Self-assembled S-scheme In_(2.77)S_(4)/K^(+)-doped g-C_(3)N_(4)photocatalyst with selective O_(2)reduction pathway for efficient H_(2)O_(2)production using water and air

The development of an efficient artificial H_(2)O_(2)photosynthesis system is a challenging work using H_(2)O and O_(2)as starting materials.Herein,3D In2.77S_(4)nanoflower precursor was in-situ deposited on K^(+)-doped g-C_(3)N_(4)(KCN)nanosheets using a solvothermal method,then In2.77S_(4)/KCN(IS/KCN)het-erojunction with an intimate interface was obtained after a calcination process.The investigation shows that the photocatalytic H_(2)O_(2)production rate of 50IS/KCN can reach up to 1.36 mmol g^(-1)h^(-1)without any sacrificial reagents under visible light irradiation,which is 9.2 times and 4.1 times higher than that of KCN and In2.77S_(4),respectively.The enhanced activity of the above composite can be mainly attributed to the S-scheme charge transfer route between KCN and In2.77S_(4)according to density functional theory calculations,electron paramagnetic resonance and free radical capture tests,leading to an expanded light response range and rapid charge separation at their interface,as well as preserving the active electrons and holes for H_(2)O_(2)production.Besides,the unique 3D nanostructure and surface hydrophobicity of IS/KCN facilitate the diffusion and transportation of O_(2)around the active centers,the energy barriers of O_(2)protonation and H_(2)O_(2)desorption steps are ef-fectively reduced over the composite.In addition,this system also exhibits excellent light harvesting ability and stability.This work provides a potential strategy to explore a sustainable H_(2)O_(2)photo-synthesis pathway through the design of heterojunctions with intimate interfaces and desired reac-tion thermodynamics and kinetics.

High selectivity to p-chloroaniline in the hydrogenation of p-chloronitrobenzene on Ni modified carbon nitride catalyst

A nanocomposite composed of Ni modified carbon nitride was synthesized and used in the hydro- genation of p-chloronitrobenzene. H/D exchange demonstrated that the hydrogen chemisorbed on the surface of this nanocomposite catalyst had a hydrogen atom density of 0.65/nm2. It was active for hydrogenation but its activity was inferior to the hydrogen adsorbed on a Ni/Al2O3 catalyst. Catalytic tests showed that this catalyst possessed a lower activity than Ni/AhO3 but the selectivity towards p-chloroaniline was above 99.9%. Even at high conversion, the catalyst maintained high selectivity, which was attributed to the unique surface property of the catalyst and the absence of a site for the adsorption ofp-chloronitrobenzene, which prevents the C-Cl bond from breaking.

Enhanced photocatalytic H_2 production over dual-cocatalyst-modified g-C_3N_4 heterojunctions

Ag nanoparticles (NPs) were deposited on the surface of g-C3N4 (CN) by an in situ calcination method. NiS was successfully loaded onto the composites by a hydrothermal method. The results showed that the 10 wt%-NiS/1.0 wt%-Ag/CN composite exhibits excellent photocatalytic H2 generation performance under solar-light irradiation. An H2 production rate of 9.728 mmol·g^-1·h^-1 was achieved, which is 10.82-, 3.45-, and 2.77-times higher than those of pure g-C3N4, 10 wt%-NiS/CN, and 1.0 wt%-Ag/CN composites, respectively. This enhanced photocatalytic H2 generation can be ascribed to the co-decoration of Ag and NiS on the surface of g-C3N4, which efficiently improves light harvesting capacity, photogenerated charge carrier separation, and photocatalytic H2 production kinetics. Thus, this study demonstrates an effective strategy for constructing excellent g-C3N4-related composite photocatalysts for H2 production by using different co-catalysts.

MXenes as noble-metal-alternative co-catalysts in photocatalysis

Photocatalysis has become a focal point in research as a clean and sustainable technology with the potential to solve environmental problems and energy crises.The loading of noble-metal co-catalysts can substantially improve the photocatalytic efficiency of semiconductors.Because the high cost and scarcity of noble metals markedly limit their large-scale applications,finding a noble-metal-alternative co-catalyst is crucial.MXene,a novel 2D transition metal material,has attracted considerable attention as a promising substitute for noble metal co-catalysts owing to its cost-efficiency,unique 2D layered structure,and excellent electrical,optical,and thermodynamic properties.This review focuses on the latest advancements in research on MXenes as co-catalysts in relatively popular photocatalytic applications(hydrogen production,CO2 reduction,nitrogen fixation,and organic pollutant oxidation).The synthesis methods and photocatalytic mechanisms of MXenes as co-catalysts are also summarized according to the type of MXene-based material.Finally,the crucial opportunities and challenges in the prospective development of MXene-based photocatalysts are outlined.We emphasize that modern techniques should be used to demonstrate the effects of MXenes on photocatalysis and that the photocatalytic activity of MXene-based photocatalysts can be further improved using defective engineering and recent phenomena such as the localized surface plasmon resonance effect and single-atom catalysis.

An efficient strategy for photocatalytic hydrogen peroxide production over oxygen-enriched graphitic carbon nitride with sodium phosphate

Photocatalytic hydrogen peroxide(H_(2)O_(2))production is a promising strategy to replace the traditional production processes;however,the inefficient H_(2)O_(2) productivity limits its application.In this study,oxygen-rich g-C_(3)N_(4) with abundant nitrogen vacancies(OCN)was synthesized for photocatalytic H_(2)O_(2) production.X-ray photoelectron spectroscopy and Fourier-transform infrared spectroscopy indicated that oxygen-containing functional groups(–COOH and C–O–C)were obtained.Electron paramagnetic resonance confirmed the successful introduction of nitrogen vacancies.OCN exhibited efficient photocatalytic H_(2)O_(2) production performance of 1965μmol L^(−1) h^(−1) in air under visible-light irradiation.The high H_(2)O_(2) production was attributed to the enhanced adsorption of oxygen,enlarged specific surface area,and promoted carrier separation.An increased H_(2)O_(2) production rate(5781μmol L^(−1) h^(−1))was achieved in a Na_(3)PO_(4) solution.The improved performance was attributed to the changed reactive oxygen species.Specifically,the adsorbed PO_(4)^(3−) on the surface of the OCN promoted the transfer of holes to the catalyst surface.•O_(2)−obtained by O_(2) reduction reacted with adjacent holes to generate 1O_(2),which could efficiently generate H_(2)O_(2) with isopropanol.Additionally,PO_(4)^(3−),as a stabilizer,inhibited the decomposition of H_(2)O_(2).

Gold/monolayer graphitic carbon nitride plasmonic photocatalyst for ultrafast electron transfer in solar-to-hydrogen energy conversion

Gold(Au)plasmonic nanoparticles were grown evenly on monolayer graphitic carbon nitride(g‐C3N4)nanosheets via a facile oil‐bath method.The photocatalytic activity of the Au/monolayer g‐C3N4 composites under visible light was evaluated by photocatalytic hydrogen evolution and environmental treatment.All of the Au/monolayer g‐C3N4 composites showed better photocatalytic performance than that of monolayer g‐C3N4 and the 1%Au/monolayer g‐C3N4 composite displayed the highest photocatalytic hydrogen evolution rate of the samples.The remarkable photocatalytic activity was attributed largely to the successful introduction of Au plasmonic nanoparticles,which led to the surface plasmon resonance(SPR)effect.The SPR effect enhanced the efficiency of light harvesting and induced an efficient hot electron transfer process.The hot electrons were injected from the Au plasmonic nanoparticles into the conduction band of monolayer g‐C3N4.Thus,the Au/monolayer g‐C3N4 composites possessed higher migration and separation efficiencies and lower recombination probability of photogenerated electron‐hole pairs than those of monolayer g‐C3N4.A photocatalytic mechanism for the composites was also proposed.

In situ synthesis of Fe-N-C catalysts from cellulose for hydrogenation of nitrobenzene to aniline

Owing to Fe being the most abundant and least expensive transition metal on the earth,the utilization of Fe-based catalysts for catalytic hydrogenation has attracted worldwide attention.In this work,a series of N-doped C supported Fe catalysts(Fe-N-C)were prepared by co-pyrolysis of cellulose and ferric chloride under ammonia atmosphere.Characterization methods such as elemental analysis,atomic absorption spectroscopy,nitrogen adsorption-desorption isotherms,transmission electron microscopy,high-resolution transmission electron microscopy,X-ray diffraction,and X-ray photoelectron spectroscopy were carried out to explore the physicochemical properties of the catalysts.Using hydrogenation of nitrobenzene as a model reaction,the catalysts prepared at different pyrolysis temperatures displayed different activities.Fe-N-C-700 exhibited the best activity among these catalysts,with the yield of aniline being up to 98.0%under 5 MPa H2 at 120℃ after 12 h.Combined with the results of catalyst characterization and comparative tests,the transformation of Fe species and the generation of N-doped C,especially graphitized N-doped C,in the catalyst may be the main factors affecting the activity.A kinetic study was carried out and the apparent activation energy was obtained as 31.53 kJ/mol.The stability of the catalyst was also tested and no significant decrease in the activity was observed after 5 runs.

The embedded CuInS2 into hollow-concave carbon nitride for photocatalytic H2O splitting into H2 with S-scheme principle

It is still a great challenge to effectively optimize the electronic structure of photocatalysts for the sustainable and efficient conversion of solar energy to H2 energy.To resolve this issue,we report on the optimization of the electronic structure of hollow-concave carbon nitride(C3N4)by deviating the sp2-hybridized structure of its tri-s-triazine component from the two-dimensional plane.The embedded CuInS2 into C3N4(CuInS2@C3N4)demonstrates an increased light-capturing capability and the promoted directional transfer of the charge carrier.Research results reveal that the hollow structure with an apparent potential difference between the concave and convex C3N4 drives the directional transfer of the photoinduced electrons from the Cu 2p orbital of CuInS2 to the N 1s orbital of C3N4 with the S-scheme principle.The H2 evolution efficiency over CuInS2@C3N4 is up to 373μmol?h^-1 g^-1 under visible irradiation,which is 1.57 and 1.35 times higher than those over the bulk g-C3N4 with 1 wt%Pt(238μmol?h^-1 g^-1)and g-C3N4 with 3 wt%Pd(276μmol?h^-1 g^-1),respectively.This suggests that the apparent potential difference of the hollow C3N4 results in an efficient reaction between the photogenerated electrons and H2O.This work supplies a new strategy for enhancing the sustainable solar conversion performance of carbon nitride,which can also be suitable for other semiconductors.

Strategies to improve electrocatalytic and photocatalytic performance of two-dimensional materials for hydrogen evolution reaction

Two-dimensional materials(2D)with unique physicochemical properties have been widely studied for their use in many applications,including as hydrogen evolution catalysts to improve the efficiency of water splitting.Recently,typical 2D materials MoS2,graphene,MXenes,and black phosphorus have been widely investigated for their application in the hydrogen evolution reaction(HER).In this review,we summarize three efficient strategies—defect engineering,heterostructure formation,and heteroatom doping—for improving the HER performance of 2D catalysts.The d-band theory,density of states,and Fermi energy level are discussed to provide guidance for the design and construction of novel 2D materials.The challenges and prospects of 2D materials in the HER are also considered.

Doping-induced metal–N active sites and bandgap engineering in graphitic carbon nitride for enhancing photocatalytic H_(2 )evolution performance

Durable and inexpensive graphitic carbon nitride(g-C_(3)N_(4))demonstrates great potential for achieving efficient photocatalytic hydrogen evolution reduction(HER).To further improve its activity,g-C_(3)N_(4)was subjected to atomic-level structural engineering by doping with transition metals(M=Fe,Co,or Ni),which simultaneously induced the formation of metal-N active sites in the g-C_(3)N_(4)framework and modulated the bandgap of g-C_(3)N_(4).Experiments and density functional theory calculations further verified that the as-formed metal-N bonds in M-doped g-C_(3)N_(4)acted as an"electron transfer bridge",where the migration of photo-generated electrons along the bridge enhanced the efficiency of separation of the photogenerated charges,and the optimized bandgap of g-C_(3)N_(4)afforded stronger reduction ability and wider light absorption.As a result,doping with either Fe,Co,or Ni had a positive effect on the HER activity,where Co-doped g-C_(3)N_(4)exhibited the highest performance.The findings illustrate that this atomic-level structural engineering could efficiently improve the HER activity and inspire the design of powerful photocatalysts.

Preparation of N‐vacancy‐doped g‐C_3N_4 with outstanding photocatalytic H_2O_2 production ability by dielectric barrier discharge plasma treatment

Dielectric barrier discharge（DBD） plasma is considered to be a promising method to synthesize solid catalysts. In this work, DBD plasma was used to synthesize a nitrogen‐vacancy‐doped g‐C3N4 catalyst in situ for the first time. X‐ray diffraction, N2 adsorption, ultraviolet–visible spectroscopy, scanning electron microscopy, transmission electron microscopy, X‐ray photoelectron spectrosco‐py, electrochemical impedance spectroscopy, electron paramagnetic resonance, O2 tempera‐ture‐programmed desorption, and photoluminescence were used to characterize the obtained cat‐alysts. The photocatalytic H2O2 production ability of the as‐prepared catalyst was investigated. The results show that plasma treatment influences the morphology, structure, and optical properties of the as‐prepared catalyst. Nitrogen vacancies are active centers, which can adsorb reactant oxygen molecules, trap photoelectrons, and promote the transfer of photoelectrons from the catalyst to the adsorbed oxygen molecules for the subsequent reduction reaction. This work provides a new strat‐egy for synthesizing g‐C3N4‐based catalysts.

Fabrication of hierarchical ZnIn2S4@CNO nanosheets for photocatalytic hydrogen production and CO2 photoreduction

Photocatalytic H2 production and CO2 reduction have attracted considerable attention for clean energy development.In this work,we designed an efficient photocatalyst by integrating lamellar oxygen-doped carbon nitride(CNO)nanosheets into ZnIn2S4(ZIS)microflowers by a one-step hydrothermal method.A well-fitted 2D hierarchical hybrid heterostructure was fabricated.Under visible light irradiation,the ZIS@CNO composite with 40 wt%CNO(ZC 40%)showed the highest hydrogen evolution rate from water(188.4μmol·h-1),which was approximately 2.1 times higher than those of CNO and ZIS(88.6 and 90.2μmol·h-1,respectively).Furthermore,the selective CO production rates of ZC 40%(12.69μmol·h-1)were 2.2 and 14.0 times higher than those of ZIS(5.85μmol·h-1)and CNO(0.91μmol·h-1),respectively,and the CH4 production rate of ZC 40%was 1.18μmol·h-1.This enhanced photocatalytic activity of CNO@ZIS is due mainly to the formation of a heterostructure that can promote the transfer of photoinduced electrons and holes between CNO and ZIS,thereby efficiently avoiding recombination of electron-hole pairs.

MXenes for electrocatalysis applications:Modification and hybridization

Two-dimensional carbides,nitrides,and carbonitrides(MXenes)play important roles in promoting the development of sustainable energy because they have abundant reactive sites on their surfaces.An increasing number of MXenes with diverse elements and composites have been predicted and synthesized for electrocatalysis applications since the first report of a Ti-Mo-based MXene for the hydrogen evolution reaction(HER).Herein,we summarize the progress of MXene-based electrocatalysts for the HER,the oxygen evolution reaction,and the oxygen reduction reaction,including regulated pristine MXenes and modified hybrid MXenes,from both theoretical and experimental perspectives.A brief overview on MXene synthesis is presented first,accompanied by a discussion on the relationship between electrocatalytic properties and M,X,T,vacancies,and morphologies.After reviewing strategies in terms of atom substitution,functional modification,defect engineering,and morphology control,we emphasize the construction of heterojunctions between MXenes and other nanostructures,such as metal nanoparticles,oxides,hydroxides,sulfides,and phosphides.We finally discuss prospects for the future development of MXene-based electrocatalysts.

Highly crystalline carbon nitride hollow spheres with enhanced photocatalytic performance

Graphitic carbon nitride(g-C_(3)N_(4))has emerged as a remarkably promising photocatalyst for addressing environmental and energy issues;however,it exhibits only moderate photocatalytic activity because of its low specific surface area and high recombination of carriers.Preparation of crystalline g-C_(3)N_(4) by the molten salt method has proven to be an effective method to improve the photocatalytic activity.However,crystalline g-C_(3)N_(4) prepared by the conventional molten salt method exhibits a less regular morphology.Herein,highly crystalline g-C_(3)N_(4) hollow spheres(CCNHS)were successfully prepared by the molten salt method using cyanuric acid-melamine as a precursor.The higher crystallization of the CCNHS samples not only repaired the structural defects at the surface of the CCNHS samples but also established a built-in electric field between heptazine-based g-C_(3)N_(4) and triazine-based g-C_(3)N_(4).The hollow structure improved the level of light energy utilization and increased the number of active sites for photocatalytic reactions.Because of the above characteristics,the as-prepared CCNHS samples simultaneously realized photocatalytic hydrogen evolution with the degradation of the plasticizer bisphenol A.This research offers a new perspective on the structural optimization of supramolecular self-assembly.

Comprehensive investigation on robust photocatalytic hydrogen production over C_(3)N_(5)

Carbon nitride has drawn numerous eyes in the past decade,whereas the photocatalytic performance is significantly limited by its wide band-gap(~2.7 e V for C_(3)N_(4))simultaneously.Recently,C_(3)N_(5)with narrower band-gap has been reported,however,a systematically investigation on its photoactivity for H_(2)production has not been reported.The present work demonstrates the synthesis of C_(3)N_(5)by thermal treatment of 3-amino-1,2,4-triazole,and the photocatalytic performance for H_(2)production of C_(3)N_(5)is investigated comprehensively.Photocatalytic H_(2)production rate of C_(3)N_(5)is~2.2 times higher than that of C_(3)N_(4) with 1.0 wt%Pt as co-catalyst,and series of experiments are carried out to explore the behind elements accounting for the high photoactivity.Combining the results of DRS,PL and photocurrent,it is found that C_(3)N_(5)possesses wider visible light absorption region,lower band-gap and quicker photogenerated e^(-)/h^(+)separation efficiency.Moreover,characterizations including in-situ DRIFTS are adopted to monitor the adsorption property of H_(2)O on C_(3)N_(5),which plays a significant role in surface water reduction reaction,and higher amount of adsorbed H_(2)O molecules on C_(3)N_(5)is confirmed.The present work exhibits new insights into the high photocatalytic performance of N-rich carbon nitride catalysts.

Fe_3C-functionalized 3D nitrogen-doped carbon structures for electrochemical detection of hydrogen peroxide

Fe3C-functionalized three-dimensional （3D） porous nitrogen-doped graphite carbon composites （Fe3C/ NG） were synthesized via a facile solution-based impreg- nation and pyrolysis strategy using the commercially available melamine foam and FeC13 as precursors. The structural characterizations confirmed that Fe3C nanoparticles with an average core size about 122 nm were assembled on the surface of the carbonized melamine foam （CMF） skeletons. The electrochemical measurements demonstrated the superior electrocatalytic activity of the advanced Fe3C/NG composite for hydrogen peroxide reduction reaction in 0.1 mol/L PBS electrolyte and the limit of detection of H2O2 is estimated to be 0.035 mmol/L at a signal-to-noise ratio of 3 with a wide linear detection range from 50 μmol/L to 15 mmol/L （R^2 = 0.999）. Compared with the pure CMF, the Fe3C/NG exhibited higher catalytic activity, more stable response, lower detection limit, higher selectivity and a wider detection range, which could be attributed to the synergic effect between the two types of active sites from the iron carbide species and the nitrogen-doped graphite carbon. Meanwhile, the large surface area, high conductivity and the improved mass transport from the 3D porous material can also promote the electrochemical sensing performance. Moreover, the Fe3C/ NG-based electrochemical sensor showed high anti-interference ability and stability for H2O2 detection. Thus, the novel and low-cost Fe3C/NG composite may be a prom- ising alternative to noble metals and offer potential appli- cations in various types of electrochemical sensors, bioelectronic devices and catalysts.

Carbon nitride with encapsulated nickel for semi-hydrogenation of acetylene: pyridinic nitrogen is responsible for hydrogen dissociative adsorption

A new mechanism of catalyst has been demonstrated in this article. With the interaction between carbon nitride(CN) and encapsulated nickel, the CN in the catalyst has been endowed with new active sites for the adsorption and activation of hydrogen while nickel itself is physically isolated from the contact with reactive molecules. For the selective hydrogenation of acetylene in large amount of ethylene, the catalyst shows excellent ethylene selectivity than the nickel catalyst itself, which is almost totally unselective. Meanwhile, the CN itself is inactive for the reaction. The results of characterization demonstrate that pyridinic nitrogen doped in the carbon matrix should be the active sites for hydrogen dissociative adsorption. The theoretical calculations further confirm the results and provide with the detail in the electron transfer between nickel and CN in the catalyst. The current results supply a new concept for design of high performance catalyst.

Ferrites boosting photocatalytic hydrogen evolution over graphitic carbon nitride: a case study of(Co, Ni)Fe_2O_4 modification

The charge cartier separation and surface catalytic redox reactions are of primary importance as elementary steps in photocatalytic hydrogen evolution. In this study, both of these two processes in photocatalytic hydrogen evolution over graphitic carbon nitride （g-C3N4） were greatly promoted with the earth-abundant ferrites （Co, Ni）Fe2O4 modification. CoFe2O4 was further demonstrated to be a better modifier for g-C3N4 as compared to NiFe2O4, due to the more efficient charge carrier transfer as well as superior surface oxidative catalytic activity. When together loading CoFe2O4 and reductive hydrogen production electrocatalyst Pt onto g-C3N4, the obtained Pt/g-C3N4/CoFe2O4 photocatalyst achieved visible-light （2 〉 420 nm） hydrogen production rate 3.5 times as high as Pt/g-C3N4, with the apparent quantum yield reaching 3.35 % at 420 nm.