Heteroatom-Induced Accelerated Kinetics on Nickel Selenide for Highly Efficient Hydrazine-Assisted Water Splitting and Zn-Hydrazine Battery

Hydrazine-assisted water electrolysis is a promising energy conversion technology for highly efficient hydrogen production.Rational design of bifunctional electrocatalysts,which can simultaneously accelerate hydrogen evolution reaction(HER)/hydrazine oxidation reaction(HzOR)kinetics,is the key step.Herein,we demonstrate the development of ultrathin P/Fe co-doped NiSe_(2) nanosheets supported on modified Ni foam(P/Fe-NiSe_(2)) synthesized through a facile electrodeposition process and subsequent heat treatment.Based on electrochemical measurements,characterizations,and density functional theory calculations,a favorable“2+2”reaction mechanism with a two-step HER process and a two-step HzOR step was fully proved and the specific effect of P doping on HzOR kinetics was investigated.P/Fe-NiSe_(2) thus yields an impressive electrocatalytic performance,delivering a high current density of 100 mA cm^(−2) with potentials of−168 and 200 mV for HER and HzOR,respectively.Additionally,P/Fe-NiSe_(2) can work efficiently for hydrazine-assisted water electrolysis and Zn-Hydrazine(Zn-Hz)battery,making it promising for practical application.

Defect Engineering of Disordered Carbon Anodes with Ultra-High Heteroatom Doping Through a Supermolecule-Mediated Strategy for Potassium-Ion Hybrid Capacitors

Amorphous carbons are promising anodes for high-rate potassium-ion batteries.Most low-temperature annealed amorphous carbons display unsatisfactory capacities.Heteroatom-induced defect engineering of amorphous carbons could enhance their reversible capacities.Nevertheless,most lignocellulose biomasses lack heteroatoms,making it a challenge to design highly heteroatom-doped carbons(>10 at%).Herein,we report a new preparation strategy for amorphous carbon anodes.Nitrogen/sulfur co-doped lignin-derived porous carbons(NSLPC)with ultra-high nitrogen doping levels(21.6 at%of N and 0.8 at%of S)from renewable lignin biomacromolecule precursors were prepared through a supramolecule-mediated pyrolysis strategy.This supermolecule/lignin composite decomposes forming a covalently bonded graphitic carbon/amorphous carbon intermediate product,which induces the formation of high heteroatom doping in the obtained NSLPC.This unique pyrolysis chemistry and high heteroatom doping of NSLPC enable abundant defective active sites for the adsorption of K+and improved kinetics.The NSLPC anode delivered a high reversible capacity of 419 mAh g^(-1)and superior cycling stability(capacity retention of 96.6%at 1 A g^(-1)for 1000 cycles).Potassiumion hybrid capacitors assembled by NSLPC anode exhibited excellent cycling stability(91%capacity retention for 2000 cycles)and a high energy density of 71 Wh kg^(-1)at a power density of 92 W kg^(-1).

Heteroatom dopant strategy triggered high-potential plateau to non-graphitized carbon with highly disordered microstructure for high-performance sodium ion storage

Non-graphitized carbon(NGC)has been extensively utilized as carbonaceous anode in sodium-ion batteries(SIBs).However,more optimization to achieve competitive capacity and stability is still challenging for SIBs.In the study,the dopant strategy is utilized to construct nitrogen/sulfur-doped non-graphitized carbon(N-NGC or S-NGC)shell decorated on three-dimensional graphene foam(GF)as a self-support electrode.The highly disordered microstructures of heteroatom doped carbons are produced by applying a low-temperature pyrolysis treatment to precursors containing nitrogen and sulfur.The DFT calculations of Na-ion adsorption energies at diverse heteroatom sites show marginal-S,pyrrolic N and pyridinic N with more intensive Na-ion adsorption ability than middle-S,C=O and pristine carbon.The N-NGC with dominant small graphitic regions delivers adsorption ability to Na-ion,while the S-NGC with significant single carbon lattice stripes demonstrates redox reaction with Na-ion.Evidently,in comparison with only adsorption-driven slope regions at high potential for N-NGC,the redox reaction-generated potentialplateau enables non-graphitized S-NGC superior discharge/charge capacity and cycle-stability in the slope region.This work could provide deep insight into the rational design of non-graphitized carbon with rich microstructure and composition.

An ensemble learning classifier to discover arsenene catalysts with implanted heteroatoms for hydrogen evolution reaction

Accurate regulation of two-dimensional materials has become an effective strategy to develop a wide range of catalytic applications.The introduction of heterogeneous components has a significant impact on the performance of materials,which makes it difficult to discover and understand the structure-property relationships at the atomic level.Here,we developed a novel and efficient ensemble learning classifier with synthetic minority oversampling technique(SMOTE) to discover all possible arsenene catalysts with implanted heteroatoms for hydrogen evolution reaction(HER).A total of 850 doped arsenenes were collected as a database and 140 modified arsenene materials with different doping atoms and doping sites were identified as promising candidate catalysts for HER,with a machine learning prediction accuracy of 81%.Based on the results of machine learning,we proposed 13 low-cost and easily synthesized two-dimensional Fe-doped arsenene catalytic materials that are expected to contribute to high-efficient HER.The proposed ensemble method achieved high prediction accuracy,but millions of times faster to predict Gibbs free energies and only required a small amount of data.This study indicates that the presented ensemble learning classifier is capable of screening high-efficient catalysts,and can be further extended to predict other two-dimensional catalysts with delicate regulation.

Heteroatomic Modification of Solid-Waste-Based Mesoporous Carbon for Volatile Organic Compound Adsorption

Solid-waste-based activated carbon(AC)was utilized as a carbon source to synthesize a series of carbon-based functional material RAC-X(X=P and S,where P and S denote phosphoric and sulfuric acids,respectively).The toluene adsorption capacities of the regeneration AC(RAC)samples can be significantly improved by adopting the heteroatomic modification strategy.RAC-P and RAC-S have the same specific surface area(1156 m^(2)/g)and similar porous structures.However,they have different toluene adsorption capacities,with 316.22 mg/g for RAC-P and 460.12 mg/g for RAC-S,which are 1.6 and 2.4 times greater than that for RAC.The X-ray photoelectron spectroscopy measurements showed that the increase in the amount ofπ–π^(2)chemical bond over the AC surface results in the improvement of the toluene adsorption performance.The density functional theory results showed that the S-containing functional groups loaded near the defect sites of RAC-S promote toluene adsorption.Moreover,reusability tests showed that RAC-S still retains 86%of its adsorption activity after four consecutive adsorption–desorption experiments.This indicates that the heteroatomic modification method affords excellent toluene adsorption performance and recycling practicability,which not only is beneficial for achieving the rational utilization of solid waste resources but also provides a practical method for the efficient elimination of volatile organic compounds.

Multi-heteroatom doped porous carbon derived from insect feces for capacitance-enhanced sodium-ion storage

The large-scale application of sodium ion batteries(SIBs)is limited by economic and environmental factors.Here,we prepare multi-heteroatom self-doped hierarchical porous carbon(HHPC)with a honeycomb-like structure by one-step carbonization method using high-yield and low-cost biomass silkworm excrement as a precursor.As an anode for SIB,HHPC-1100 exhibits a capacity of 331.7 mA h g^(-1) at 20 mA g^(-1),while it also reveals remarkable rate performance and stable long cycle capability due to its abundant pore structure and proper amount of hetero atom doping.Moreover,the synergistic effect of O,N,S,P co-doping in carbon materials on sodium ion adsorption is verified by the first-principles study,which provide a theoretical basis for the prominent electrochemical performance of the material.

Heteroatom-doped porous carbon from methyl orange dye wastewater for oxygen reduction

Banana peel-derived porous carbon(BPPC) was prepared from banana peel and used as an adsorbent for methyl orange(MO) wastewater removal. BPPC-MO50 is a N,S-doped BPPC obtained via secondary carbonization. The BPPC-MO50 exhibited a high specific surface area of1774.3 m^2/g. Heteroatom-doped porous carbon(PC) was successfully synthesized from the BPPC absorbed MO at high temperature and used for oxygen reduction. The BPPC-MO50 displayed the highest ORR onset potential among all carbon-based electrocatalysts, i.e., 0.93 V vs.reversible hydrogen electrode(RHE). This is the first report to describe porous carbon-activated materials from agriculture and forestry waste that is used for adsorption of dyes from wastewater via an enhanced heteroatom(N,S) content. These results may contribute to the sustainable development of dye wastewater treatment by transforming saturated PC into an effective material and has potential applications in fuel cells or as energy sources.

Regio-and Diasteroselectivity of Rhodium-catalyzed Ring Opening Reaction of Oxabenzonorbornadienes with Heteroatom Nucleophiles

A new rhodium catalyzed ring opening reaction of oxabenzonorbornadienes and its derivatives was described. This reaction forms a new carbon-nitrogen bond via an intermolecular allylic displacement of the bridgehead oxygen with a piperazine's derivatives, which proceeds with very high regioselectivity.

Heteroatom substitution-induced asymmetric A–D–A type non-fullerene acceptor for efficient organic solar cells

Research on asymmetric A–D–A structured non-fullerene acceptors has lagged far behind the development of symmetric counterpart.In this contribution,by simply replacing one sulfur atom in indacenodithiophene unit with a selenium atom,an asymmetric building block Se PT and a corresponding asymmetric non-fullerene acceptor Se PT-IN have been developed.Asymmetric Se PT-IN achieved a high efficiency of 10.20% in organic solar cells when blended with PBT1-C,much higher than that of symmetric TPT-IN counterpart(8.91%).Our results demonstrated an effective heteroatom substitution strategy to develop asymmetric A–D–A structured non-fullerene acceptors.

Biomass-derived activated carbon materials with plentiful heteroatoms for high-performance electrochemical capacitor electrodes

Activated carbons for electrochemical capacitor electrodes are prepared from soyabean using chemical activation with KOH. The pore size is easily controllable by changing the mass ratio between KOH and carbonized product. The as-prepared materials possess a large specific surface area, unique structure, well- developed hierarchical porosity and plentiful heteroatoms（mainly O and N）. Thus resulted in its high specific capacitance,good rate capacity and cycling stability. Moreover, attributing to worldwide availability, renewable nature and low-cost, activated carbon prepared from soyabean has a good potential in energy conversion and storage devices.

Review on Heteroatom Doping Carbonaceous Materials Toward Electrocatalytic Carbon Dioxide Reduction

Carbon dioxide(CO_(2))reduction into chemicals or fuels by electrocatalysis can eff ectively reduce greenhouse gas emissions and alleviate the energy crisis.Currently,CO_(2)electrocatalytic reduction(CO_(2)RR)has been considered as an ideal way to achieve“carbon neutrality.”In CO_(2)RR,the characteristics and properties of catalysts directly determine the reaction activity and selectivity of the catalytic process.Much attention has been paid to carbon-based catalysts because of their diversity,low cost,high availability,and high throughput.However,electrically neutral carbon atoms have no catalytic activity.Incorpo-rating heteroatoms has become an eff ective strategy to control the catalytic activity of carbon-based materials.The doped carbon-based catalysts reported at present show excellent catalytic performance and application potential in CO_(2)RR.Based on the type and quantity of heteroatoms doped into carbon-based catalysts,this review summarizes the performances and catalytic mechanisms of carbon-based materials doped with a single atom(including metal and without metal)and multi atoms(including metal and without metal)in CO_(2)RR and reveals prospects for developing CO_(2)electroreduction in the future.

Heteroatom Doped Multi-Layered Graphene Material for Hydrogen Storage Application

A variety of distinctive techniques have been developed to produce graphene sheets and their functionalized subsidiaries or composites. The production of graphene sheets by oxidative exfoliation of graphite can be a suitable route for the preparation of high volumes of graphene derivatives. P-substituted graphene material is developed for its application in hydrogen sorption in room temperature. Phosphorous doped graphene material with multi-layers of graphene shows a nearly ~2.2 wt% hydrogen sorption capacity at 298 K and 100 bar. This value is higher than that for reduced graphene oxide (RGO without phosphorous).

The Influence of Heteroatom M(M = B, Al, Ge, Ga, Fe)on the Adsorption Properties of M-ZSM-12 Zeolites

Heteroatom M-ZSM-12 zeolites(M=B, Al, Ge, Ga, Fe) are hydrothermally synthesized and it is proved that the heteroatom M is involved in the framework of synthesized molecular sieves by means of XRD, IR spectra. The results of adsorption and diffusion experiments indicate that the heteroatom M modifies the pore volume, specific surface area, and the channel of ZSM-12 molecular sieves.

Heteroatom-doped porous carbon-supported single-atom catalysts for electrocatalytic energy conversion

Electrocatalysts play a crucial role in the development of renewable energy conversion and storage nanotechnologies.The unique advantages of heteroatom-doped porous carbon-supported single-atom electrocatalysts(SAC-HDPCs)are clear.These SAC-HDPCs exhibit outstanding activity,selectivity and stability due to their distinct electronic structure,satisfactory conductivity,controllable porosity and heteroatomdoping effect.Rapid and significant developments involving the synthesis,characterization,and structure-property-function relationship of SAC-HDPCs have been made in recent years.In this review,we describe recent research efforts involving advanced(in situ)characterization techniques,innovative synthetic strategies,and electrochemical energy conversion examples of SAC-HDPCs.The electrocatalytic performance of SAC-HDPCs is further considered at an atomic level,and the mechanisms underlying this performance are also discussed in detail.We expect that these analyses and deductions will be useful for the design of new materials and may help to establish a foundation for the design of future SAC-HDPCs.

STUDY ON THERMAL AND HYDROTHERMAL STABILITY OF HETEROATOM MCM－41 MOLECULAR SIEVES

Five samples of SiMCM-41, AlSiMCM-41, FeSiMCM-41, LaSiMCM-41 andAILaSiNCM-41 were synthesised and their good thermal stability was proved-by TG/DTAand XRD. All the samples were thermal stable up to abode 1150-1160 K. LaSiMCM-41 andFeSiMCM-41 showed better hydrothermal stability. Due to the cllalinel diameter within 1.5-10 urn, the synthesis ofmesoPOrous molecularsieve MCM41 by Mobil in 1992 anew new light on the conventional concept of SyntheSisofarelitCslll. For its POtential application, the studies on this novel matchal family are veryactive reCently, but few papers t'.ere published about their thennal and hydrithennal stability.

Role of carbon matrix heteroatoms at synthesis of carbons for catalysis and energy applications

The conceptual ideas about the positive effects of N- and O-heteroatoms on the reactivity of carbons in gasification processes, their catalytic activity in electron transfer reactions, as well as the performance of the electrode double-layer supercapacitors due to their electron-donating influence on the 7r-conjugated system of graphene layers have been developed. This influence decreases both work function and band gap of carbons, and also significantly affects their electron-donating properties. As a result of our investigations based on quantum chemical calculations of model graphene clusters with N- and O-heteroatoms in different positions, prognostic data have been obtained. These data have been confirmed by our experimental results of catalytic activity of corresponding carbons in H202 decomposition reaction, their reactivity in gasification processes, and also their performance as electrodes in supercapacitors.

Electron-transporting boron-doped polycyclic aromatic hydrocarbons:Facile synthesis and heteroatom doping positions-modulated optoelectronic properties

While heteroatom doping serves as a powerful strategy for devising novel polycyclic aromatic hydrocarbons(PAHs), the further fine-tuning of optoelectronic properties via the precisely altering of doping patterns remains a challenge. Herein, by changing the doping positions of heteroatoms in a diindenopyrene skeleton, we report two isomeric boron, sulfur-embedded PAHs, named Anti-B_(2)S_(2) and Syn-B_(2)S_(2), as electron transporting semiconductors. Detailed structure-property relationship studies revealed that the varied heteroatom positions not only change their physicochemical properties, but also largely affect their solid-state packing modes and Lewis base-triggered photophysical responses. With their low-lying frontier molecular orbital levels, n-type characteristics with electron mobilities up to 1.5 × 10^(-3)cm^(2)V^(-1)s^(-1)were achieved in solution-processed organic field-effect transistors. Our work revealed the critical role of controlling heteroatom doping patterns for designing advanced PAHs.

Applying heteroatom co-doped carbon nanotube for manifesting high performance in the electrochemical reduction of aqueous nitrogen oxide by gold nanoparticles

Electrochemical NO-to-NH_(3) under ambient conditions could be a viable alternative having advantages in terms of energy consumption and exhaust gas recycling of NO,replacing a traditional ammonia synthesis method of the Haber–Bosch process.In synthesizing boron(B-)and nitrogen(N-)co-doped carbon nanotube(CNT)based gold(Au)catalysts,B-dopants elevate the conductivity of carbon nanotube by sp2 hybridization on graphene and implant B–N domains within the graphene layer,and result in facilitating the embedding amount of Au accompanied by high dispersibility with low particle size.Theoretical density functional theory(DFT)calculations elucidate that the electron cloud transmitted from B-dopant to the active site of Au induces the Lewis acidic site,and the O-distal pathway occurs following a spontaneous reaction.Increment of the electron-deficient B-doping area accompanied by N-defects and B–O edges retains the major valence state of Au as Au^(δ+),and suppresses hydrogen evolution reaction(HER)by repulsing the hindrance of H*.This record exhibits the highest faradaic efficiency(FE)of 94.7%,and NH_(3) yield rate of 1877.4μg·h^(-1)·mg_(cat)^(-1),which is the optimal yield over energy consumption in the field of the ambient reduction of aqueous NO.

Heteroatom doping regulates the catalytic performance of singleatom catalyst supported on graphene for ORR

Replacing fossil fuels with fuel cells is a feasible way to reduce global energy shortages and environmental pollution.However,the oxygen reduction reaction(ORR)at the cathode has sluggish kinetics,which limits the development of fuel cells.It is significant to develop catalysts with high catalytic activity of ORR.The single-atom catalysts(SACs)of Pt supported on heteroatom-doped graphene are potential candidates for ORR.Here we studied the SACs of Pt with different heteroatoms doping and screened out Pt-C_(4) and Pt-C_(3)O_(1) structures with only 0.13 V overpotential for ORR.Meanwhile,it is found that B atoms doping could weaken the adsorption capacity of Pt,while N or O atoms doping could enhance it.This regularity was verified on Fe SACs.Through the electronic interaction analysis between Pt and adsorbate,we explained the mechanism of this regularity and further proposed a new descriptor named corrected d-band center(ε_(d-corr))to describe it.This descriptor is an appropriate reflection of the number of free electrons of the SACs,which could evaluate its adsorption capacity.Our work provides a purposeful regulatory strategy for the design of ORR catalysts.