Sulfur-doped hard carbon hybrid anodes with dual lithium-ion/metal storage bifunctionality for high-energy-density lithium-ion batteries

Bifunctional hybrid anodes(BHAs),which are both a high-performance active host material for lithium-ion storage as well as a guiding agent for homogeneous lithium metal nucleation and growth,exhibit significant potential as anodes for next-generation high-energy-density lithium-ion batteries(LIBs).In this study,sulfur-doped hard carbon nanosphere assemblies(S-HCNAs)were prepared through a hydrothermal treatment of a liquid organic precursor,followed by high-temperature thermal annealing with elemental sulfur for application as BHAs for LIBs.In a carbonate-based electrolyte containing fluoroethylene carbonate additive,the S-HCNAs showed high lithium-ion storage capacities in sloping as well as plateau voltage sections,good rate capabilities,and stable cyclabilities.In addition,high average Coulombic efficiencies(CEs)of~96.9%were achieved for dual lithium-ion and lithium metal storage cycles.In the LIB full-cell tests with typical NCM811 cathodes,the S-HCNA-based BHAs containing~400 mA h g^(−1) of excess lithium led to high energy and power densities of~500Wh kg^(−1) and~1695Wkg^(−1),respectively,and a stable cycling performance with~100%CEs was achieved.

Understanding the improved performance of sulfur-doped interconnected carbon microspheres for Na-ion storage

As one of the low-cost energy storage systems,Na-ion batteries(NIBs)have received tremendous attention.However,the performance of current anode materials still cannot meet the requirements of NIBs.In our work,we obtain sulfur-doped interconnected carbon microspheres(S-CSs)via a simple hydrothermal method and subsequent sulfurizing treatment.Our S-CSs exhibit an ultrahigh reversible capacity of 520 mAh g^(-1) at 100 mA g^(-1) after 50 cycles and an excellent rate capability of 257 mAh g^(-1),even at a high current density of 2 A g^(-1).The density functional theory calculations demonstrate that sulfur doping in carbon favors the adsorption of Na atom during the sodiation process,which is accountable for the performance enhancement.Furthermore,we also utilize operando Raman spectroscopy to analyze the electrochemical reaction of our S-CSs,which further highlights the sulfur doping in improving Na-ion storage performance.

One-step Synthesis and Photocatalytic Degradation Performance of Sulfur-doped Porous g-C_(3)N_(4)Nanosheets

In this study,the sulfur-doped porous g-C_(3)N_(4) nanosheets(CN-T-U 1.75)were synthesized successfully by onestep calcination utilizing urea and thiourea as precursors.Under visible light irradiation,CN-T-U 1.75 showed remarkable photocatalytic activity for Rhodamine B(RhB)degradation with a kinetic reaction rate constant of 0.01838 min^(-1).The characterization analysis indicated that CN-T-U 1.75 had a higher specific surface area and the doping altered the energy band structure.This work offers a new viewpoint on modifying the band structure of a photocatalyst using a doping strategy,as well as new insights into the generation routes of active species involved in the photocatalytic process.

Surface defect-rich ceria quantum dots anchored on sulfur-doped carbon nitride nanotubes with enhanced charge separation for solar hydrogen production

Designing defect-engineered semiconductor heterojunctions can effectively promote the charge carrier separation.Herein,novel ceria(CeO2) quantum dots(QDs) decorated sulfur-doped carbon nitride nanotubes(SCN NTs) were synthesized via a thermal polycondensation coupled in situ depositionprecipitation method without use of template or surfactant.The structure and morphology studies indicate that ultrafine CeO2 QDs are well distributed inside and outside of SCN NTs offering highly dispersed active sites and a large contact interface between two components.This leads to the promoted formation of rich Ce^(3+) ion and oxygen vacancies as confirmed by XPS.The photocatalytic performance can be facilely modulated by the content of CeO2 QDs introduced in SCN matrix while bare CeO2 does not show activity of hydrogen production.The optimal catalyst with 10% of CeO2 loading yields a hydrogen evolution rate of 2923.8 μmol h-1 g-1 under visible light,remarkably higher than that of bare SCN and their physical mixtures.Further studies reveal that the abundant surface defects and the created 0 D/1 D junctions play a critical role in improving the separation and transfer of charge carriers,leading to superior solar hydrogen production and good stability.

Fabrication of sulfur-doped cove-edged graphene nanoribbons on Au(111)

The on-surface synthesis from predesigned organic precursors can yield graphene nanoribbons(GNRs)with atomically precise widths,edge terminations and dopants,which facilitate the tunning of their electronic structures.Here,we report the synthesis of novel sulfur-doped cove-edged GNRs(S-CGNRs)on Au(111)from a specifically designed precursor containing thiophene rings.Scanning tunneling microscopy and non-contact atomic force microscopy measurements elucidate the formation of S-CGNRs through subsequent polymerization and cyclodehydrogenation,which further result in crosslinked branched structures.Scanning tunneling spectroscopy results reveal the conduction band minimum of the S-CGNR locates at 1.2 e V.First-principles calculations show that the S-CGNR possesses an energy bandgap of 1.17 e V,which is evidently smaller than that of an undoped cove-edged GNR(1.7 e V),suggesting effective tuning of the bandgap by introducing sulfur atoms.Further increasing the coverage of precursors close to a monolayer results in the formation of linear-shaped S-CGNRs.The fabrication of S-CGNRs provides one more candidate in the GNR toolbox and promotes the future applications of heteroatom-doped graphene nanostructures.

Kinetics of photoelectrocatalytic degradation of endocrine disrupting chemicals using sulfur-doped TiO_2 /Ti photoelectrodes

In this study,sulfur-doped TiO2 /Ti photoelectrodes were prepared by anodization. The morphology, crystalline structure,composition of sulfur-doped TiO2 /Ti film and light absorption property were examined by SEM,XRD,XRF,XPS and UV/VIS respectively. Dimethyl phthalate( DMP) ,one kind of environmental disrupting chemicals( EDCs) ,was degraded by the optimized photoelectrodes. Power of xenon light,initial concentration of DMP,photoelectrocatalytic( PEC) area of photoelectrode and bias were investigated in the study on kinetics of PEC degradation of DMP. Hence,this study concluded that the optimum conditions were power of xenon light 150 W,initial concentration of DMP 1 mg/L,PEC area of sulfur-doped TiO2 /Ti photoelectrode 10 cm2,bias 1. 3 V in the PEC reaction system.

One-step fabrication of mesoporous sulfur-doped carbon nitride for highly selective photocatalytic transformation of native lignin to monophenolic compounds

Photocatalytic selective transform native lignin into valuable chemicals is an attractive but challenging task.Herein,we report a mesoporous sulfur-doped carbon nitride(MSCN-0.5)which is prepared by a facile one-step thermal condensation strategy.It is highly active and selective for the cleavage Cα-Cβbond inβ-O-4 lignin model compound under visible light radiation at room temperature,achieving 99%substrate conversion and 98%Cα-Cβbond cleavage selectivity.Mechanistic studies revealed that the Cβ-H bond of lignin model compounds activated by holes and generate key Cβradical intermediates,further induced the Cα-Cβbond cleavage by superoxide anion radicals(·O2-)to produce aromatic oxygenates.Waste Camellia oleifera shell(WCOS)was taken as a representative to further understand the reaction mechanisms on native lignin.33.2 mg of monophenolic compounds(Vanillin accounted for 22%and Syringaldehyde for 34%)can be obtained by each gram of WCOS lignin,which is 2.5 times as that of the pristine carbon nitride.The present work offers useful guidance for designing metal-free heterogeneous photocatalysts for Cα-Cβbond cleavage to harvest monophenolic compounds.

Sulfur-doped CMK-5 with expanded lattice for high-performance lithium ion batteries

Heteroatom-doped porous carbon materials are very attractive for lithium ion batteries(LIBs) owing to their high specific surface areas, open pore structures, and abundant active sites. However, heteroatomdoped porous carbon with very high surface area and large pore volume are highly desirable but still remain a big challenge. Herein, we reported a sulfur-doped mesoporous carbon(CMK-5-S) with nanotubes array structure, ultrahigh specific surface area(1390 m^(2)/g), large pore volume(1.8 cm^(3)/g), bimodal pore size distribution(2.9 and 4.6 nm), and high sulfur content(2.5 at%). The CMK-5-S used as an anode material for LIBs displays high specific capacity, excellent rate capability and highly cycling stability. The initial reversible specific capacity at 0.1 A/g is as high as 1580 mAh/g and simultaneously up to 701 mAh/g at 1A/g even after 500 cycles. Further analysis reveals that the excellent electrochemical storage performances is attributed to its unique structures as well as the expanded lattice by sulfur-doping.

Sulfur-doped g-C3N4/rGO porous nanosheets for highly efficient photocatalytic degradation of refractory contaminants

Graphitic carbon nitride(g-C3N4,CN)has attracted increasing interests in the field of photocatalysis due to its high visible-light-response.However,its photocatalytic activity is still lower for degradation of refractory contaminants such as Cr(Ⅵ)and Rhodamine B(RhB)etc.Herein,we report a facile method to synthesize a novel sulfur(S)-doped CN/reduced graphene oxide(rGO)porous nanosheet(S-CN/rGO PNs)via a supramolecular self-assembling followed by a solvothermal treatment.The as-prepared porous SCN/rGO PNs are stable with high specific surface area^188.5 m2 g-1 and exhibit a significantly enhanced photocatalytic activity of^17-fold and 15-fold higher than that of bulk CN for the degradation of RhB and Cr(Ⅵ)under visible light irradiation,respectively.Typically,50 mL of 15 mg/mL RhB can be degraded within 20 min by 10 mg S-CN/rGO PNs.The mechanism can be explained by the synergistic effect of S doping and porous structure which can effectively reduce the band gap of CN and increase the specific surface area to promote the separation and transfer of photo-generated charge carriers.The results have provided a new way to significantly enhance the photocatalytic activity of g-C3N4 for degradation of refractory contaminants.

Three Dimensional Sulfur-doped Graphene Hydrogels with Tetrathiafulvalene for High Performance Supercapacitors

By using tetrathiafulvalene as reducing and doping agents, three-dimensional （3D） sulfur-doped graphene hydrogels （SGHs） were facilely prepared in mixed solvents of dimethyl formamide and water. Several investigations reveal that TTF plays a critical role in the formation of such unique 3D architecture, as it not only reduces GO to self-assembly into 3D structures, but also can be transformed to TTF^·＋ and TTF^2＋ as doping agents in the reduction process. The morphology, crystal structure, chemical bonding, elemental composition and porosity of the as-prepared SGHs have been studied. Benefiting from well-defined and cross-linked 3D porous network architectures, the supercapacitors based on the SGHs in KOH 212.5 F·g^-1 at 0.3 A·g^-1. Furthermore, this capacitance also degree of reversibility in the repetitive charge/discharge cycling electrolyte exhibited a high specific capacitance of showed good electrochemical stability and a high test.

Sulfur-doped graphene anchoring of ultrafine Au25 nanoclusters for electrocatalysis

The biggest challenge of exploring the catalytic properties of under-coordinated nanoclusters is the issue of stability.We demonstrate herein that chemical dopants on sulfur-doped graphene(S-G)can be utilized to stabilize ultrafine(sub-2 nm)Au_(25)(PET)18 clusters to enable stable nitrogen reduction reaction(NRR)without significant structural degradation.The Au_(25)@S-G exhibits an ammonia yield rate of 27.5μgNH_(3)·mgAu^(-1)·h^(-1)at-0.5 V with faradic efficiency of 2.3%.More importantly,the anchored clusters preserve~80%NRR activity after four days of continuous operation,a significant improvement over the 15%remaining ammonia production rate for clusters loaded on undoped graphene tested under the same conditions.Isotope labeling experiments confirmed the ammonia was a direct reaction product of N2 feeding gas instead of other chemical contaminations.Ex-situ X-ray photoelectron spectroscopy and X-ray absorption near-edge spectroscopy of post-reaction catalysts reveal that the sulfur dopant plays a critical role in stabilizing the chemical state and coordination environment of Au atoms in clusters.Further ReaxFF molecular dynamics(RMD)simulation confirmed the strong interaction between Au nanoclusters(NCs)and S-G.This substrate-anchoring process could serve as an effective strategy to study ultrafine nanoclusters’electrocatalytic behavior while minimizing the destruction of the under-coordinated surface motif under harsh electrochemical reaction conditions.

In-situ Construction of Sulfur-doped g-C_(3)N_(4)/defective g-C_(3)N_(4) Isotype Step-scheme Heterojunction for Boosting Photocatalytic H_(2) Evolution

The rational construction of a high-efficiency stepscheme heterojunctions is an effective strategy to accelerate the photocatalytic H_(2).Unfortunately,the variant energy-level matching between two different semiconductor confers limited the photocatalytic performance.Herein,a newfangled graphitic-carbon nitride(g-C_(3)N_(4))based isotype step-scheme heterojunction,which consists of sulfur-doped and defective active sites in one microstructural unit,is successfully developed by in-situ polymerizing N,N-dimethylformamide(DMF)and urea,accompanied by sulfur(S)powder.Therein,the polymerization between the amino groups of DMF and the amide group of urea endows the formation of rich defects.The propulsive integration of S-dopants contributes to the excellent fluffiness and dispersibility of lamellar g-C_(3)N_(4).Moreover,the developed heterojunction exhibits a significantly enlarged surface area,thus leading to the more exposed catalytically active sites.Most importantly,the simultaneous introduction of S-doping and defects in the units of g-C_(3)N_(4) also results in a significant improvement in the separation,transfer and recombination efficiency of photo-excited electron-hole pairs.Therefore,the resulting isotype step-scheme heterojunction possesses a superior photocatalytic H_(2) evolution activity in comparison with pristine g-C_(3)N_(4).The newly afforded metal-free isotype step-scheme heterojunction in this work will supply a new insight into coupling strategies of heteroatoms doping and defect engineering for various photocatalytic systems.

Sulfur-doped 3D hierarchical porous carbon network toward excellent potassium-ion storage performance

Carbonaceous materials are promising anode candidates for potassium-ion batteries, but currently the unsatisfactory cycling and rate performances due to the sluggish diffusion kinetic and serious structure damage during K+ insertion/extraction limit their practical application. Herein, a series of sulfur-doped porous carbons(SPCs) were prepared via a template-assisted freeze-drying followed by the carbonization and sulfuration processes at different temperatures. Among the three as-synthesized samples, SPC-600 exhibits the highest specific capacity(407 mAh·g^(-1) at 0.10 A·g^(-1)), the best rate(242 mAh·g^(-1) at 2.00 A·g^(-1)) and cycling performance(286 m Ah·g^(-1) after 800 cycles at 0.50 A·g^(-1)). All the SPCs display higher capacities than the undoped carbon materials. The excellent electrochemical performance of SPC can be ascribed to the abundant three-dimensional porous structure together with S-doping in the disordered carbon, which is favor of providing adequate reaction active sites as well as fast ion/electron transport paths. The density functional theory(DFT) calculations further demonstrate that the sulfurdoping can promote K-ion adsorption and storage. Meanwhile, the kinetic analyses reveal that surface-induced capacitive mechanism dominates the K-ion storage process in SPCs, which contributes to ultrafast charge storage. This work provides an effective strategy for fabricating highperformance potassium-ion storage electrode materials.

Mitigating the Reconstruction of Metal Sulfides for Ultrastable Oxygen Evolution at High Current Density

Metal sulfides are emerging highly active electrocatalysts for the oxygen evolution reaction(OER),but still suffer from the instability caused by their inevitable reconstruction,especially at industrial-level current density.Here,it is discovered that Fe-incorporated Ni3S2 nanowires can deliver extraordinary durability with an ultralow potential degradation rate of 0.006 mV/h in alkaline electrolytes made with fresh water and seawater at a benchmark of 500 mA cm^(-2) while meeting the industrial activity requirement for overpotential less than 300 mV(290 mV).Systematic experiments and theoretical simulations suggest that after forming the S-doped NiFeOOH shell to boost intrinsic activity,Fe incorporation effectivelymitigates the reconstruction of the Ni_(3)S_(2) nanowire core by restraining Ni oxidation and S dissolution,justifying the performance.This work highlights the significance of circumventing reconstruction and provides a strategy to explore practical chalcogenides-based OER electrocatalysts.

硫掺杂氮化碳纳米片棒状聚集体用于光催化析氢

合成具有较宽吸收光谱的少层氮化碳是一个具有吸引力的课题.杂原子掺杂(特别是硫掺杂)可以有效地避免纳米级片层氮化碳中由于量子限制效应所引起的带隙加宽.与二次煅烧硫化不同的是,预硫化超分子前驱体可以原位地形成硫掺杂氮化碳纳米片堆叠聚集体(SCN).这种少层的框架结构呈现出了更大的比表面积(139.06 m^(2)g^(−1)),暴露了更多的活性位点.此外,硫的引入使原七嗪环的共轭结构发生扭曲,从而通过激活价带电子的n→π*跃迁而缩小带隙.在模拟日光条件下,SCN0.8(3925.8μmol g^(−1)h^(−1))的析氢速率是块体氮化碳(BCN,485.2μmol g^(−1)h^(−1))的8.1倍.本工作旨在最大限度地利用杂原子掺杂和形态调控的协同效应来提高光催化活性,且为光催化剂的多维同步优化提供了新的视角.

Porous FeO_x/BiVO_(4-δ)S_(0.08): Highly efcient photocatalysts for the degradation of Methylene Blue under visible-light illumination

Porous S-doped bismuth vanadate with an olive-like morphology and its supported iron oxide （y wt.% FeOx/BiVO4-δS0.08, y = 0.06, 0.76, and 1.40） photocatalysts were fabricated using the dodecylamine-assisted alcohol-hydrothermal and incipient wetness impregnation methods, respectively. It is shown that the y wt.% FeOx/BiVO4-δS0.08 photocatalysts contained a monoclinic scheetlite BiVO4 phase with a porous olive-like morphology, a surface area of 8.8-9.2 m^2/g, and a bandgap energy of 2.38-2.42 eV. There was co-presence of surface Bi^5＋, Bi^3＋, V^5＋, V^3＋, Fe^3＋, and Fe^2＋ species in y wt.% FeOx/BiVO4-δS0.08. The 1.40 wt.% FeOx/BiVO4-δS0.08 sample performed the best for Methylene Blue degradation under visible-light illumination. The photocatalytic mechanism was also discussed. We believe that the sulfur and FeOx co-doping, higher oxygen adspecies concentration, and lower baudgap energy were responsible for the excellent visible-light-driven catalytic activity of 1.40 wt.% FeOx/BiVO4-δS0.08.

Porous surfur-doped hard carbon for excellent potassium storage

Hard carbon is promising anode for potassium-ion batteries(PIBs),however,the poor rate capability hinders its development as potential anode.To address this question,we design a sulfur-doped porous hard carbon(S-HC)for PIBs through the combination of structural design and composition adjustment.The as-designed S-HC exhibits a long cycling life with^191 mAh/g after 300 cycles at 1 A/g,and an excellent rate capability with^100 mAh/g at 5 A/g,which was attributed to its structural characteristics and compositions.The S-HC demonstrates to be promising anode in the future.