Sulfur Functionalities Research Articles

A simple and low-cost method of sulfur functionalization and aqueous dispersion of graphene driven by gas-liquid non-thermal plasma discharge

A simple and low-cost method of sulfur functionalization and aqueous dispersion of graphene driven by gas-liquid non-thermal plasma discharge

Deciphering the Influence of Anionic Electrons of Surface-Functionalized Two-Dimensional Electrides in Lithium-Sulfur Batteries.

Using transition metal compounds as sulfur hosts is regarded as a promising approach to suppress the polysulfide shuttle and accelerate redox kinetics for lithium-sulfur (Li-S) batteries. Herein, we report that a new kind of compound, electrides (exotic ionic crystalline materials in which electrons serve as anions), is efficient sulfur hosts for Li-S batteries for the first time. Based on the first-principles calculations, we found that two-dimensional (2D) electrides M2C (M = Sc, Y) exhibit unprecedentedly strong binding strength toward sulfur species and surface functionalization is necessary to passivate their activity. The 2D electrides modified with the F-functional group exhibit the best performance in terms of the adsorption energy and sulfur reduction process. A comparative study with a nonelectride reveals that the anionic electrons (AEs) of electrides aid in anchoring the soluble polysulfides. These results open an avenue for the application of electrides in Li-S batteries.

Sulfur-aided aerobic biostabilization of swine manure and sawdust mixture: Humification and carbon loss

To investigate how sulfur addition affects humification and carbon loss during swine manure (SM) biostabilisation, various proportions of sulfur, i.e., 0 (CK), 0.2%-0.8% (S1-S4) were added to SM in a 70-day pilot-scale test. Compared to CK (16.07%), sulfur addition resulted in the mineralization of 17.05%-24.27% of the total organic carbon. Sulfur addition also reduced CH4 emissions, which were 3.7%-29.3% lower than that of CK. The total global warming potential values were in the range of 913.1–968.2 g CO2 eq kg−1 for all treatments. Although the sulfur-added treatments showed lower HA/FA ratios than CK after 70 days, no significant impact on the maturity of the final products was observed. Sulfur addition impacted the microbial community, CH4, CO2, N2O emissions, and affected the variation of temperature in biowaste biostabilization. These discoveries provided an important basis for understanding the function of sulfur in regulating the aerobic bio-decomposition of organic waste.

Dimensionality Engineering of Single-Atom Nanozyme for Efficient Peroxidase-Mimicking.

In nature, enzymatic reactions occur in well-functioning catalytic pockets, where substrates bind and react by properly arranging the catalytic sites and amino acids in a three-dimensional (3D) space. Single-atom nanozymes (SAzymes) are a new type of nanozymes with active sites similar to those of natural metalloenzymes. However, the catalytic centers in current SAzymes are two-dimensional (2D) architectures and the lack of collaborative substrate-binding features limits their catalytic activity. Herein, we report a dimensionality engineering strategy to convert conventional 2D Fe-N-4 centers into 3D structures by integrating oxidized sulfur functionalities onto the carbon plane. Our results suggest that oxidized sulfur functionalities could serve as binding sites for assisting substrate orientation and facilitating the desorption of H2O, resulting in an outstanding specific activity of up to 119.77 U mg-1, which is 6.8 times higher than that of conventional FeN4C SAzymes. This study paves the way for the rational design of highly active single-atom nanozymes.

Phosphorus-mediated succession of microbial nitrogen, carbon, and sulfur functions in rice-driven saline-alkali soil remediation

Although rice cultivation holds potential for restoring unproductive saline-alkali soils and increasing food production, the mechanisms underlying the relationship between microbial functions and soil element turnover remain unclear. To clarify this relationship, this study investigated the soil physicochemical properties and microbial functions during remediation in saline-alkali soil by rice cultivation over 2, 4, 6, 8, 11, 12, 20, and 23 years. The results indicated rice cultivation markedly improved soil nutrients, soil nutrient stoichiometry, and soil aggregate stability. Additionally, rice cultivation significantly increased the microbial functions involved in nutrient cycling, such as nitrogen fixation, carbon fixation, methanogenesis, dissimilatory sulfate reduction, and thiosulfate oxidation. However, these nitrogen (N), carbon (C), and sulfur (S) cycle-related functions exhibited a similar “increase-peak-decrease” successional pattern with the years of remediation, reaching optimal levels when rice was continuously grown for 11–16 years. Furthermore, correlation analysis demonstrated that the succession of soil microbial N, C, and S functions during saline-alkali soil restoration closely related to changes in soil properties, particularly the availability of phosphorus (P). Therefore, we propose to prioritize the management of P during saline-alkali soil remediation. In conclusion, this study provides a comprehensive understanding of the microbial N, C, and S functions and soil P in the remediation of saline-alkali soils mediated by rice crop.

Ex situ Generation of Thiazyl Trifluoride (NSF3) as a Gaseous SuFEx Hub**

AbstractSulfur(VI)‐fluoride exchange (SuFEx) chemistry, an all‐encompassing term for substitution events that replace fluoride at an electrophilic sulfur(VI), enables the rapid and flexible assembly of linkages around a SVI core. Although a myriad of nucleophiles and applications works very well with the SuFEx concept, the electrophile design has remained largely SO2‐based. Here, we introduce S≡N‐based fluorosulfur(VI) reagents to the realm of SuFEx chemistry. Thiazyl trifluoride (NSF3) gas is shown to serve as an excellent parent compound and SuFEx hub to efficiently synthesize mono‐ and disubstituted fluorothiazynes in an ex situ generation workflow. Gaseous NSF3 was evolved from commercial reagents in a nearly quantitative fashion at ambient conditions. Moreover, the mono‐substituted thiazynes could be extended further as SuFEx handles and be engaged in the synthesis of unsymmetrically disubstituted thiazynes. These results provide valuable insights into the versatility of these understudied sulfur functionalities paving the way for future applications.

Ex situ Generation of Thiazyl Trifluoride (NSF3 ) as a Gaseous SuFEx Hub.

Sulfur(VI)-fluoride exchange (SuFEx) chemistry, an all-encompassing term for substitution events that replace fluoride at an electrophilic sulfur(VI), enables the rapid and flexible assembly of linkages around a SVI core. Although a myriad of nucleophiles and applications works very well with the SuFEx concept, the electrophile design has remained largely SO2 -based. Here, we introduce S≡N-based fluorosulfur(VI) reagents to the realm of SuFEx chemistry. Thiazyl trifluoride (NSF3 ) gas is shown to serve as an excellent parent compound and SuFEx hub to efficiently synthesize mono- and disubstituted fluorothiazynes in an ex situ generation workflow. Gaseous NSF3 was evolved from commercial reagents in a nearly quantitative fashion at ambient conditions. Moreover, the mono-substituted thiazynes could be extended further as SuFEx handles and be engaged in the synthesis of unsymmetrically disubstituted thiazynes. These results provide valuable insights into the versatility of these understudied sulfur functionalities paving the way for future applications.

Metal‐Free Carbonaceous Catalytic Materials: Biomass Feedstocks for a Greener Future

AbstractMetal‐free catalytic systems (MFCS) have emerged as sustainable and cost‐efficient heterogeneous catalysts, particularly in the case of carbonaceous materials with oxygen, nitrogen, boron, sulfur or phosphorus functionalities. This contribution aims to provide a general overview of the recent advances on the design of such materials, with emphasis on those derived from biomass waste and on the relationship between their structure and their activity. The opportunities of using MFCS in different areas of catalysis, including thermo‐, electro‐, and photo‐catalysis, will be addressed for applications towards the upgrading of renewable feedstocks. This analysis will describe sustainable approaches not only with respect to the nature of catalyst but also for the employment of non‐toxic and sustainable precursors, and for the efficiency of the synthetic protocol and its carbon footprint.

Revisiting the Role of Sulfur Functionality in Regulating the Electron Distribution of Single‐Atomic Fe Sites Toward Enhanced Oxygen Reduction

AbstractIntroducing sulfur functionalities is reported as an efficacious route to regulate the electron distribution of single‐atomic Fe sites for improving the oxygen reduction reaction (ORR) activity, however, it remains controversial about the role of type of sulfur functionalities in enhancing the ORR activity. Herein, this study revisits the role of sulfur functionalities in regulating the electron distribution of single‐atomic Fe sites by the construction of single‐atomic Fe‐N4 sites with sulfur functionalities (FeSNC) using sulfur‐containing molecules with different molecular structures. X‐ray absorption spectroscopy and theoretical calculations confirm that thiophene S and oxidized S both possess the electron‐donating properties for regulating the electronic distribution of Fe‐N4 sites, which is beneficial to weaken the adsorption of the ORR intermediates. As expected, the optimal FeSNC has attractive ORR activity with half‐potential of 0.76 V in 0.5 m H2SO4 and 0.91 V in 0.1 m KOH along with remarkable Zn‐air battery performance. Moreover, the developed synthetic method has also been extended to construct B and P regulated FeNC catalysts.

Covalent Scrambling in Porous Polyarylthioethers through a Stepwise SNAr for Tunable Bandgap and Porosity

AbstractPorous poly(aryl thioether)s offer stability and electronic tunability by robust sulfur‐aryl conjugated architecture, but synthetic access is hindered due to limited control over the nucleophilic nature of sulfides and the air sensitivity of aromatic thiols. Here, we report a simple, one‐pot, inexpensive, regioselective synthesis of highly porous poly(aryl thioether)s through polycondensation of perfluoroaromatic compounds with sodium sulfide. The unprecedented temperature‐dependent para‐directing formation of thioether linkages leads to a stepwise transition of the polymer extension into a network, thereby allowing fine control of the porosity and optical band gaps. The obtained porous organic polymers with ultra‐microporosity (<1 nm) and sulfur as the surface functional groups show size‐dependent separation of organic micropollutants and selective removal of mercury ions from water. Our findings offer easy access to poly(aryl thioether)s with accessible sulfur functionalities and higher complexity, which will help in realizing advanced synthetic designs in applications such as adsorption, (photo)catalysis, and (opto)electronics.

Covalent Scrambling in Porous Polyarylthioethers through a Stepwise SN Ar for Tunable Bandgap and Porosity.

Porous poly(aryl thioether)s offer stability and electronic tunability by robust sulfur-aryl conjugated architecture, but synthetic access is hindered due to limited control over the nucleophilic nature of sulfides and the air sensitivity of aromatic thiols. Here, we report a simple, one-pot, inexpensive, regioselective synthesis of highly porous poly(aryl thioether)s through polycondensation of perfluoroaromatic compounds with sodium sulfide. The unprecedented temperature-dependent para-directing formation of thioether linkages leads to a stepwise transition of the polymer extension into a network, thereby allowing fine control of the porosity and optical band gaps. The obtained porous organic polymers with ultra-microporosity (<1 nm) and sulfur as the surface functional groups show size-dependent separation of organic micropollutants and selective removal of mercury ions from water. Our findings offer easy access to poly(aryl thioether)s with accessible sulfur functionalities and higher complexity, which will help in realizing advanced synthetic designs in applications such as adsorption, (photo)catalysis, and (opto)electronics.

Novel Sulfur‐Containing Carbon Nanotubes with Graphene Nanoflaps for Stretchable Sensing, Joule Heating, and Electro‐Thermal Actuating

AbstractStretchable conductors based on nanopercolation networks have garnered great attention for versatile applications. Carbon nanotubes (CNTs) are well‐suited for creating high‐efficiency nanopercolation networks. However, the weak interfacial shear strength (IFSS) between CNTs and elastomer hardly dissipates the deformation energy and thus deteriorates the conductive network. Herein, a novel sulfur‐containing CNTs attached with abundant graphene nanoflaps using a two‐step sulfidation strategy are developed. The sulfur functionality creates a strong interfacial interaction with the elastomer polymer, while the graphene nanoflaps provide an enhanced, intertwined shear interface with elastomer that is capable of efficiently dissipating the deformation energy. As a result, the optimized nanocomposite significantly improves the IFSS between nanofiller and elastomer, displaying remarkable conductive robustness (ΔR/R0≈1.8 under 200%), superior stretchability (&gt; 450%), and excellent mechanical durability (≈30 000 cycles). Moreover, the nanocomposite demonstrates excellent Joule heating efficiency (≈150 °C in 12 V), stretchable heating conversion (≈200%), and long‐term stability (&gt; 24 h). To illustrate its capabilities, the nanocomposite is used to track human physiological signals and perform electric‐thermal actuating as a set of soft tongs. It is believed that this innovative approach will provide value for the development of wearable/stretchable devices, as well as human‐machine interaction, and bio‐robotics in the future.

One-pot synthesis of self S-doped porous carbon for efficient CO2 adsorption

Considering the rising environmental and efficiency concerns, the development of porous carbon via a surface decoration approach has received great attention for selectively adsorb CO2 from the flue gas. Herein, self-S-doped porous carbon was prepared from petroleum coke with high sulfur content (PHS) utilizing KOH as an activating agent. The effect of the activating temperatures and the KOH/PHS mass ratio on the physical feature and CO2 uptake performance of the as-synthesis porous carbons was fully examined. The optimal sample (PHS-650-3) presents the specific BET surface area and total pore volume of 1278 m2/g and 0.56 cm3/g, respectively. The PHS-650-3 sample displayed the maximum CO2 adsorption capacity of 4.18 and 5.57 mmol g−1 at 25 and 0 °C and 1 bar thanks to its enhanced textural characteristics and high amount of sulfur functionality on the surface. Last but not least, the as-synthesized S-doped porous carbon shows ideal adsorption solution theory (IAST) CO2/N2 selectivity of 21, fast adsorption kinetics, suitable heat of adsorption value and stable uptake capacity upon consecutive adsorption cycles, claiming its readily potential CO2 adsorption applications.

Study on the coordination conduct and kinetic insights within the oxo-vanadate and organic reductive nitrogen and sulfur functionalities during the reduction coupled adsorption processes: Implications in practical applications

Vanadium(V) is arising wastewater contaminant recently. Although bio-reduction of vanadium(V) is effective, the knowledge of electron transfer pathways and coordination nature by cellular organic functionalities is seriously lacking. Herein, the coordination conduct and kinetic modes for the reduction of V(V) by organic nitrogen and sulfur functionalities in working pHs are comprehensively investigated for the first time. The kinetics follow 3 steps; (1) diffusion of V(V) species, (2) reduction of V(V) to V(IV), and (3) adsorption of existing V species. The diffusion of V(V) is controlled by the protonated =NH2+, −SH2+, −CSH+ functional groups and oxo-vanadate speciation. The reduction of V(V) to V(IV) was efficient by −SH than =NH, −NH− , because of the higher oxidation potential of sulfur and which acted as the sole electron donor in the process. The coordination of V(V)/V(IV) species interacted with oxygen, nitrogen and sulfur atoms via parallel orientation and leads to multi-docking or single-ionic interactions, revealing the previously unrecognized track. Hence, the system tested in four types of wastewaters with different pHs and resulted the comprehensive practical applicability of the system. This study proposes a novel tactic to design an efficient V(V) wastewater treatment system by considering its water parameters.

Thiol functionalized activated carbon for gold thiosulfate recovery, an analysis of the interactions between gold and sulfur functions

Cyanide salts are currently used as leaching agents in gold extraction processes despite their toxicity. Thiosulfate is a greener choice, but its employment is constrained by the difficulty at recovering gold thiosulfate from the leachate using activated carbon, which in contrast, works well for gold-cyanide adsorption. Aiming to solve this problem, activated carbon has been covalently functionalized with thiol groups (-SH) through a peptide bond formation with cysteamine, as thiol-carrier molecule. The functionalized carbon accomplishes up to 100% Au recovery (with 2 and 25 ppm Au solution) in 8 h contact and its performance seems independent on the solution's pH. In-depth solid characterization techniques (XPS, TOF-SIMS, FTIR, PXRD, TEM, N₂ physisorption, elemental analysis) have been used to unravel the interactions between Au thiosulfate and thiol functions and two different gold adsorption mechanisms have been demonstrated: under acid conditions, the formation of Au1+- S chains has been proven. Under basic conditions, Au⁰ species have been detected in addition to Au1+- S chains. Elution of the gold loaded samples has been accomplished at a 71% level using Na₂S₂O₃ and NH₄OH as eluents.

Utilization of sulfur function in directed catalytic C-H transformation: site-selective substitution on indole and naphthalene skeletons

Sulfur-containing functional groups, among various coordinating functions, have recently attracted attention as useful directing groups for the direct catalytic C-H transformation of aromatic and heteroaromatic compounds. Herein we briefly summarize our recent work on the site-selective substitution on indole and naphthalene skeletons using thioether directing groups under either Cp*Rh(III) or Cp*Ir(III) catalysis. The thioether groups can readily be removed and transformed to other functional groups. The reactions developed appear to be of importance in pharmaceutical and materials chemistry.

Steering Local Electronic Configuration of Fe–N–C‐Based Coupling Catalysts via Ligand Engineering for Efficient Oxygen Electroreduction

AbstractFe–N–C materials are prospective candidates to displace platinum‐group‐based oxygen reduction reaction (ORR) catalysts, but their application is still impeded by the conundrums of unsatisfactory activity and stability. Herein, a feasible strategy of ligand engineering of the metal‐organic framework is proposed to steer the local electronic configuration of Fe–N–C‐based coupling catalysts by incorporating engineered sulfur functionalities. The obtained catalysts with rich Fe‐N4 sites and FeS nanoparticles are embedded on N/S‐doped carbon (denoted as FeS/FeNSC). In this unique structure, the engineered FeS nanoparticles and oxidized sulfur synergistically induce electron redistribution and modulate electronic configuration of Fe‐N4 sites, contributing to substantially accelerated kinetics and improved activity. Consequently, the optimized FeS/FeNSC catalyst displays outstanding ORR performance with a half‐wave potential of 0.91 V, better four electron pathway selectivity, lower H2O2 yield, and superior long‐term stability. As a proof‐of‐concept, zinc‐air batteries based on FeS/FeNSC deliver high capacity of 807.54 mA h g−1, a remarkable peak power density of 256.06 mW cm−2, and outstanding cycling stability over 600 h at 20 mA cm−2. This study delivers an efficacious approach to manipulate the electronic configuration of Fe–N–C catalysts toward elevated catalytic activity and stability for various energy conversion/storage devices.

Metagenomic Features Characterized with Microbial Iron Oxidoreduction and Mineral Interaction in Southwest Indian Ridge.

The Southwest Indian Ridge (SWIR) is one of the typical representatives of deep-sea ultraslow-spreading ridges, and has increasingly become a hot spot of studying subsurface geological activities and deep-sea mining management. However, the understanding of microbial activities is still limited on active hydrothermal vent chimneys in SWIR. In this study, samples from an active black smoker and a diffuse vent located in the Longqi hydrothermal region were collected for deep metagenomic sequencing, which yielded approximately 290 GB clean data and 295 mid-to-high-quality metagenome-assembled genomes (MAGs). Sulfur oxidation conducted by a variety of Gammaproteobacteria, Alphaproteobacteria, and Campylobacterota was presumed to be the major energy source for chemosynthesis in Longqi hydrothermal vents. Diverse iron-related microorganisms were recovered, including iron-oxidizing Zetaproteobacteria, iron-reducing Deferrisoma, and magnetotactic bacterium. Twenty-two bacterial MAGs from 12 uncultured phyla harbored iron oxidase Cyc2 homologs and enzymes for organic carbon degradation, indicated novel chemolithoheterotrophic iron-oxidizing bacteria that affected iron biogeochemistry in hydrothermal vents. Meanwhile, potential interactions between microbial communities and chimney minerals were emphasized as enriched metabolic potential of siderophore transportation, and extracellular electron transfer functioned by multi-heme proteins was discovered. Composition of chimney minerals probably affected microbial iron metabolic potential, as pyrrhotite might provide more available iron for microbial communities. Collectively, this study provides novel insights into microbial activities and potential mineral-microorganism interactions in hydrothermal vents. IMPORTANCE Microbial activities and interactions with minerals and venting fluid in active hydrothermal vents remain unclear in the ultraslow-spreading SWIR (Southwest Indian Ridge). Understanding about how minerals influence microbial metabolism is currently limited given the obstacles in cultivating microorganisms with sulfur or iron oxidoreduction functions. Here, comprehensive descriptions on microbial composition and metabolic profile on 2 hydrothermal vents in SWIR were obtained based on cultivation-free metagenome sequencing. In particular, autotrophic sulfur oxidation supported by minerals was presumed, emphasizing the role of chimney minerals in supporting chemosynthesis. Presence of novel heterotrophic iron-oxidizing bacteria was also indicated, suggesting overlooked biogeochemical pathways directed by microorganisms that connected sulfide mineral dissolution and organic carbon degradation in hydrothermal vents. Our findings offer novel insights into microbial function and biotic interactions on minerals in ultraslow-spreading ridges.

Insight into the shaping of microbial communities in element sulfur-based denitrification at different temperatures

Nitrate pollution is an important cause of eutrophication and ecological disruption. Recently, element sulfur-based denitrification (ESDeN) has attracted increasing attention because of its non-carbon source dependence, low sludge yield, and cost-effectiveness. Although the denitrification performance of sulfur autotrophic denitrifying bacteria at different temperatures has been widely studied, there are still many unknown factors about the adaptability and the shaping of microbial community. In this study, we comprehensively understood the shaping of ESDeN microbial communities under different temperature conditions. Results revealed that microbial communities cultivated at temperatures ranging from 10 °C to 35 °C could be classified as high-temperature (35 °C), middle-temperature (30, 25 and 20 °C), and low-temperature (15 and 10 °C) communities. Dissolved oxygen in water was an important factor that, in combination with temperature, shaped microbial community structure. According to network analysis, the composition of keystone taxa was different for the three groups of communities. Some bacteria that did not have sulfur compound oxidation function were identified as the “keystone species”. The abundances of carbon, nitrogen, and sulfur metabolism of the three microbial communities were significantly changed, which was reflected in that the high-temperature and middle-temperature communities were dominated by dark oxidation of sulfur compounds and dark sulfide oxidation, while the low-temperature community was dominated by chemoheterotrophy and aerobic chemoheterotrophy. The fact that the number of microorganisms with dark oxidation of sulfur compounds capacity was quite higher than that of microorganisms with dark sulfur oxidation capacity suggested that the sulfur bioavailability at different temperatures, especially low temperature, was the main challenge for the development of efficient ESDeN process. This study provided a biological basis for developing a high-efficiency ESDeN process to cope with temperature changes in different seasons or regions.

Preparation and characterization of cotton/silver nanocomposite materials by surface post-modification with methylthiocarbene

Cotton/silver nanocomposite materials have been intensively investigated owing to their excellent microbial resistance of natural cottons, allowing wide employment in health care products and medical science. In this paper, a one-step modification by carbenes was used for the methylthio functionalization of cottons, and the subsequent coordination of methylthio groups with Ag NPs gave cotton/Ag NPs materials. Application to various substrates including cotton fibers, cotton fabrics, and filter papers demonstrated the method to be effective and universal. Moreover, a bioassay experiment showed excellent antibacterial activity of these materials, which further confirmed the success of the strategy. This would be a pioneer for the carbene modification to introduce sulfur functions onto surfaces and interfaces, as well as the extending development of cotton/Ag NPs materials by typical Ag–S coordination.