High-Performance Na-Ion Storage of S-Doped Porous Carbon Derived from Conjugated Microporous Polymers

Na-ion batteries(NIBs)have attracted considerable attention in recent years owing to the high abundance and low cost of Na.It is well known that S doping can improve the electrochemical performance of carbon materials for NIBs.However,the current methods for S doping in carbons normally involve toxic precursors or rigorous conditions.In this work,we report a creative and facile strategy for preparing S-doped porous carbons(SCs)via the pyrolysis of conjugated microporous polymers(CMPs).Briefly,thiophene-based CMPs served as the precursors and doping sources simultaneously.Simple direct carbonization of CMPs produced S-doped carbon materials with highly porous structures.When used as an anode for NIBs,the SCs exhibited a high reversible capacity of 440 mAh g?1 at 50 mA g?1 after 100 cycles,superior rate capability,and excellent cycling stability(297 mAh g?1 after 1000 cycles at 500 mA g?1),outperforming most S-doped carbon materials reported thus far.The excellent performance of the SCs is attributed to the expanded lattice distance after S doping.Furthermore,we employed ex situ X-ray photoelectron spectroscopy to investigate the electrochemical reaction mechanism of the SCs during sodiation-desodiation,which can highlight the role of doped S for Na-ion storage.

Robust S-doped TiO_(2)@N,S-codoped carbon nanotube arrays as free-binder anodes for efficient sodium storage

Titanium dioxide(TiO_2) has been investigated broadly as a stable,safe,and cheap anode material for sodium-ion batteries in recent years.However,the poor electronic conductivity and inherent sluggish sodium ion diffusion hinder its practical applications.Herein,a self-template and in situ vulcanization strategy is developed to synthesize self-supported hybrid nanotube arrays composed of nitrogen/sulfur-codoped carbon coated sulfur-doped TiO_2 nanotubes(S-TiO_2@NS-C) starting from H_2 Ti_2 O_5-H_2 O nanoarrays.The S-TiO_2@NS-C composite with one-dimensional nano-sized subunits integrates several merits.Specifically,sulfur doping strongly improves the Na~+ storage ability of TiO_2@C-N nanotubes by narrowing the bandgap of original TiO_2.Originating from the nanoarrays structures built from hollow nanotubes,carbon layer and sulfur doping,the sluggish Na~+ insertion/extraction kinetics is effectively improved and the volume variation of the electrode material is significantly alleviated.As a result,the S-TiO_2@NS-C nanoarrays present efficient sodium storage properties.The greatly improved sodium storage performances of S-TiO_2@NS-C nanoarrays confirm the importance of rational engineering and synthesis of hollow array architectures with higher complexity.

S-doped porous carbon fibers with superior electrode behaviors in lithium ion batteries and fuel cells

The orientation construction of S-doped porous carbon fibers(SPCFs)is realized by the facile template-directed methodology using asphalt powder as carbon source.The unique fiber-like morphology without destruction can be well duplicated from the template by the developed methodology.MgSO4 fibers serve as both templates and S dopant,realizing the in-situ S doping into carbon frameworks.The effects of different reaction temperatures on the yield and S doping level of SPCFs are investigated.The S doping can not only significantly enhance the electrical conductivity,but also introduce more defects or disorders.As anode material for lithium ion batteries(LIBs),SPCFs electrode delivers better rate capability than undoped PCFs.And the capacity of SPCFs electrode retains around 90%after 300 cycles at 2 A g1,exhibiting good cycling stability.As the electrocatalysts for fuel cells,the onset potentials of SPCFs obtained at 800 and 900C are concentrated at 0.863 V,and the higher kinetic current densities at 0.4 V of them are larger than that of PCFs,demonstrating the superior electrocatalytic performance.Due to the synergistic effect of abundant pore channels and S doping,SPCFs electrode exhibits superior electrochemical performances as anode for LIBs and elecctrocatalyst for fuel cells,respectively.Additionally,the oriented conversion of asphalt powder into high-performance electrode material in this work provides a new way for the high value application of asphalt.

Synthesis of S-doped Sb_2O_3 Visible Light-driven Photocatalyst and Its Facets-dependent Performance for the Degradation of Methyl Orange

S-doped Sb_2O_3 nanocrystals were synthesized using SbCl3 and thioacetamide（TAA） as starting materials by a hydrothermal method and the effects of TAA dosage on the composition and properties of resultant nanocrystals were determined.Their photocatalytic performance was evaluated using the degradation of methyl orange（MO） as a model reaction.The results suggest that TAA dosage can affect the preferential growth direction of Sb_2O_3,and further influences its photocatalytic activity.S doping can extend the optical absorption edge of Sb_2O_3 to the visible light religion,and thus endows its ability to photocatalyze the degradation of MO under visible light illumination.Based on these results,the correlations between the photocatalytic activity of S-doped Sb_2O_3 and the ratio between exposed facets,specific surface area and crystallographic defects were discussed.

Porous S-doped carbon nitride foam with accelerated charge dynamics for synchronous photocatalytic hydrogen production and highly selective oxidation of amines

Photocatalytic hydrogen evolution coupled with organic oxidation holds great promise for converting solar energy into high-valueadded chemicals,but it is hampered by sluggish charge dynamics and limited redox potential.Herein,a porous S-doped carbon nitride(S-C_(3)N_(4−y))foam assembled from ultrathin nanosheets with rich nitrogen vacancies was synthesized using a molecular selfassembly strategy.The S dopants and N vacancies synergistically adjusted the band structure,facilitating light absorption and enhancing the oxidation ability.Moreover,the ultrathin nanosheets and porous structure provided more exposed active sites and facilitated mass and charge transfer.Consequently,S-C_(3)N_(4−y) foam exhibited enhanced photocatalytic activities for synchronous hydrogen evolution(4960μmol/(h·g))and benzylamine oxidation to N-benzylidenebenzylamine(4885μmol/(h·g))with high selectivity of>99%,which were approximately 17.6 and 72.9 times higher than those of bulk CN,respectively.The photocatalytic coupling pairing reaction promotes the water splitting by consuming H2O2,thereby improving the hydrogen evolution efficiency and achieving the production of high value-added imines.This study provides an effective route for regulating the morphology and band structure of carbon nitride for synthesizing highly valuable chemicals.

Highly conductive S-doped FeSe_(2-x)S_(x)microsphere with high tap density for practical sodium storage

Metal selenides have been explored as promising sodium storage materials owing to their high theoretical capacity.However,sluggish Naþdiffusion and low electronic conductivity of selenides still hinder their practical applications.Herein,FeSe_(2-x)S_(x)microspheres have been prepared via a self-doping solvothermal method using NH4Fe(SO4)2 as both the Fe and S source,followed by gas phase selenization.The density functional theory calculation results reveal that S doping not only improves the Na adsorption,but also lower the diffusion energy barrier of Na atoms at the S doping sites,at the same time enhance the electronic conductivity of FeSe_(2-x)S_(x).The carbon-free nature of the FeSe_(2-x)S_(x)microspheres results in a low specific surface area and a high tap density,leading to an initial columbic efficiency of 85.6%.Compared with pure FeSe_(2),such FeSe_(2-x)S_(x)delivers a high reversible capacity of 373.6 mAh⋅g^(-1)at a high current density of 5 A⋅g^(-1)after 2000 cycles and an enhanced rate performance of 305.8 mAh⋅g^(-1)at even 50 A⋅g1.Finally,the FeSe_(2-x)S_(x)//NVP pouch cells have been assembled,achieving high energy and volumetric energy densities of 118 Wh⋅kg1 and 272 mWh⋅cm3,respectively,confirming the potential of applications for the FeSe_(2-x)S_(x)microspheres.

Heterointerface engineering of Ru/RuS_(2) on N/S-doped hollow mesoporous carbon for promoting alkaline hydrogen evolution

Alkaline hydrogen evolution reaction (HER) suffers from a sluggish kinetic,which requires the elaborate catalytic interface and micro-nanoscale architecture engineering of the electrocatalysts to accelerate the water dissociation and hydrogen evolution.Herein,the heterointerface engineering was proposed for promoting the alkaline HER by constructing the highly exposed Ru/RuS_(2) heterostructures homogeneously distributed on hollow N/S-doped carbon microspheres (Ru/RuS_(2)@h-NSC).Benefited from the synergistic effect of heterointerfacial Ru/RuS_(2),the high accessibility of the active sites on both inner and outer surface of mesoporous shells and the efficient mass transport,Ru/RuS_(2)@h-NSC affords a remarkable catalytic performance with an overpotential of 26 mV@10 mA/cm^(2) for alkaline HER,outperforming most of the state-of-the-art catalysts.Further applying Ru/RuS_(2)@h-NSC and its oxidized derivate for the overall alkaline water splitting,the required cell voltage is much lower than that of the commercial Pt/C||RuO_(2)pair to achieve the same current density.Our study may allow us to guide the design of micro-nanoreactors with optimal catalytic interfaces for promising electrocatalytic applications.

Single-atom rhodium anchored on S-doped black phosphorene as a promising bifunctional electrocatalyst for overall water splitting

Superior bifunctional electrocatalysts with ultra-high stability and excellent efficiency are crucial to boost the oxygen evolution reaction(OER) and the hydrogen evolution reduction(HER) in the overall water splitting(OWS) for the sustainable production of clean fuels. Herein, comprehensive density functional theory(DFT) computations were performed to explore the potential of several single transition metal(TM) atoms anchored on various S-doped black phosphorenes(TM/Snx-BP) for bifunctional OWS electrocatalysis. The results revealed that these candidates display good stability, excellent electrical conductivity, and diverse spin moments. Furthermore, the Rh/S12-BP catalyst was identified as an eligible bifunctional catalyst for OWS process due to the low overpotentials for OER(0.43 V) and HER(0.02 V), in which Rh and its adjacent P atoms were identified as the active sites. Based on the computed Gibbs free energies of OH~*, O~*, OOH~* and H~*, the corresponding volcano plots for OER and HER were established.Interestingly, the spin moments and the charge distribution of the active sites determine the catalytic trends of OER and HER. Our findings not only propose a promising bifunctional catalyst for OWS, but also widen the potential application of BP in electrocatalysis.

Uniform assembly of gold nanoparticles on S-doped g-C3N4 nanocomposite for effective conversion of 4-nitrophenol by catalytic reduction

In this work,a simple synthesis of sulfur doped graphitic carbon nitride(S-g-C3N4)act as a support cum stabilizers for gold nanoparticles(Au)and its was characterized by UV–vis and XRD to measure the absorbance and crystallinity,respectively.The functional group and morphology of the samples were identified using FT-IR and TEM.Finally,the Au@S-g-C3N4 nanocatalyst exhibits good catalytic performance and stability in the reduction of hazardous 4-nitrophenol(NP)compared to S-g-C3N4 using Na BH4.Moreover,the Au@S-g-C3N4 nanocomposite holds a good catalytic efficiency(near 100%)achieved by within 5 min.The highest catalytic reduction of NP is due to the synergistic effect of Au nanoparticles decorated on S-g-C3N4.The fast electron transfer reduction mechanism was elucidated and discussed.Excellent reusability and stability of the developed nanocomposites were also observed in consecutive reduction experiments.The filtering and catalyzing device was used for the direct conversion of NP polluted water.This method can open a new avenue for the metal nanoparticles based carbon materials heterogeneous catalyst and its reduction of toxic contaminants.

Tribological properties of Cu-based composites with S-doped NbSe_2

In this study, S-doped NbSea （NbSo.aSel.8） powders were fabricated, and the corresponding Cu-based composites （Cu/NbSo.eSe1.8） were obtained by powder metallurgy technique. The phase compositions, physical, and tribological properties of Cu-based composites were investigated systematically. The results show that Cu matrix reacts with NbSo.2Sel.8 to produce Cu2Se and Cu0.38NbSo.2Se1.8 during sintering process, which influences the physical and tribological properties of Cu-based composites significantly. Specially, with NbS0.2Se1.8 content increasing, the density of Cu/ NbSo.2Se1.8 composites decreases, and the hardness increases firstly and then decreases, while the electric resistivity in- creases slightly. In addition, the incorporation of NbSo.2Se1.8 enhances the tribological properties of Cu greatly, which is attributed to the lubricating effect of Cuo,38NbSo.2Se1.8 and the reinforcement effect of Cu2Se. In particular, when the content of NbSo.2Sel.8 is 6 wt%, the Cu-based composite has the best tribological properties.

Microwave Pyrolysis and Electrochemical Supercapacitor of S-doped g-C_(3)N_(4)Nanoparticles

In this study,S-doped g-C_(3)N_(4)nanoparticles were successfully prepared by one-step solid-state microwave synthesis.The detailed characterizations through XRD,FT-IR,SEM and XPS were studied.In addition,the electrochemical properties as supercapacitor of the sample were tested by cyclic voltammetry(CV),galvanostatic charge-discharge(GCD)and electrochemical impedance spectroscopy(EIS)techniques.The results showed a high specific capacitance of 691 F/g at current density of 4 A/g in 2 M KOH+0.15 M K3[Fe(CN)_(6)]electrolyte.This study shows that the microwave synthesis is a promising way to design carbon-based electrodes for supercapacitor.

S-doped graphene quantum dots as nanophotocatalyst for visible light degradation

Graphene quantum dots （GODs） recently emerge as the new and appealing nanophotocatalyst because of their low-cost, environmental compatibility and the ability to facilitate the charge migration and prolong the charge lifetimes. In this work, a visible photocatalyst of S-doped graphene quantum dots （S-GQDs） was prepared by a facile hydrothermal synthesis using 1,3,6-trinitropyrene and Na2S as precursors. The well crystallization and monodispersity as well as the chemical environment of S-GQDs were characterized by transmission electron microscopy, atom force microscopy and X-ray photoelectron spectrum. A superior photocatalytic performance of S-GQDs was demonstrated for degradation of basic fuchsin under visible light irradiation. Furthermore, the possible photocatalytic mechanism was proposed based on the trapping experiments of active species.

High efficiency visible-light-driven Fe_2O_3-xS_x/S-doped g-C_3N_4 heterojunction photocatalysts: Direct Z-scheme mechanism

Several nanoporous Fe2 O3-xSx/S-doped g-C3 N4（CNS） Z-scheme hybrid heterojuctions have been successfully synthesized by one-pot in situ growth of the Fe2O3-xSx particles on the surface of CNS. The characterization results show that S-doping in the g-C3 N4 backbone can greatly enhance the charge mobility and visible light harvesting capability. In addition, porous morphology of hybrid composite provides available open pores for guest molecules and also improves light absorbing property due to existence of multiple scattering effects. More importantly, the Fe2 O3-xSx nanoparticles formed intimate heterojunction with CNS and developed the efficient charge transfer by extending interfacial interactions occurred at the interfaces of both components. It has been found that the Fe2 O3-xSx/CNS composites have an enhanced photocatalytic activity under visible light irradiation compared with isolated Fe2 O3 and CNS components toward the photocatalytic degradation of methylene blue（MB）. The optimal loaded Fe2 O3-xSx value obtained is equal to 6.6 wt% that provided 82% MB photodegradation after 150 min with a reaction rate constant of 0.0092 min（-1） which was faster than those of the pure Fe2 O3（0.0016 min（-1））and CNS（0.0044 min（-1）） under the optimized operating variables acquired by the response surface methodology. The specific surface area and the pore volume of Fe2 O3（6.6）/CNS hybrid are 33.5 m2/g and0.195 cm3/g, which are nearly 3.8 and 7.5 times greater compared with those of the CNS, respectively. The TEM image of Fe2 O3（6.6）/CNS nanocomposite exhibits a nanoporous morphology with abundant uniform pore sizes of around 25 nm. Using the Mott-Schottky plot, the conduction and valence bands of the CNS are measured（at pH = 7） equal to-1.07 and 1.48 V versus normal hydrogen electrode（NHE）, respectively.Trapping tests prove that ·OH-and ·O2-radicals are major active species in the photocatalytic reaction.It has been established that formation of the Z-scheme Fe2 O3（6.6）/CNS heterojunction between CNS and Fe2 O3 directly produces ·OH as well as ·O2-radicals which is consistent with the results obtained from trapping experiments.

Enhanced photocatalytic performance of S-doped covalent triazine framework for organic pollutant degradation

Photocatalysis using the abundant solar energy is an environmentally friendly and efficient way to degrade organic matter.Covalent triazine frameworks(CTFs),a new class of metal-free organic semiconductors responsive to visible light,are promising materials for water treatment.In this study,an original CTF,namely CTF-1,was modified by S-doping to form CTFSx,which were used as metal-free catalysts for degradation of methyl orange(MO)and bisphenol A(BPA).The outcomes demonstrated that the photocatalytic degradation of MO and BPA by CTFSxwas superior to that by CTF-1,with better stability and reusability.Within 6 h,53.2%MO and 84.7%BPA were degraded by CTFS5,and the degradation rate constants were 0.145 h-1and 0.29 h-1,respectively,which were 3.6 and 5.8 times higher than those of CTF-1.Further investigation revealed that enhanced visible light absorption,a reduced degree of free carrier recombination,rapid separation and transfer of photogenerated electrons and holes,and improved·OH oxidation capacity were important factors contributing to the significantly enhanced photocatalytic activity.The S-doping method effectively improved the light absorption performance,electronic structure,and modulation band structure of CTF-1.This work highlights the potential application of low-cost metal-free catalysts driven by visible light for the removal of organic pollutants from wastewater.

Electronic structure and spin state regulation of vanadium nitride via a sulfur doping strategy toward flexible zinc-air batteries

Owing to the distinctive structural characteristics,vanadium nitride(VN)is highly regarded as a catalyst for oxygen reduction reaction(ORR)in zinc-air batteries(ZABs).However,VN exhibits limited intrinsic ORR activity due to the weak adsorption ability to O-containing species.Here,the S-doped VN anchored on N,S-doped multi-dimensional carbon(S-VN/Co/NS-MC)was constructed using the solvothermal and in-situ doping methods.Incorporating sulfur atoms into VN species alters the electron spin state of vanadium in the S-VN/Co/NS-MC for regulating the adsorption energy of vanadium sites to oxygen molecules.The introduced sulfur atoms polarize the V 3d_(z)^(2) electrons,shifting spin-down electrons closer to the Fermi level in the S-VN/Co/NS-MC.Consequently,the introduction of sulfur atoms into VN species enhances the adsorption energy of vanadium sites for oxygen molecules.The*OOH dissociation transitions from being unspontaneous on the VN surface to a spontaneous state on the S-doped VN surface.Then,the ORR barrier on the S-VN/Co/NS-MC surface is reduced.The S-VN/Co/NS-MC demonstrates a higher half-wave potential and limiting current density compared to the VN/Co/N-MC.The S-VN/Co/NS-MC-based liquid ZABs display a power density of 195.7 m W cm^(-2),a specific capacity of 815.7 m A h g^(-1),and a cycling stability exceeding 250 h.The S-VN/Co/NS-MC-based flexible ZABs are successfully employed to charge both a smart watch and a mobile phone.This approach holds promise for advancing the commercial utilization of VN-based catalysts in ZABs.

N/S-Doped Hierarchical Porous Bamboo Carbon Fibers with Ultra-Large Surface Area and Highly Exposed Active Sites for Flexible Zinc-Air Battery

Facile mass transport channel and accessible active sites are crucial for binder-free air electrode catalysts in rechargeable flexible zinc-air battery(ZAB).Herein,a ZnS/NH3 dual-assisted pyrolysis strategy is proposed to prepare N/S-doped hierarchical porous bamboo carbon cloth(HP-NS-BCC)as binder-free air electrode catalyst for ZAB.BCC fabric with abundant micropores is firstly used as flexible carbon support to facilitate the heteroatom-doping and construct the hierarchical porous structure.ZnS nanospheres and NH3 activization together facilitate the electronic modulation of carbon matrix by N/S-doping and optimize the macro/meso/micropores structure of carbon fibers.Benefiting from the highly-exposed N/S-induced sites with enhanced intrinsic activity,the optimized mass transport of biocarbon fibers,as well as the ultra-large specific surface area of 2436.1 m^(2)·g^(-1),the resultant HP-NS-BCC catalyst exhibits improved kinetics for oxygen reduction/evolution reaction.When applied to rechargeable aqueous ZABs,it achieves a significant peak power density of 249.1 mW·cm^(-2).As binder-free air electrode catalyst,the flexible ZAB also displays stable cycling over 500 cycles with a minimal voltage gap of 0.42 V,showcasing promising applications in flexible electronic devices.

Development of nitrogen and sulfur-doped carbon dots for cellular imaging

Heteroatom-doped carbon dots(CDs) have attracted extensive interest because of their improved electronic and fluorescence properties with heteroatom doping. In this study, a new synthetic method for nitrogen(N) and sulfur(S)-doped CDs was developed via a hydrothermal method using methionine and citric acid as raw materials. The as-prepared CDs exhibit excellent optical properties and good biocompatibility. The spherical N,S-doped CDs have an average diameter of 5 nm. They consist of C, O, N and S, and take on excellent water solubility due to the hydroxyl and carboxyl, amino groups on the surface.The CDs have a photoluminescence quantum yield of 13.8% using quinine sulfate as a reference; the average fluorescence lifetime of the CDs was 3.67 ns. The CDs solution present good photoluminescence properties, and the maximum excitation wavelength and emission wavelength locate at 330 nm and405 nm, respectively. In addition, their fluorescence intensity almost does not change under the conditions of acid, alkali, and high salt, which indicated their anti-photobleaching property and good light stability. Based on the good biocompatibility and strong fluorescence emission of the CDs, they can be used as fluorescent imaging reagents.

In situ sulfur-doped graphene nanofiber network as efficient metal-free electrocatalyst for polysulfides redox reactions in lithium–sulfur batteries

The major challenge for realistic application of Li-S batteries lies in the great difficulty in breaking through the obstacles of the sluggish kinetics and polysulfides shuttle of the sulfur cathode at high sulfur loading for continuously high sulfur utilization during prolonged charge-discharge cycles.Here we demonstrate that large percentage of sulfur can be effectively incorporated within a three-dimensional(3D)nanofiber network of high quality graphene from chemical vapor deposition(CVD),through a simple ball-milling process.While high quality graphene network provided continuous and durable channels to enable efficient transport of lithium ions and electrons,the in-situ sulfur doping from the alloying effect of ball milling facilitated desirable affinity with entire sulfur species to prevent sulfur loss and highly active sites to propel sulfur redox reactions over cycling.This resulted in remarkable rate-performance and excellent cycling stability,together with large areal capacity at very high sulfur mass loading(Specific capacity over 666 mAh g-1after 300 cycles at 0.5 C,and areal capacity above 5.2 mAh cm-2at 0.2C at sulfur loading of 8.0 mg cm-2 and electrolyte/sulfur(E/S)ratio of 8μL mg-1;and high reversible areal capacities of 13.1 m Ah cm-2 at a sulfur load of 15 mg cm-2 and E/S of 5μL mg-1).

N/S co-doped 3D carbon framework prepared by a facile morphology-controlled solid-state pyrolysis method for oxygen reduction reaction in both acidic and alkaline media

Developing high-performance non-precious metal electrocatalysts for oxygen reduction reaction(ORR)is crucial for the commercialization of fuel cells and metal-air batteries.However,doped carbon-based materials only show good ORR activity in alkaline medium,and become less effective in acidic environment.We believe that an appropriate combination of both ionic and electronic transport path,and well dopant distribution of doped carbon-based materials would help to realize high ORR performance un-der both acidic and alkaline cond让ions.Accordingly,a nitrogen and sulfur co-doped carbon framework with hierarchical through-hole structure is fabricated by morphology-controlled solid-state pyrolysis of poly(aniline-co-2-ami no thiophenol)foam.The uniform high concentrations of nitrogen and sulfur,high intrinsic conductivity,and integrated three dimensional ionic and electronic transfer passageways of the 3D porous structure lead to synergistic effects in catalyzing ORR.As a result,the limiting current density of the carbonized poly(aniline-co-2-aminothiophenol)foam is equivalent to commercial Pt/C in acidic environment,and twice the latter in alkaline medium.

Semiconducting single-walled carbon nanotubes synthesized by S-doping

An approach was presented for synthesis of semiconducting single-walled carbon nanotubes(SWNTs) by sulfur(S) doping with the method of graphite arc discharge. Raman spectroscopy, UV-vis-NIR absorption spectroscopy and electronic properties measurements indicated the semconducting properties of the SWNTs samples. Simulant calculation indicated that S doping could induce convertion of metallic SWNTs into semiconducting ones. This strategy may pave a way for the direct synthesis of pure semiconducting SWNTs.