Tandem Co–O dual sites on halloysite with promoted reaction kinetics for sulfur reduction

Facilitating sulfur reduction reaction(SRR)is a promising pathway to tackle the polysulfide shuttle effect and enhance the electrochemical performance of lithium-sulfur(Li-S)batteries.Catalysts with a solo active site can reduce a reaction barrier of a certain transition-intermediate,but the linear scaling relationship between multi-intermediates still obstructs overall SRR.Herein,we construct tandem Co–O dual sites with accelerating SRR kinetics by loading highly dispersed cobalt sulfide clusters on halloysite.This catalyst features Co with upshifted d-orbital and O with downshifted p-orbital,which cooperatively adsorb long-chain polysulfide and dissociate an S–S bond,thus achieving both optimal adsorption–desorption strength and reduced conversion energy barrier of multi-intermediates in SRR.The Li-S coin batteries using the electrocatalyst endows a high specific capacity of 1224.3 m Ah g^(-1)at 0.2 C after 200cycles,and enhances cycling stability with a low-capacity decay rate of 0.03%per cycle at 1 C after1000 cycles.Moreover,the strategy of the tandem Co–O dual sites is further verified in a practical Li-S pouch battery that realizes 1014.1 m Ah g^(-1)for 100 cycles,which opens up a novel avenue for designing electrocatalysts to accelerate multi-step reactions.

Preparation of the complex metallic oxides additive for naphtha sulfur reduction in FCC

The M/USY/Al2O3/kaolinite sulfur reduction additive systems containing vanadium were prepared by different methods. The influence of the preparation methods, the active constituent forerunners, the vanadium content and the type of molecular sieves on sulfur reduction of fluid catalytic cracking （FCC） gasoline were studied by a small fixed bed. The results showed that when FCC catalyst was blended with the sulfur reduction additives prepared by the special method at the ratio of 95：5, the relative sulfur reduction rate reached 35% and there was little influence on distribution of the products and quality of the gasoline. The XRD analysis indicated that the Y molecular sieve crystal structure in the additives prepared by the specific method retained integrity.

Design principle of single-atom catalysts for sulfur reduction reaction—interplay between coordination patterns and transition metals

The polysulfide shuttling effect is the primary bottleneck restricting the industrial application of Li-S batteries,and the electrocatalytic sulfur reduction reaction(SRR)has emerged as an effective solution.Carbon-based singleatom catalysts(SACs),which promotes SRR,show great potential in inhibiting the shuttling effect of polysulfides.Meanwhile,the optimization and rational design of such catalysts requires a deep understanding to the fundamental SRR mechanism and remains highly nontrivial.In this work,we construct a comprehensive database of carbon-based SACs,covering different coordination patterns,heteroatoms,and transition metals.The SRR activities are determined using density functional theory calculations,revealing a synergistic effect between the p orbital of the heteroatom and the d orbital of the transition metal.This interplay underscores the critical importance of the coordination environment for SRR under the ortho-P_(2)C_(2)structure.Regardless of the transition metal type,the ortho-P_(2)C_(2)coordination pattern significantly enhances the SRR performance of SACs,surpassing the widely reported N_(3)C_(1)and N_(4)coordinated graphene-based SACs.Furthermore,heteroatoms with ortho-P_(2)C_(2)may exhibit SRR activity.In a word,by using this comprehensive dataset and data-driven framework,we propose a promising novel class of coordination structure(ortho-P_(2)C_(2)structure)and neglected design principle.

MOF-related electrocatalysts for sulfur reduction/evolution reactions:Composition modulation,structure design,and mechanism research

The electrocatalytic sulfur reduction reaction(SRR)and sulfur evolution reaction(SER),two fundamental multistep conversion processes in lithium–sulfur batteries(LSBs),are root-cause solutions to overcome sluggish redox kinetics and the polysulfide shuttling effect.Metal–organic framework(MOF)electrocatalysts have emerged as good platforms for catalyzing SRR and SER,but their catalytic performance is challenged by poor electrical conductivity and limited chemical stability.Functionalized MOFs and their hybrids may be beneficial for stabilizing and improving the desired catalytic properties to achieve high-performance LSBs.This review provides a detailed overview of engineering principles for improving the activity,selectivity,and stability of MOFrelated electrocatalysts via composition modulation and nanostructure design as well as hybrid assembly.It presents and discusses the various advances achieved by using in situ characterization techniques,simulations,and theoretical calculations to reveal the dynamic evolution of MOF-related electrocatalysts,enabling an in-depth understanding of the catalysis mechanism at the molecular/atomic level.Lastly,prospects and possible research directions for MOF-related sulfur electrocatalysts are proposed.

Boosting Lean Electrolyte Lithium-Sulfur Battery Performance with Transition Metals: A Comprehensive Review

Lithium–sulfur(Li–S) batteries have received widespread attention, and lean electrolyte Li–S batteries have attracted additional interest because of their higher energy densities. This review systematically analyzes the effect of the electrolyte-to-sulfur(E/S) ratios on battery energy density and the challenges for sulfur reduction reactions(SRR) under lean electrolyte conditions. Accordingly, we review the use of various polar transition metal sulfur hosts as corresponding solutions to facilitate SRR kinetics at low E/S ratios(< 10 μL mg~(-1)), and the strengths and limitations of different transition metal compounds are presented and discussed from a fundamental perspective. Subsequently, three promising strategies for sulfur hosts that act as anchors and catalysts are proposed to boost lean electrolyte Li–S battery performance. Finally, an outlook is provided to guide future research on high energy density Li–S batteries.

Acid deposition critical loads modeling for the simulation of sulfur exceedance and reduction in Guangdong, China

The current acid deposition critical loads in Guangdong, China were calculated using the PROFILE model with a 3 km × 3 km resolution. Calculations were carded out for critical loads of potential acidity, actual acidity, sulfur and nitrogen, with values in extents of 0-3.5, 0-14.0, 0-26.0 and 0-3.5 kmol/（hrnE.year）, respectively. These values were comparable to previously reported results and reflected the influences of vegetation and soil characteristics on the soil acid buffering capacity. Simulations of SO2 emission and sulfur deposition in this study showed that sulfur deposition core areas mirrored SO2 emission centers. The prediction of sulfur deposition after 20% and 40% reduction of SO2 emission suggested that the reduction of area sources contributed greatly to the decrease of sulfur deposition. Thus, abatement of area source emissions could be the primary way to mitigate sulfur deposition in Guangdong to meet both the provincial and national regulations of air pollution control.

Constructing Abnormal Step-Scheme Nano-Heterointerfaces as Sulfur Electrocatalysts with Desirable Electron Confinement for Practical Li-S Battery

Heterostructured sulfur electrocatalysts have long been heralded as an effective approach to settle the issues of the shuttle effect and sluggish reaction kinetics of lithium polysulfides(LiPSs)in lithium-sulfur(Li-S)batteries.However,the limited active sites on the interface of the heterostructure offer unsatisfactory LiPSs conversion capability,rendering sluggish reaction kinetics.Herein,we have designed abnormal step-scheme nano-heterointerfaces,containing P-N,N-semimetal,and P-semimetal heterostructures as sulfur electrocatalysts to regulate the LiPSs catalytic conversion behavior,which demonstrates efficient catalytic activity and robust structural stability.The excellent electron-confinement contributed by the step-scheme barrier endows the electron gathering at the nano-heterointerfaces,conferring high selectivity and durability of electrocatalyst for an accelerated sulfur reduction reaction.The unique robust structure design further bestows the sulfur composite with favored ion/mass transportation within the electrode.Attributed to these structural features,the Li-S cell delivers excellent performance under high areal capacity over 7 mAh cm^(−2) and lean electrolyte/sulfur ratio below 2.5μL mg^(−1),decent rate capability up to 8 C,remarkable cyclic stability over 500 cycles,and satisfactory energy density of 386.3 Wh kg^(−1) in a 7.5 Ah pouch cell.This nano-heterointerface structure design strategy endows a sulfur cathode with superior LiPSs catalytic activity,opening new insights into high-performance Li-S batteries.

Effect of liming on sulfate transformation and sulfur gas emissions in degraded vegetable soil treated by reductive soil disinfestation

Reductive soil disinfestation（RSD）, namely amending organic materials and mulching or flooding to create strong reductive status, has been widely applied to improve degraded soils.However, there is little information available about sulfate（SO4^2-） transformation and sulfur（S）gas emissions during RSD treatment to degraded vegetable soils, in which S is generally accumulated. To investigate the effects of liming on SO4^2-transformation and S gas emissions,two SO4^2--accumulated vegetable soils（denoted as S1 and S2） were treated by RSD, and RSD plus lime, denoted as RSD0 and RSD1, respectively. The results showed that RSD0 treatment reduced soil SO4^2-by 51% and 61% in S1 and S2, respectively. The disappeared SO4^2-was mainly transformed into the undissolved form. During RSD treatment, hydrogen sulfide（H2S）,carbonyl sulfide（COS）, and dimethyl sulfide（DMS） were detected, but the total S gas emission accounted for 〈 0.006% of total S in both soils. Compared to RSD0, lime addition stimulated the conversion of SO42-into undissolved form, reduced soil SO4^2-by 81% in S1 and 84% in S2 and reduced total S gas emissions by 32% in S1 and 57% in S2, respectively. In addition to H2S, COS and DMS, the emissions of carbon disulfide, methyl mercaptan, and dimethyl disulfide were also detected in RSD1 treatment. The results indicated that RSD was an effective method to remove SO4^2-, liming stimulates the conversion of dissolved SO4^2-into undissolved form,probably due to the precipitation with calcium.

A review of transition metal chalcogenide/graphene nanocomposites for energy storage and conversion

To meet the ever-increasing energy demands, advanced electrode materials are strongly requested for the exploration of advanced energy storage and conversion technologies, such as Li-ion batteries, Li-S batteries, Li-]Zn-air batteries, supercapacitors, dye-sensitized solar cells, and other electrocatalysis process （e.g., oxygen reductionlevolution reaction, hydrogen evolution reaction）. Transition metal chalcogenides （TMCs, Le., sulfides and selenides） are forcefully considered as an emerging candidate, owing to their unique physical and chemical properties. Moreover, the integration of TMCs with conductive graphene host has enabled the significant improvement of electrochemical performance of devices. In this review, the recent research progress on TMC]graphene composites for applications in energy storage and conversion devices is summarized. The preparation process of TMC]graphene nanocomposites is also included. In order to promote an in-depth understanding of performance improvement for TMC/graphene materials, the operating principle of various devices and technologies are briefly presented. Finally, the perspectives are given on the design and construction of advanced electrode materials.