Ice‐Assisted Synthesis of Black Phosphorus Nanosheets as a Metal‐Free Photocatalyst: 2D/2D Heterostructure for Broadband H2 Evolution

A 2D/2D heterojunction of black phosphorous (BP)/graphitic carbon nitride (g‐C₃N₄) is designed and synthesized for photocatalytic H₂ evolution. The ice‐assisted exfoliation method developed herein for preparing BP nanosheets from bulk BP, leads to high yield of few‐layer BP nanosheets (≈6 layers on average) with large lateral size at reduced duration and power for liquid exfoliation. The combination of BP with g‐C₃N₄ protects BP from oxidation and contributes to enhanced activity both under λ > 420 nm and λ > 475 nm light irradiation and to long‐term stability. The H₂ production rate of BP/g‐C₃N₄ (384.17 µmol g^?1 h^?1) is comparable to, and even surpasses that of the previously reported, precious metal‐loaded photocatalyst under λ > 420 nm light. The efficient charge transfer between BP and g‐C₃N₄ (likely due to formed N? P bonds) and broadened photon absorption (supported both experimentally and theoretically) contribute to the excellent photocatalytic performance. The possible mechanisms of H₂ evolution under various forms of light irradiation is unveiled. This work presents a novel, facile method to prepare 2D nanomaterials and provides a successful paradigm for the design of metal‐free photocatalysts with improved charge‐carrier dynamics for renewable energy conversion.     

Unique PCoN Surface Bonding States Constructed on g‐C3N4 Nanosheets for Drastically Enhanced Photocatalytic Activity of H2 Evolution

Developing high‐efficiency and low‐cost photocatalysts by avoiding expensive noble metals, yet remarkably improving H₂ evolution performance, is a great challenge. Noble‐metal‐free catalysts containing Co(Fe)?N?C moieties have been widely reported in recent years for electrochemical oxygen reduction reaction and have also gained noticeable interest for organic transformation. However, to date, no prior studies are available in the literature about the activity of N‐coordinated metal centers for photocatalytic H₂ evolution. Herein, a new photocatalyst containing g‐C₃N₄ decorated with CoP nanodots constructed from low‐cost precursors is reported. It is for the first time revealed that the unique P(δ^?)?Co(δ⁺)?N(δ^?) surface bonding states lead to much superior H₂ evolution activity (96.2 µmol h^?1) compared to noble metal (Pt)‐decorated g‐C₃N₄ photocatalyst (32.3 µmol h^?1). The quantum efficiency of 12.4% at 420 nm is also much higher than the record values (≈2%) of other transition metal cocatalysts‐loaded g‐C₃N₄. It is believed that this work marks an important step toward developing high‐performance and low‐cost photocatalytic materials for H₂ evolution.     

Targeted Exfoliation and Reassembly of Polymeric Carbon Nitride for Efficient Photocatalysis

Switching the properties of photocatalytic materials targetedly and exerting these advantages fully in different photoredox reactions are crucial for the sufficient utilization of solar energy but still presents a significant challenge. This study presents a facile, green, and reversible exfoliation–reassembly strategy to switch the features of polymeric carbon nitride (CN) favorably for different photoredox reactions. The giant expansion effect of in situ‐generated H₂O molecules confined to the interlayer results in the mass production of ultrathin polymeric CN nanosheets, giving a high yield, i.e., up to 48%, of ultrathin nanosheets in a mild solution (pH ≈1.3). Interestingly, the exfoliation–reassembly process as well as the properties of CN are largely reversible via alternating the interlayer groups. Moreover, the exfoliated and reassembled CN achieve a superior photocatalytic activity for isopropanol degradation (acetone: 345 µmol h^?1; CO₂: 23 µmol h^?1) and H₂ evolution (1370 µmol h^?1), resulting in a high apparent quantum yield of 27% and 46%, respectively, at ≈420 nm.     

Edge‐Enriched Ultrathin MoS2 Embedded Yolk‐Shell TiO2 with Boosted Charge Transfer for Superior Photocatalytic H2 Evolution

Exploring TiO₂‐photocatalysts for sunlight conversion has high demand in artificial photosynthesis. In this work, edge‐enriched ultrathin molybdenum disulfide (MoS₂) flakes are uniformly embedded into the bulk of yolk‐shell TiO₂ as a cocatalyst to accelerate photogenerated‐electron transfer from the bulk to the surface of TiO₂. The as‐formed MoS₂/TiO₂ (0.14 wt%) hybrids exhibit a high hydrogen evolution rate (HER) of 2443 µmol g^?1 h^?1, about 1000% and 470% of that of pristine TiO₂ (247 µmol g^?1 h^?1) and bulk MoS₂ decorated TiO₂ (513 µmol g^?1 h^?1). Such a greatly enhanced HER is attributed to the exposed catalytic edges of the ultrathin MoS₂ flakes with a robust chemical linkage (Ti? S bond), providing rapid charge transfer channels between TiO₂ and MoS₂. The catalytic stability is promoted by the antiaggregation of the highly dispersed MoS₂ flakes in the bulk of yolk‐shell TiO₂. The exponential fitted decay kinetics of time‐resolved photoluminescence (ns‐PL) spectra illustrates that embedding ultrathin MoS₂ flakes in TiO₂ effectively decreases the average lifetime of PL in the MoS₂/TiO₂ hybrids (τ_ave = 4.55 ns), faster than that of pristine TiO₂ (≈7.17 ns) and the bulk MoS₂/TiO₂ (≈6.13 ns), allowing a superior charge separation and charge trapping process for reducing water.     

Unique P?Co?N Surface Bonding States Constructed on g‐C3N4 Nanosheets for Drastically Enhanced Photocatalytic Activity of H2 Evolution

Developing high‐efficiency and low‐cost photocatalysts by avoiding expensive noble metals, yet remarkably improving H₂ evolution performance, is a great challenge. Noble‐metal‐free catalysts containing Co(Fe)? N? C moieties have been widely reported in recent years for electrochemical oxygen reduction reaction and have also gained noticeable interest for organic transformation. However, to date, no prior studies are available in the literature about the activity of N‐coordinated metal centers for photocatalytic H₂ evolution. Herein, a new photocatalyst containing g‐C₃N₄ decorated with CoP nanodots constructed from low‐cost precursors is reported. It is for the first time revealed that the unique P(δ^?)? Co(δ⁺)? N(δ^?) surface bonding states lead to much superior H₂ evolution activity (96.2 µmol h^?1) compared to noble metal (Pt)‐decorated g‐C₃N₄ photocatalyst (32.3 µmol h^?1). The quantum efficiency of 12.4% at 420 nm is also much higher than the record values (≈2%) of other transition metal cocatalysts‐loaded g‐C₃N₄. It is believed that this work marks an important step toward developing high‐performance and low‐cost photocatalytic materials for H₂ evolution.     

Coupling Piezocatalysis and Photocatalysis in Bi4NbO8X (X = Cl,Br) Polar Single Crystals

Reactive oxygen species (ROS) as green oxidants are of great importance for environmental and biological applications. Photocatalysis is one of the major routes for ROS evolution, which is seriously restricted by rapid charge recombination. Herein, piezocatalysis and photocatalysis (i.e., piezo–photocatalysis) are coupled to efficiently produce superoxide radicals (?O₂^?), hydrogen peroxide (H₂O₂), and hydroxyl radicals (?OH) via oxygen reduction reaction (ORR), by using Bi₄NbO₈X (X = Cl, Br) single crystalline nanoplates. Significantly, the piezo‐photocatalytic process leads to the highest ORR performance of the Bi₄NbO₈Br nanoplates, exhibiting ?O₂^?, H₂O₂, and ?OH evolution rates of 98.7, 792, and 33.2 µmol g^?1 h^?1, respectively. The formation of a polarized electric field and band bending allows directional separation of charge carriers, promoting the catalytic activity. Furthermore, the reductive active sites are found enriched on all the facets in the piezo–photocatalytic process, also contributing to the ORR. By piezo–photodeposition of Pt to artificially plant reductive reactive sites, the Bi₄NbO₈Br plates demonstrate largely enhanced photocatalytic H₂ production activity with a rate of 203.7 µmol g^?1 h^?1. The present work advances piezo–photocatalysis as a new route for ROS generation, but also discloses the potential of piezo–photocatalytic active sites enriching for H₂ evolution.     

Anisotropic Ag2S–Au Triangular Nanoprisms with Desired Configuration for Plasmonic Photocatalytic Hydrogen Generation in Visible/Near‐Infrared Region

Anisotropic Ag₂S‐edged Au‐triangular nanoprisms (TNPs) are constructed by controlling preferential overgrowth of Ag₂S as plasmonic photocatalysts for hydrogen generation. Under visible and near‐infrared light irradiation, Ag₂S‐edged Au‐TNPs exhibit almost fourfold higher efficiency (796 µmol h⁻¹ g⁻¹) than those of Ag₂S‐covered Au‐TNPs (216 µmol h⁻¹ g⁻¹) and pure Au‐TNPs in hydrogen generation. A single‐particle photoluminescence study demonstrates that the plasmon‐induced hot electrons transfer from Au‐TNPs to Ag₂S for hydrogen generation. Finite‐difference‐time‐domain simulations verify that the corners/edges of Au‐TNPs are high‐curvature sites with maximum electric field distributions facilitating hot electron generation and transfer. Therefore, Ag₂S‐edged Au‐TNPs are efficient plasmonic photocatalyst with the desired configurations for charge separation boosting hydrogen generation.     

Photocatalyst Interface Engineering: Spatially Confined Growth of ZnFe2O4 within Graphene Networks as Excellent Visible‐Light‐Driven Photocatalysts

High‐performance photocatalysts should have highly crystallized nanocrystals (NCs) with small sizes, high separation efficiency of photogenerated electron–hole pairs, fast transport and consumption of photon‐excited electrons from the surface of catalyst, high adsorption of organic pollutant, and suitable band gap for maximally utilizing sunlight energy. However, the design and synthesis of these versatile structures still remain a big challenge. Here, we report a novel strategy for the synthesis of ultrasmall and highly crystallized graphene–ZnFe₂O₄ photocatalyst through interface engineering by using interconnected graphene network as barrier for spatially confined growth of ZnFe₂O₄, as transport channels for photon‐excited electron from the surface of catalyst, as well as the electron reservoir for suppressing the recombination of photogenerated electron–hole pairs. As a result, about 20 nm ZnFe₂O₄ NCs with highly crystallized (311) plane confined in the graphene network exhibit an excellent visible‐light‐driven photocatalytic activity with an ultrafast degradation rate of 1.924 × 10^?7 mol g^?1 s^?1 for methylene blue, much higher than those of previously reported photocatalysts such as spinel‐based photocatalysts (20 times), TiO₂‐based photocatalysts (4 times), and other photocatalysts (4 times). Our strategy can be further extended to fabricate other catalysts and electrode materials for supercapacitors and Li‐ion batteries.     

Refining Energy Levels in ReS2 Nanosheets by Low‐Valent Transition‐Metal Doping for Dual‐Boosted Electrochemical Ammonia/Hydrogen Production

Electrocatalytic nitrogen reduction reaction (NRR) and hydrogen evolution reaction (HER) are intriguing approaches to nitrogen fixation and hydrogen production under ambient conditions, given the need to discover efficient and stable catalysts to light up the “green chemistry” future. However, bottlenecks are often found during N₂/H₂O activation, the very first step of NRR/HER, due to energetic electron injection from the surface of electrocatalysts. It is reported that the bottlenecks for both NRR and HER can be tackled by engineering the energy level via low‐valent transition‐metal doping, simultaneously, where rhenium disulfide (ReS₂) is employed as a model platform to prove the concept. The doped low‐valent transition‐metal domains (e.g., Fe, Co, Ni, Cu, Zn) in ReS₂ provide more active sites for N₂/H₂O chemisorption and electron transfer, not only weakening the N?N/O? H bonds for easier dissociation through proton coupling, but also elevating d‐band center toward the Fermi level with more electron energy for N₂/H₂O reduction. As a result, it is found that iron‐doped ReS₂ nanosheets wrapped nitrogen‐doped carbon nanofiber (Fe‐ReS₂@N‐CNF) catalyst exhibits superior electrochemical activity with eightfold higher ammonia production yield of 80.4 µg h^?1 mg^?1_cat., and lower onset overpotential of 146 mV and Tafel slope of 63 mV dec^?1, when comparing with the pristine ReS₂.     

Apparent Potential Difference Boosting Directional Electron Transfer for Full Solar Spectrum‐Irradiated Catalytic H2 Evolution

Directional charge transfer among nanolayers of graphitic carbon nitride (g‐C₃N₄) is still inefficient because of the interlayer electrostatic potential barrier, which tremendously restricts the utilization of charges in conversion of solar energy into fuel. Herein, an apparent potential among nanolayers is introduced to boost interlayer electron transfer by curving planar g‐C₃N₄ nanosheets into carbon nitride square tubes (C₃N₄Ts), and Ni₂P nanoparticles as electron acceptors are loaded on C₃N₄Ts (Ni₂P/C₃N₄Ts) for highly efficient H₂ evolution. Study results present H₂‐evolution efficiency over the constructed Ni₂P/C₃N₄Ts up to 19.25 mmol g^?1 h^?1 with a large number of visible H₂ bubbles, which is more than 1.9 and 2.6 times of that over g‐C₃N₄ supported 1 wt%Pt and 3 wt%Pd, respectively. Density functional theory (DFT) and characterizations reveal efficient directional transfer through C₃N₄T interlayer (001) to Ni₂P (111) is achieved under the apparent potential difference of C₃N₄Ts, which therefore ensures the high H₂‐evolution performance of Ni₂P/C₃N₄Ts. These results in the field of material engineering supply a novel strategy to boost directional charge transfer for solar energy conversion efficiency by introducing apparent potential difference.     

Delocalized Electron Accumulation at Nanorod Tips: Origin of Efficient H2 Generation

Photocatalytic hydrogen (H₂) evolution requires efficient electron transfer to catalytically active sites in competition with charge recombination. Thus, controlling charge‐carrier dynamics in the photocatalytic H₂ evolution process is essential for optimized photocatalyst nanostructures. Here, the efficient delocalization of electrons is demonstrated in a heterostructure consisting of optimized MoS₂ tips and CdS nanorods (M‐t‐CdS Nrs) synthesized by amine‐assisted oriented attachment. The heterostructure achieves photocatalytic H₂ activity of 8.44 mmol h^?1 g^?1 with excellent long‐term durability (>23 h) without additional passivation under simulated solar light (AM 1.5, 100 mW cm^?2). This activity is nearly two orders of magnitude higher than that of pure CdS Nrs. The impressive photocatalytic H₂ activity of M‐t‐CdS Nrs reflects favorable charge‐carrier dynamics, as determined by steady‐state PL and time‐correlated single photon counting correlation analysis at low temperature. The MoS₂ cocatalysts precisely located at the end of the CdS Nrs exhibit ultrafast charge transfer and slow charge recombination via spatially localized deeper energy states, resulting in a highly efficient H₂ evolution reaction in lactic acid containing an electrolyte.     

A Cocatalytic Electron‐Transfer Cascade Site‐Selectively Placed on TiO2 Nanotubes Yields Enhanced Photocatalytic H2 Evolution

Separation and transfer of photogenerated charge carriers are key elements in designing photocatalysts. TiO₂ in numerous geometries has been for many years the most studied photocatalyst. To overcome kinetic limitations and achieve swift charge transfer, TiO₂ has been widely investigated with cocatalysts that are commonly randomly placed nanoparticles on a TiO₂ surface. The poor control over cocatalyst placement in powder technology approaches can drastically hamper the photocatalytic efficiencies. Here in contrast it is shown that the site‐selective placement of suitable charge‐separation and charge‐transfer cocatalysts on a defined TiO₂ nanotube morphology can provide an enhancement of the photocatalytic reactivity. A TiO₂–WO₃–Au electron‐transfer cascade photocatalyst is designed with nanoscale precision for H₂ production on TiO₂ nanotube arrays. Key aspects in the construction are the placement of the WO₃/Au element at the nanotube top by site‐selective deposition and self‐ordered thermal dewetting of Au. In the ideal configuration, WO₃ acts as a buffer layer for TiO₂ conduction band electrons, allowing for their efficient transfer to the Au nanoparticles and then to a suitable environment for H₂ generation, while TiO₂ holes due to intrinsic upward band bending in the nanotube walls and short diffusion length undergo a facilitated transfer to the electrolyte where oxidation of hole‐scavenger molecules takes place. These photocatalytic structures can achieve H₂ generation rates significantly higher than any individual cocatalyst–TiO₂ combination, including a classic noble metal–TiO₂ configuration.     

A Self‐Standing High‐Performance Hydrogen Evolution Electrode with Nanostructured NiCo2O4/CuS Heterostructures

An efficient self‐standing 3D hydrogen evolution cathode has been developed by coating nickel cobaltite (NiCo₂O₄)/CuS nanowire heterostructures on a carbon fiber paper (CFP). The obtained CFP/NiCo₂O₄/CuS electrode shows exceptional hydrogen evolution reaction (HER) performance and excellent durability in acidic conditions. Remarkably, as an integrated 3D hydrogen‐evolving cathode operating in acidic electrolytes, CFP/NiCo₂O₄/CuS maintains its activity more than 50 h and exhibits an onset overpotential of 31.1 mV, an exchange current density of 0.246 mA cm^?2, and a Tafel slope of 41 mV dec^?1. Compared to other non‐Pt electrocatalysts reported to date, CFP/NiCo₂O₄/CuS exhibits the highest HER activity and can be used in HER to produce H₂ with nearly quantitative faradaic yield in acidic aqueous media with stable activity. Furthermore, by using CFP/NiCo₂O₄/CuS as a self‐standing electrode in a water electrolyzer, a current density of 18 mA cm^?2 can be achieved at a voltage of 1.5 V which can be driven by a single‐cell battery. This strategy provides an effective, durable, and non‐Pt electrode for water splitting and hydrogen generation.     

Localized Surface Plasmon Resonance Enhanced Photocatalytic Hydrogen Evolution via Pt@Au NRs/C3N4 Nanotubes under Visible‐Light Irradiation

Au nanorods (NRs) decorated carbon nitride nanotubes (Au NRs/CNNTs) photocatalysts have been designed and prepared by impregnation–annealing approach. Localized surface plasmon resonance (LSPR) peaks of Au NRs can be adjusted by changing the aspect ratios, and the light absorption range of Au NRs/CNNTs is extended to longer wavelength even near‐infrared light. Optimal composition of Pt@Au NR₇₆₉/CNNT₆₅₀ has been achieved by adjusting the LSPR peaks of Au NRs and further depositing Pt nanoparticles (NPs), and the photocatalytic H₂ evolution rate is 207.0 µmol h^?1 (20 mg catalyst). Preliminary LSPR enhancement photocatalytic mechanism is suggested. On one hand, LSPR of Au NRs is beneficial for visible‐light utilization. On the other hand, Pt NPs and Au NRs have a synergetic enhancement effect on photocatalytic H₂ evolution of CNNTs, in which the local electromagnetic field can improve the photogenerated carrier separation and direct electron transfer increases the hot electron concentration while Au NRs as the electron channel can well restrain charge recombination, finally Pt as co‐catalyst can boost H⁺ reduction rate. This work provides a new way to develop efficient photocatalysts for splitting water, which can simultaneously extend light absorption range and facilitate carrier generation, transportation and reduce carrier recombination.     

A Facet‐Dependent Schottky‐Junction Electron Shuttle in a BiVO4{010}–Au–Cu2O Z‐Scheme Photocatalyst for Efficient Charge Separation

Interfacial charge separation and transfer are the main challenges of efficient semiconductor‐based Z‐scheme photocatalytic systems. Here, it is discovered that a Schottky junction at the interface between the BiVO₄ {010} facet and Au is an efficient electron‐transfer route useful for constructing a high‐performance BiVO₄{010}–Au–Cu₂O Z‐scheme photocatalyst. Spectroscopic and computational studies reveal that hot electrons in BiVO₄ {010} more easily cross the Schottky barrier to expedite the migration from BiVO₄ {010} to Au and are subsequently captured by the excited holes in Cu₂O. This crystal‐facet‐dependent electron shuttle allows the long‐lived holes and electrons to stay in the valence band of BiVO₄ and conduction band of Cu₂O, respectively, contributing to improved light‐driven CO₂ reduction. This unique semiconductor crystal‐facet sandwich structure will provide an innovative strategy for rational design of advanced Z‐scheme photocatalysts.     

In Situ Grown Pristine Cobalt Sulfide as Bifunctional Photocatalyst for Hydrogen and Oxygen Evolution

Herein, transition metal chalcogenides of pristine cobalt sulfides are rationally designed to act as robust bifunctional photocatalysts for visible‐light‐driven water splitting for the first time. Through moderate solvothermal route, cobalt sulfides are synthesized in situ growth and observed by scanning electron microscope image analysis. Noteworthily, 3D hierarchical cobalt sulfides acting as bifunctional photocatalysts are implemented to catalyze the visible‐light‐driven oxygen evolution reaction and hydrogen evolution reaction. This efficient, earth‐abundant, and nonnoble water splitting catalyst for artificial photosynthesis is thoroughly analyzed by various spectroscopic techniques with the aim of investigating its photocatalytic mechanism under visible‐light illumination. The main catalyst of CoS‐2 exhibits considerable H₂ evolution rate of 1196 µmol h^?1 g^?1 and O₂ yield of 63.5%. The efficient activity is attributed to the effective electron transfer between the photosensitizer and catalyst, which is verified by transient absorption experiments. The effective electron transfer between the photosensitizer and catalyst during water oxidation is verified by the dramatic decline of [Ru(bpy)₃]³⁺ concentration in the presence of the catalyst CoS‐2. At the same time, transient absorption experiments support a rapid electron transfers from ³EY* (excited photosensitizer eosin‐Y) to the catalyst CoS‐2 for efficient hydrogen evolution.     

Facile “Spot‐Heating” Synthesis of Carbon Dots/Carbon Nitride for Solar Hydrogen Evolution Synchronously with Contaminant Decomposition

The use of solar energy to produce the clean hydrogen (H₂) energy from water splitting is a promising means of renewable energy conversion. High activation barriers for O₂ generation associated with the rate‐limiting steps require utilization of noble metal‐based cocatalysts, which complicates the fabrication procedure and compromises the stability of the catalyst. Here, a homogenous “spot heating” approach is designed via the ultrasonic cavitation effect for evenly embedding highly crystalline carbon quantum dots (CQDs) on 2D C₃N₄ nanosheets. Based on density functional calculations and electrochemical experiments, the optimal introduction of CQDs into C₃N₄ not only extends light absorption spectrum, but also reduces effective mass of electrons (e^?), facilitating photocarrier transport from excited sites. And, more importantly, the well‐organized CQDs with superior peroxidase mimetic activity can increase catalytic H₂ production through the process of (i) 2H₂O → H₂O₂ + H₂; (ii) H₂O₂→2 ? OH; (iii) ?OH + bisphenol A→ Final Products, with H₂ production rate (152 µmol g^?1 h^?1) several times higher than that for pure C₃N₄. This work demonstrates an ideal platform for efficient H₂ production with synergetic organic contaminant degradation, thereby opening possibilities for coupling energy conversion with environmental remediation.     

Cocatalyst‐Free Photocatalysts for Efficient Visible‐Light‐Induced H2 Production: Porous Assemblies of CdS Quantum Dots and Layered Titanate Nanosheets

Highly efficient, visible‐light‐induced H₂ generation can be achieved without the help of a Pt cocatalyst by new hybrid photocatalysts, in which CdS quantum dots (QDs) (particle size ≈2.5 nm) are incorporated in the porous assembly of sub‐nanometer‐thick layered titanate nanosheets. Due to the very‐limited crystal dimension of component semiconductors, the electronic structure of CdS QDs is strongly coupled with that of the layered titanate nanosheets, leading to an efficient electron transfer between them and the enhancement of the CdS photostability. As a consequence of the promoted electron transfer, the photoluminescence of CdS QDs is nearly quenched after hybridization, indicating the almost‐suppression of electron‐hole recombination. These Pt‐cocatalyst‐free, CdS‐layered titanate nanohybrids show much‐higher photocatalytic activity for H₂ production than the precursor CdS QDs and layered titanate, which is due to the increased lifetime of the electrons and holes, the decrease of the bandgap energy, and the expansion of the surface area upon hybridization. The observed photocatalytic efficiency of these Pt‐free hybrids (≈1.0 mmol g^?1 h^?1) is much greater than reported values of other Pt‐free CdS‐TiO₂ systems. This finding highlights the validity of 2D semiconductor nanosheets as effective building blocks for exploring efficient visible‐light‐active photocatalysts for H₂ production.     

A Composite of Carbon‐Wrapped Mo2C Nanoparticle and Carbon Nanotube Formed Directly on Ni Foam as a High‐Performance Binder‐Free Cathode for Li‐O2 Batteries

Cathode design is indispensable for building Li‐O₂ batteries with long cycle life. A composite of carbon‐wrapped Mo₂C nanoparticles and carbon nanotubes is prepared on Ni foam by direct hydrolysis and carbonization of a gel composed of ammonium heptamolybdate tetrahydrate and hydroquinone resin. The Mo₂C nanoparticles with well‐controlled particle size act as a highly active oxygen reduction reactions/oxygen evolution reactions (ORR/OER) catalyst. The carbon coating can prevent the aggregation of the Mo₂C nanoparticles. The even distribution of Mo₂C nanoparticles results in the homogenous formation of discharge products. The skeleton of porous carbon with carbon nanotubes protrudes from the composite, resulting in extra voids when applied as a cathode for Li‐O₂ batteries. The batteries deliver a high discharge capacity of ≈10 400 mAh g^?1 and a low average charge voltage of ≈4.0 V at 200 mA g^?1. With a cutoff capacity of 1000 mAh g^?1, the Li‐O₂ batteries exhibit excellent charge–discharge cycling stability for over 300 cycles. The average potential polarization of discharge/charge gaps is only ≈0.9 V, demonstrating the high ORR and OER activities of these Mo₂C nanoparticles. The excellent cycling stability and low potential polarization provide new insights into the design of highly reversible and efficient cathode materials for Li‐O₂ batteries.     

Engineering the Photocatalytic Behaviors of g/C3N4‐Based Metal‐Free Materials for Degradation of a Representative Antibiotic

Graphitic carbon nitride (g/C₃N₄) is of promise as a highly efficient metal‐free photocatalyst, yet engineering the photocatalytic behaviours for efficiently and selectively degrading complicated molecules is still challenging. Herein, the photocatalytic behaviors of g/C₃N₄ are modified by tuning the energy band, optimizing the charge extraction, and decorating the cocatalyst. The combination shows a synergistic effect for boosting the photocatalytic degradation of a representative antibiotic, lincomycin, both in the degradation rate and the degree of decomposition. In comparison with the intrinsic g/C₃N₄, the structurally optimized photocatalyst shows a tenfold enhancement in degradation rate. Interestingly, various methods and experiments demonstrate the specific catalytic mechanisms for the multiple systems of g/C₃N₄‐based photocatalysts. In the degradation, the active species, including ·O₂^?, ·OH, and h⁺, have different contributions in the different photocatalysts. The intermediate, H₂O₂, plays an important role in the photocatalytic process, and the detailed functions and originations are clarified for the first time.