Members of the genus Shewanella are known for their versatile electron accepting routes, which allow them to couple decomposition of organic matter to reduction of various terminal electron acceptors for heterotrophic growth in diverse environments. Here, we report autotrophic growth of Shewanella oneidensis MR-1 with photoelectrons provided by illuminated biogenic CdS nanoparticles. This hybrid system enables photosynthetic oscillatory acetate production from CO2 for over five months, far exceeding other inorganic-biological hybrid system that can only sustain for hours or days. Biochemical, electrochemical and transcriptomic analyses reveal that the efficient electron uptake of S. oneidensis MR-1 from illuminated CdS nanoparticles supplies sufficient energy to stimulate the previously overlooked reductive glycine pathway for CO2 fixation. The continuous solar-to-chemical conversion is achieved by photon induced electric recycling in sulfur species. Overall, our findings demonstrate that this mineral-assisted photosynthesis, as a widely existing and unique model of light energy conversion, could support the sustained photoautotrophic growth of non-photosynthetic microorganisms in nutrient-lean environments and mediate the reversal of coupled carbon and sulfur cycling, consequently resulting in previously unknown environmental effects. In addition, the hybrid system provides a sustainable and flexible platform to develop a variety of solar products for carbon neutrality.

Selective CO2-to-CO photoreduction is under intensive research and requires photocatalysts with tuned microstructures to accelerate the reaction kinetics. Here, we report CuInS2 nanosheet arrays with sulfur vacancies (VS) grown on the two-dimensional (2D) support of Ti3C2Tx MXene for CO2-to-CO photoreduction. Our results reveal that the use of Ti3C2Tx induces strong support effect, which causes the hierarchical nanosheet arrays growth of CuInS2 and simultaneously leads to charge transfer from CuInS2 to Ti3C2Tx support, resulting in VS formed in CuInS2. The strong support effect based on Ti3C2Tx is proven to be applicable to prepare a series of different metal indium sulfide arrays with VS. CuInS2 nanosheet arrays with VS supported on Ti3C2Tx benefit the photocatalytic selective reduction of CO2 to CO, manifesting a remarkable over 14.8-fold activity enhancement compared with pure CuInS2. The experimental and computational investigations pinpoint that VS of CuInS2 resulting from the support effect of Ti3C2Tx lowers the barrier of the rate-limiting step of *COOH → *OH + *CO, which is the key to the photoactivity enhancement. This work demonstrates MXene support effects and offers an effective approach to regulate the atomic microstructure of metal sulfides toward enhancing photocatalytic performance.

Inorganic metal sulfides have received extensive investigation as anode materials in lithium-ion batteries (LIBs). However, applications of crystalline organic hybrid metal sulfides as anode materials in LIBs are quite rare. In addition, combining the nanoparticles of crystalline organic hybrid metal sulfides with conductive materials is expected to enhance the electrochemical lithium storage performance. Nevertheless, due to the difficulty of harvesting the nanoparticles of crystalline organic hybrid metal sulfides, this approach has never been tried to date. Herein, nanoparticles of a crystalline organic hybrid cadmium antimony sulfide (1,4-DABH2)Cd2Sb2S6 (DCAS) were prepared by a top-down method, including the procedures of solvothermal synthesis, ball milling, and ultrasonic pulverization. Thereafter, the nanoparticles of DCAS with sizes of ∼500 nm were intercalated into graphene oxide nanosheets through a freeze-drying treatment and a DCAS@GO composite was obtained. Compared with the reported Sb2S3- and CdS-based composites, the DCAS@GO composite exhibited superior electrochemical Li+ ion storage performance, including a high capacity of 1075.6 mAh g-1 at 100 mA g-1 and exceptional rate tolerances (646.8 mAh g-1 at 5000 mA g-1). In addition, DCAS@GO can provide a high capacity of 705.6 mAh g-1 after 500 cycles at 1000 mA g-1. Our research offers a viable approach for preparing the nanoparticles of crystalline organic hybrid metal sulfides and proves that intercalating organic hybrid metal sulfide nanoparticles into GO nanosheets can efficiently boost the electrochemical Li+ ion storage performance.

The design and fabrication of a lithiophilic skeleton are highly important for constructing advanced Li metal anodes. In this work, a new lithiophilic skeleton is reported by planting metal sulfides (e.g., Ni3S2) on vertical graphene (VG) via a facile ultrafast Joule heating (UJH) method, which facilitates the homogeneous distribution of lithiophilic sites on carbon cloth (CC) supported VG substrate with firm bonding. Ni3S2 nanoparticles are homogeneously anchored on the optimized skeleton as CC/VG@Ni3S2, which ensures high conductivity and uniform deposition of Li metal with non-dendrites. By means of systematic electrochemical characterizations, the symmetric cells coupled with CC/VG@Ni3S2 deliver a steady long-term cycle within 14 mV overpotential for 1800 h (900 cycles) at 1 mA cm-2 and 1 mAh cm-2. Meanwhile, the designed CC/VG@Ni3S2-Li||LFP full cell shows notable electrochemical performance with a capacity retention of 92.44% at 0.5 C after 500 cycles and exceptional rate performance. This novel synthesis strategy for metal sulfides on hierarchical carbon-based materials sheds new light on the development of high-performance lithium metal batteries (LMBs).

Metal-organic framework derived materials received a lot of attention due to their significant benefits in photocatalytic reactions. In this work, a Z-scheme ZnIn2S4/Bi2S3 hierarchical heterojunction is first developed by a one-pot method using CAU-17 as a template. The specific preparation method endows an intimate interface contact between these two monomers, and CAU-17-derived Bi2S3 possesses a high surface area and porosity, resulting in an efficient charge separation and O2 capture. Thus, for photocatalytic H2O2 production from the O2 reduction reaction, the ZnIn2S4/Bi2S3 heterojunction can achieve an H2O2 yield of 995 µmol L-1 in pure water and ambient air under visible light, 4.5 and 4 times that of ZnIn2S4 and Bi2S3, respectively. In addition, in tetracycline solution, ZnIn2S4/Bi2S3 can degrade tetracycline with a degradation rate of 95% by photocatalysis, and at the same time, a final H2O2 production yield of 1223 µmol L-1 is reached. Similarly, high yields of H2O2 are also obtained from wastewater containing o-nitrophenol, acid golden yellow, or acid red, and these pollutants are effectively degraded. This work reveals the potential of metal-organic framework-derived materials in photocatalysis, as well as provides insights into H2O2 green synthesis and wastewater treatment.

Metal sulfides in waste rocks and tailings are susceptible to serious soil and water contamination due to the generation of acid mine drainage (AMD) during stockpiling. The hydrometallurgical process is one of the most essential heavy metal remediation technologies through harmless disposal and resource utilization of the waste sulfides. However, atmospheric hydrometallurgy of sulfides still faces great challenges due to low leaching efficiency and high cost. In this work, we proposed a cooperative leaching system (Fe2(SO4)3-O3) and investigated the oxidative dissolution process of sphalerite (ZnS). Under the optimal conditions, the extracted zinc reached 97.8%. Reactive oxygen species (ROS) (·OH, 1O2 and ·O2-) were identified in the radical quenching experiments. The dissolution of sphalerite did not show passivation due to the ozone\'s capability to oxidize the sulfur in sphalerite to sulfate. In addition, stirring rate, O3 inlet concentration, and Fe2(SO4)3 concentration had a significant effect on the dissolution of sphalerite. Meanwhile, the apparent activation energy was 24.11 kJ/mol based on kinetic fitting, which indicated that the controlling step of the reaction was mainly a diffusion process. This work demonstrated the cooperative effect of sphalerite leaching in the O3-Fe2(SO4)3 system and provided a theoretical reference for efficient and atmospheric dissolution of sphalerite.

Metal-organic framework materials can be converted into carbon-based nanoporous materials by pyrolysis, which have a wide range of applications in energy storage. Here, we design special interface engineering to combine the carbon skeleton and nitrogen-doped carbon nanotubes (CNTs) with the transition metal compounds (TMCs) well, which mitigates the bulk effect of the TMCs and improves the conductivity of the electrodes. Zeolitic imidazolate framework-67 is used as a precursor to form a carbon skeleton and a large number of nitrogen-doped CNTs by pyrolysis followed by the in situ formation of Co3O4 and CoS2, and finally, Co3O4@CNTs and CoS2@CNTs are synthesized. The obtained anode electrodes exhibit a long cycle life and high-rate properties. In lithium-ion batteries (LIBs), Co3O4@CNTs have a high capacity of 581 mAh g-1 at a high current of 5 A g-1, and their reversible capacity is still 1037.6 mAh g-1 after 200 cycles at 1 A g-1. In sodium-ion batteries (SIBs), CoS2@CNTs have a capacity of 859.9 mAh g-1 at 0.1 A g-1 and can be retained at 801.2 mAh g-1 after 50 cycles. The unique interface engineering and excellent electrochemical properties make them ideal anode materials for high-rate, long-life LIBs and SIBs.

The means of structural hybridization such as heterojunction construction and carbon-coating engineering for facilitating charge transfer and electron transport are considered viable strategies to address the challenges associated with the low rate capability and poor cycling stability of sulfide-based anodes in potassium-ion batteries (PIBs). Motivated by these concepts, we have successfully prepared a hydrangea-like bimetallic sulfide heterostructure encapsulated in nitrogen-doped carbon (FMS@NC) using a simple solvothermal method, followed by poly-dopamine wrapping and a one-step sulfidation/carbonization process. When served as an anode for PIBs, this FMS@NC demonstrates a high specific capacity (585 mAh g-1 at 0.05 A/g) and long cycling stability. Synergetic effects of mitigated volume expansions and enhanced conductivity that are responsbile for such high performance have been verified to originate from the heterostructured sulfides and the N-doped carbon matrix. Meanwhile, comprehensive characterization reveals existence of an intercalation-conversion hybrid K-ion storage mechanism in this material. Impressively, a K-ion capacitor with the FMS@NC anode and a commercial activated carbon cathode exhibits a superior energy density of up to 192 Wh kg-1, a high power density, and outstanding cycling stability. This study provides constructive guidance for designing high-performance and durable potassium-ion storage anodes for next-generation energy storage devices.

The reactive oxygen species (ROS) produced through the Fenton reaction, induces lipid peroxide (LPO), causing cellular structural damage and ultimately triggering ferroptosis. However, the generation of ROS in the tumor microenvironment (TME) is limited by the catalytic efficiency of the Fenton reaction. Herein, a novel hollow mesoporous silica nanoparticle (HMSN) combined with multi-metal sulfide-doped mesoporous silica nanocatalyzers (NCs) was developed, namely MxSy-HMSN NCs (M represents Cu Mn and Fe, S denotes sulfur). The MxSy-HMSN can dramatically enhanced the ferroptosis by: (1) facilitating the conversion of H2O2 to ·OH through Fenton or Fenton-like reactions through co-catalysis; (2) weakening ROS scavenging systems by depleting the over expressed glutathione (GSH) in TME; (3) providing exceptional photothermal therapy to augment ferroptosis. The MxSy-HMSN can also act as smart cargos for anticancer drug-doxorubicin (DOX). The release of DOX is responsive to GSH/pH/Near-infrared Light (NIR) irradiation at the tumor lesion, significantly improving therapeutic outcomes while minimizing side effects. Additionally, the MxSy-HMSN has demonstrated excellent magnetic resonance imaging (MRI) potential. This smart MxSy-HMSN offer a synergetic approach combining ferroptosis with chemo-photothermal therapy and magnetic resonance imaging (MRI) diagnose, which could be an informative guideline for the design of future NCs.

Metal sulfides are highly promising anode materials for sodium-ion batteries due to their high theoretical capacity and ease of designing morphology and structure. In this study, a metal-organic framework (ZIF-8/67 dodecahedron) was used as a precursor due to its large specific surface area, adjustable pore structure, morphology, composition, and multiple active sites in electrochemical reactions. The ZIF-8/67/GO was synthesized using a water bath method by introducing graphene; the dispersibility of ZIF-8/67 was improved, the conductivity increased, and the volume expansion phenomenon that occurs during the electrochemical deintercalation of sodium was prevented. Furthermore, vulcanization was carried out to obtain ZnS/CoS@C/rGO composite materials, which were tested for their electrochemical properties. The results showed that the ZnS/CoS@C/rGO composite was successfully synthesized, with dodecahedrons dispersed in large graphene layers. It maintained a capacity of 414.8 mAh g-1 after cycling at a current density of 200 mA g-1 for 70 times, exhibiting stable rate performance with a reversible capacity of 308.0 mAh g-1 at a high current of 2 A g-1. The excellent rate performance of the composite is attributed to its partial pseudocapacitive contribution. The calculation of the diffusion coefficient of Na+ indicates that the rapid sodium ion migration rate of this composite material is also one of the reasons for its excellent performance. This study highlights the broad application prospects of metal-organic framework-derived metal sulfides as anode materials for sodium-ion batteries.