exposed edge planes on the cylindrical and conical carbon shells is estimated to be 2.5 and 15.5 % respectively. The more abundant exposed edge planes on the conical nanofiber decrease the overpotential and increase the voltammetric resolution during electrochemical detection of uric acid and ascorbic acid. Our results suggest that the density of edge‐plane sites estimated from Raman scattering is not necessarily equal to the density of exposed edge‐plane sites, and only carbon electrodes with a large density of exposed edge planes or free graphene sheet ends exhibit better electrochemical performance.     

3D Nitrogen-Doped Graphene Encapsulated Metallic Nickel–Iron Alloy Nanoparticles for Efficient Bifunctional Oxygen Electrocatalysis

It is extremely desirable to explore high-efficient, affordable and robust oxygen electrocatalysts toward rechargeable Zn–air batteries (ZABs). A 3D porous nitrogen-doped graphene encapsulated metallic Ni₃Fe alloy nanoparticles aerogel (Ni₃Fe-GA₁) was constructed through a facile hydrothermal assembly and calcination process. Benefiting from 3D porous configuration with great accessibility, high electrical conductivity, abundant active sites, optimal nitrogen content and strong electronic interactions at the Ni₃Fe/N-doped graphene heterointerface, the obtained aerogel showed outstanding catalytic performance toward the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). Specifically, it exhibited an overpotential of 239 mV to attain 10 mA cm⁻² for OER, simultaneously providing a positive onset potential of 0.93 V within a half-wave potential of 0.8 V for ORR. Accordingly, when employed in the aqueous ZABs, Ni₃Fe-GA₁ achieved higher power density and superior reversibility than Pt/C−IrO₂ catalyst, making it a potential candidate for rechargeable ZABs.     

Hydroboration of Graphene Oxide: Towards Stoichiometric Graphol and Hydroxygraphane

Covalently functionalized graphene materials with well‐defined stoichiometric composition are of a very high importance in the research of 2D carbon material family due to their well‐defined properties. Unfortunately, most of the contemporary graphene‐functionalized materials do not have this kind of defined composition and, usually, the amount of heteroatoms bonded to graphene framework is in the range of 1–10 at. %. Herein, we show that by a well‐established hydroboration reaction chain, which introduces ?BH₂ groups into the graphene oxide structure, followed by H₂O₂ or CF₃COOH treatment as source of ?OH or ?H, we can obtain highly hydroxylated compounds of precisely defined composition with a general formula (C₁O_0.78H_0.75)_n, which we named graphol and highly hydroxylated graphane (C₁(OH)_0.51H_0.14)_n, respectively. These highly functionalized materials with an accurately defined composition are highly important for the field of graphene derivatives. The enhanced electrochemical performance towards important biomarkers as well as hydrogen evolution reaction is demonstrated.     

Surface‐Electron Coupling for Efficient Hydrogen Evolution

Maximizing the activity of materials towards the alkaline hydrogen evolution reaction while maintaining their structural stability under realistic working conditions remains an area of active research. Herein, we report the first controllable surface modification of graphene(G)/V₈C₇ heterostructures by nitrogen. Because the introduced N atoms couple electronically with V atoms, the V sites can reduce the energy barrier for water adsorption and dissociation. Investigation of the multi‐regional synergistic catalysis on N‐modified G/V₈C₇ by experimental observations and density‐functional‐theory calculations reveals that the increase of electron density on the epitaxial graphene enable it to become favorable for H* adsorption and the subsequent reaction with another H₂O molecule. This work extends the range of surface‐engineering approaches to optimize the intrinsic properties of materials and could be generalized to the surface modification of other transition‐metal carbides.     

Nanostructured MoS2 Nanorose/Graphene Nanoplatelet Hybrids for Electrocatalysis

Tailoring and enhancing electrocatalytic activity is of the utmost importance from the viewpoints of sustainable energy and sensing. MoS₂ and graphene show great promise for the electrocatalysis of many reactions. Given that both graphene and MoS₂ are highly anisotropic in nature, with edge planes that are several orders of magnitude more catalytically active than basal planes, a new hybrid material with maximized edge‐plane density to provide efficient electron transfer, high catalytic activity, and conductive cores was engineered. The hybrid material consists of radial MoS₂ nanosheets with a high density of edge planes and unsaturated active sulfur atoms as well as interspersed with conductive graphene nanoplatelets. This hybrid material exhibits excellent activity for the hydrogen evolution reaction and the detection of DNA nucleobases. Such a nanoengineered, nanostructured hybrid material may play a major role in future electrocatalytic devices.     

3D Carbon Foam Supported Edge-Rich N-Doped MoS2 Nanoflakes for Enhanced Electrocatalytic Hydrogen Evolution

Molybdenum disulfide (MoS₂) is one of the most promising alternatives to the Pt-based electrocatalysts for the hydrogen evolution reaction (HER). However, its performance is currently limited by insufficient active edge sites and poor electron transport. Hence, enormous efforts have been devoted to constructing more active edge sites and improving conductivity to obtain enhanced electrocatalytic performance. Herein, the 3D carbon foam (denoted as CF) supported edge-rich N-doped MoS₂ nanoflakes were successfully fabricated by using the commercially available polyurethane foam (PU) as the 3D substrate and PMo₁₂O₄₀³⁻ clusters (denoted as PMo₁₂) as the Mo source through redox polymerization, followed by sulfurization. Owing to the uniform distribution of nanoscale Mo sources and 3D carbon foam substrate, the as-prepared MoS₂-CF composite possessed well-exposed active edge sites and enhanced electrical conductivity. Systematic investigation demonstrated that the MoS₂-CF composite showed high HER performance with a low overpotential of 92 mV in 1.0 m KOH and 155 mV in 0.5 m H₂SO₄ at a current density of 10 mA cm⁻². This work offers a new pathway for the rational design of MoS₂-based HER electrocatalysts.     

Controlled Synthesis of 3D Flower‐like Ni2P Composed of Mesoporous Nanoplates for Overall Water Splitting

Developing efficient non‐noble metal and earth‐abundant electrocatalysts with tunable microstructures for overall water splitting is critical to promote clean energy technologies for a hydrogen economy. Herein, novel three‐dimensional (3D) flower‐like Ni₂P composed of mesoporous nanoplates with controllable morphology and high surface area was prepared by a hydrothermal method and low‐temperature phosphidation as efficient electrocatalysts for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Compared with the urchin‐like Ni_x P_y , the 3D flower‐like Ni₂P with a diameter of 5 μm presented an efficient and stable catalytic performance in 0.5 m H₂SO₄, with a small Tafel slope of 79 mV dec⁻¹ and an overpotential of about 240 mV at a current density of 10 mA cm⁻² with a mass loading density of 0.283 mg cm⁻². In addition, the catalyst also exhibited a remarkable performance for the OER in 1.0 m KOH electrolyte, with an overpotential of 320 mV to reach a current density of 10 mA cm⁻² and a small Tafel slope of 72 mV dec⁻¹. The excellent catalytic performance of the as‐prepared Ni₂P may be ascribed to its novel 3D morphology with unique mesoporous structure.     

Graphene‐Coated ZnO and SiO2 as Supports for CoO Nanoparticles with Enhanced Reducibility

The insertion of a graphene layer between cobalt and a substrate modifies the morphology and the oxidation/reduction properties of supported cobalt particles. Co forms a relatively flat structure on ZnO and SiO₂, whereas individual Co nanoparticles are formed after graphene coating of these substrates. The graphene layer moderates the formation of cobalt oxide in 5×10^?7 mbar O₂ and promotes the reduction of oxidized Co in H₂ at lower temperature. Angle‐resolved XPS measurements indicate that this is mainly a consequence of the restricted interaction of cobalt with the oxide supports. After the low‐pressure redox treatments, the graphene layer maintains a relatively high quality with a small number of defect sites.     

Tailoring Copper Nanocrystals towards C2 Products in Electrochemical CO2 Reduction

Favoring the CO₂ reduction reaction (CO2RR) over the hydrogen evolution reaction and controlling the selectivity towards multicarbon products are currently major scientific challenges in sustainable energy research. It is known that the morphology of the catalyst can modulate catalytic activity and selectivity, yet this remains a relatively underexplored area in electrochemical CO₂ reduction. Here, we exploit the material tunability afforded by colloidal chemistry to establish unambiguous structure/property relations between Cu nanocrystals and their behavior as electrocatalysts for CO₂ reduction. Our study reveals a non‐monotonic size‐dependence of the selectivity in cube‐shaped copper nanocrystals. Among 24 nm, 44 nm and 63 nm cubes tested, the cubes with 44 nm edge length exhibited the highest selectivity towards CO2RR (80 %) and faradaic efficiency for ethylene (41 %). Statistical analysis of the surface atom density suggests the key role played by edge sites in CO2RR.     

CO2 Laser-Induced Graphene with an Appropriate Oxygen Species as an Efficient Electrocatalyst for Hydrogen Peroxide Synthesis

Oxygen species functionalized graphene (O−G) is an effective electrocatalyst for electrochemically synthesizing hydrogen peroxide (H₂O₂) by a 2 e⁻ oxygen reduction reaction (ORR). The type of oxygen species and degree of carbon crystallinity in O−G are two key factors for the high catalytic performance of the 2 e⁻ ORR. However, the general preparing method of O−G by the precursor of graphite has the disadvantages of consuming massive strong oxidant and washing water. Herein, the biomass-based graphene with tunable oxygen species is rapidly fabricated by a CO₂ laser. In a flow cell setup, the laser-induced graphene (LIG) with abundant active oxygen species and graphene structure shows high catalytic performance including high Faraday efficiency (over 78 %) and high mass activity (814 mmolg_catalyst⁻¹ h⁻¹), superior to most of the reported carbon-based electrocatalysts. Density function theory demonstrates the meta-C atoms at nearby C−O, O−C=O species are the key catalytic sites. Therefore, we develop one facile method to rapidly convert biomass to graphene electrocatalyst used for H₂O₂ synthesis.     

Selenium‐Enriched Nickel Selenide Nanosheets as a Robust Electrocatalyst for Hydrogen Generation

To address the urgent need for clean and sustainable energy, the rapid development of hydrogen‐based technologies has started to revolutionize the use of earth‐abundant noble‐metal‐free catalysts for the hydrogen evolution reaction (HER). Like the active sites of hydrogenases, the cation sites of pyrite‐type transition‐metal dichalcogenides have been suggested to be active in the HER. Herein, we synthesized electrodes based on a Se‐enriched NiSe₂ nanosheet array and explored the relationship between the anion sites and the improved hydrogen evolution activity through theoretical and experimental studies. The free energy for atomic hydrogen adsorption is much lower on the Se sites (0.13 eV) than on the Ni sites (0.87 eV). Notably, this electrode benefits from remarkable kinetic properties, with a small overpotential of 117 mV at 10 mA cm^?2, a low Tafel slope of 32 mV per decade, and excellent stability. Control experiments showed that the efficient conversion of H⁺ into H₂ is due to the presence of an excess of selenium in the NiSe₂ nanosheet surface.     

Electrochemically Prepared Three‐dimensional Porous Nitrogen‐doped Graphene Modified Electrode for Non‐enzymatic Detection of Hydrogen Peroxide

A facile and green electrochemical method for the fabrication of three‐dimensional porous nitrogen‐doped graphene (3DNG) modified electrode was reported. This method embraces two consecutive steps: First, 3D graphene/polypyrrole (ERGO/PPy) composite was prepared by electrochemical co‐deposition of graphene and polypyrrole on a gold foil. Subsequently, the ERGO/PPy composite modified gold electrode was annealed at high temperature. Thus 3DNG modified electrode was obtained. Scanning electron microscopy (SEM), X‐ray photoelectron spectroscopy (XPS) and Raman spectroscopy were used to characterize the structure and morphology of the electrode. The electrode exhibits excellent electroanalytical performance for the reduction of hydrogen peroxide (H₂O₂). By linear sweep voltammetric measurement, the cathodic peak current was linearly proportional to H₂O₂ concentration in the range from 0.6 μM to 2.1 mM with a sensitivity of 1.0 μA μM⁻¹ cm⁻². The detection limit was ascertained to be 0.3 μM. The anti‐interference ability, reproducibility and stability of the electrode were carried out and the electrode was applied to the detection of H₂O₂ in serum sample with recoveries from 98.4 % to 103.2 %.     

Palladium Nanoparticles Embedded into Graphene Nanosheets: Preparation,Characterization, and Nonenzymatic Electrochemical Detection of H2O2

A novel nonenzymatic H₂O₂ sensor based on a palladium nanoparticles/graphene (Pd‐NPs/GN) hybrid nanostructures composite film modified glassy carbon electrode (GCE) was reported. The composites of graphene (GN) decorated with Pd nanoparticles have been prepared by simultaneously reducing graphite oxide (GO) and K₂PdCl₄ in one pot. The Pd‐NPs were intended to enlarge the interplanar spacing of graphene nanosheets and were well dispersed on the surface or completely embedded into few‐layer GN, which maintain their high surface area and prevent GN from aggregating. XPS analysis indicated that the surface Pd atoms are negatively charged, favoring the reduction process of H₂O₂. Moreover, the Pd‐NPs/GN/GCE could remarkably decrease the overpotential and enhance the electron‐transfer rate due to the good contact between Pd‐NPs and GN sheets, and Pd‐NPs have high catalytical effect for H₂O₂ reduction. Amperometric measurements allow observation of the electrochemical reduction of H₂O₂ at 0.5 V (vs. Ag/AgCl). The H₂O₂ reduction current is linear to its concentration in the range from 1×10^?9 to 2×10^?3 M, and the detection limit was found to be 2×10^?10 M (S/N=3). The as‐prepared nonenzymatic H₂O₂ sensor exhibits excellent repeatability, selectivity and long‐term stability.     

High Catalytic Activity of Nitrogen and Sulfur Co‐Doped Nanoporous Graphene in the Hydrogen Evolution Reaction

Chemical doping has been demonstrated to be an effective way to realize new functions of graphene as metal‐free catalyst in energy‐related electrochemical reactions. Although efficient catalysis for the oxygen reduction reaction (ORR) has been achieved with doped graphene, its performance in the hydrogen evolution reaction (HER) is rather poor. In this study we report that nitrogen and sulfur co‐doping leads to high catalytic activity of nanoporous graphene in HER at low operating potential, comparable to the best Pt‐free HER catalyst, 2D MoS₂. The interplay between the chemical dopants and geometric lattice defects of the nanoporous graphene plays the fundamental role in the superior HER catalysis.     

Active Edge‐Site‐Rich Carbon Nanocatalysts with Enhanced Electron Transfer for Efficient Electrochemical Hydrogen Peroxide Production

A highly efficient, metal‐free carbon nanocatalyst is presented that possesses abundant active, oxygenated graphitic edge sites. The edge site‐rich nanocarbon catalyst exhibits about 28 times higher activity for H₂O₂ production than a basal plane‐rich carbon nanotube with a H₂O₂ selectivity over 90 %. The oxidative treatment further promotes the H₂O₂ generation activity to reach close to the thermodynamic limit. The optimized nanocarbon catalyst shows a very high H₂O₂ production activity, surpassing previously reported catalysts in alkaline media. Moreover, it can stably produce H₂O₂ for 16 h with Faradaic efficiency reaching 99 % and accumulated H₂O₂ concentration of 24±2 mm . Importantly, we find that the heterogeneous electron transfer kinetics of the carbon‐based catalyst is closely related to the electrocatalytic activity, suggesting that first outer‐sphere electron transfer to O₂ is an important step governing the H₂O₂ production rate.