In supported metal catalysts, the supports would strongly interact with the metal components instead of just acting as a carrier, which greatly affects both of their synthesis and catalytic activity, ...selectivity, and stability. Carbon is considered as very important but inert support and thus hard to induce strong metal‐support interaction (SMSI). This mini‐review highlights that sulfur—a documented poison reagent for metal catalysts—when doped in a carbon supports can induce diverse SMSI phenomenon, including electronic metal‐support interaction (EMSI), classic SMSI, and reactive metal‐support interaction (RMSI). These SMSI between metal and sulfur‐doped carbon (S−C) supports enables the catalysts with extraordinary resistance to sintering at high temperatures of up to 1100 °C, which allows the general synthesis of single‐atom, alloy cluster, and intermetallic compound catalysts with high dispersion and metal loading for a variety of applications.
This mini‐review highlights that sulfur—a documented poison reagent for metal catalysts—when doped in a carbon supports can induce diverse SMSI phenomena, including electronic metal‐support interaction (EMSI), classic SMSI, and reactive metal‐support interaction (RMSI). These SMSI phenomena made it possible to synthesize a variety of catalysts with enhanced performance.
Atomically ordered intermetallic nanoparticles are promising for catalytic applications but are difficult to produce because the high-temperature annealing required for atom ordering inevitably ...accelerates metal sintering that leads to larger crystallites. We prepared platinum intermetallics with an average particle size of <5 nanometers on porous sulfur-doped carbon supports, on which the strong interaction between platinum and sulfur suppresses metal sintering up to 1000°C. We synthesized intermetallic libraries of small nanoparticles consisting of 46 combinations of platinum with 16 other metal elements and used them to study the dependence of electrocatalytic oxygen-reduction reaction activity on alloy composition and platinum skin strain. The intermetallic libraries are highly mass efficient in proton-exchange-membrane fuel cells and could achieve high activities of 1.3 to 1.8 amperes per milligram of platinum at 0.9 volts.
Metal-support interaction is of great significance for catalysis as it can induce charge transfer between metal and support, tame electronic structure of supported metals, impact adsorption energy of ...reaction intermediates, and eventually change the catalytic performance. Here, we report the metal size-dependent charge transfer reversal, that is, electrons transfer from platinum single atoms to sulfur-doped carbons and the carbon supports conversely donate electrons to Pt when their size is expanded to ~1.5 nm cluster. The electron-enriched Pt nanoclusters are far more active than electron-deficient Pt single atoms for catalyzing hydrogen evolution reaction, exhibiting only 11 mV overpotential at 10 mA cm
and a high mass activity of 26.1 A mg
at 20 mV, which is 38 times greater than that of commercial Pt/C. Our work manifests that the manipulation of metal size-dependent charge transfer between metal and support opens new avenues for developing high-active catalysts.
Lithium (Li) metal has been considered as an important substitute for the graphite anode to further boost the energy density of Li‐ion batteries. However, Li dendrite growth during Li ...plating/stripping causes safety concern and poor lifespan of Li metal batteries (LMB). Herein, fluoroethylene carbonate (FEC) additives are used to form a LiF‐rich solid electrolyte interphase (SEI). The FEC‐induced SEI layer is compact and stable, and thus beneficial to obtain a uniform morphology of Li deposits. This uniform and dendrite‐free morphology renders a significantly improved Coulombic efficiency of 98% within 100 cycles in a Li | Cu half‐cell. When the FEC‐protected Li metal anode matches a high‐loading LiNi0.5Co0.2Mn0.3O2 (NMC) cathode (12 mg cm−2), a high initial capacity of 154 mAh g−1 (1.9 mAh cm−2) at 180.0 mA g−1 is obtained. This LMB with conversion‐type Li metal anode and intercalation‐type NMC cathode affords an emerging energy storage system to probe the energy chemistry of Li metal protection and demonstrates the material engineering of batteries with very high energy density.
Fluoroethylene carbonate (FEC) additive is used to form a LiF‐rich solid electrolyte interphase (SEI). The FEC‐induced SEI layer is compact and stable, and therefore beneficial to obtain a uniform morphology of Li deposits. When the FEC‐protected Li metal anode matches a high‐loading oxide cathode, a high initial capacity and stable cycling are achieved.
Safe and rechargeable lithium metal batteries have been difficult to achieve because of the formation of lithium dendrites. Herein an emerging electrolyte based on a simple solvation strategy is ...proposed for highly stable lithium metal anodes in both coin and pouch cells. Fluoroethylene carbonate (FEC) and lithium nitrate (LiNO3) were concurrently introduced into an electrolyte, thus altering the solvation sheath of lithium ions, and forming a uniform solid electrolyte interphase (SEI), with an abundance of LiF and LiNxOy on a working lithium metal anode with dendrite‐free lithium deposition. Ultrahigh Coulombic efficiency (99.96 %) and long lifespans (1000 cycles) were achieved when the FEC/LiNO3 electrolyte was applied in working batteries. The solvation chemistry of electrolyte was further explored by molecular dynamics simulations and first‐principles calculations. This work provides insight into understanding the critical role of the solvation of lithium ions in forming the SEI and delivering an effective route to optimize electrolytes for safe lithium metal batteries.
Not dead ′Li′: Fluoroethylene carbonate (FEC) and lithium nitrate (LiNO3) were concurrently introduced into an electrolyte, thus altering the solvation sheath of lithium ions and forming a uniform solid electrolyte interphase (SEI). An abundance of LiF and LiNxOy is formed on the working lithium metal anode and contributes to dendrite‐free lithium deposition.
Up to 10–20% of patients with coronavirus disease 2019 (COVID‐19) develop a severe pulmonary disease due to immune dysfunction and cytokine dysregulation. However, the extracellular proteomic ...characteristics in respiratory tract of these critical COVID‐19 patients still remain to be investigated. In the present study, we performed a quantitative proteomic analysis of the bronchoalveolar lavage fluid (BALF) from patients with critical COVID‐19 and from non‐COVID‐19 controls. Our study identified 358 differentially expressed BALF proteins (P < 0.05), among which 41 were significantly changed after using the Benjamini–Hochberg correction (q < 0.05). The up‐regulated signaling was found to be mainly involved in inflammatory signaling and response to oxidative stress. A series of increased extracellular factors including Tenascin‐C (TNC), Mucin‐1 (KL‐6 or MUC1), Lipocalin‐2 (LCN2), periostin (POSTN), Chitinase 3‐like 1 (CHI3L1 or YKL40), and S100A12, and the antigens including lymphocyte antigen 6D/E48 antigen (LY6D), CD9 antigen, CD177 antigen, and prostate stem cell antigen (PSCA) were identified, among which the proinflammatory factors TNC and KL‐6 were further validated in serum of another thirty‐nine COVID‐19 patients and healthy controls, showing high potentials of being biomarkers or therapeutic candidates for COVID‐19. This BALF proteome associated with COVID‐19 would also be a valuable resource for researches on anti‐inflammatory medication and understanding the molecular mechanisms of host response.
Database
Proteomic raw data are available in ProteomeXchange (http://proteomecentral.proteomexchange.org) under the accession number PXD022085, and in iProX (www.iprox.org) under the accession number IPX0002429000.
Here, we use quantitative proteomics to analyze alterations in the bronchoalveolar lavage fluid of patients with critical COVID‐19 relative to non‐COVID‐19 controls. We find that up‐regulated signaling mainly involves inflammatory signaling and response to oxidative stress and identify increases in extracellular factors and in their related interaction networks. The bronchoalveolar proteome of COVID‐19 patients provides a valuable resource for future research.
High‐energy‐density Li metal batteries suffer from a short lifespan under practical conditions, such as limited lithium, high loading cathode, and lean electrolytes, owing to the absence of ...appropriate solid electrolyte interphase (SEI). Herein, a sustainable SEI was designed rationally by combining fluorinated co‐solvents with sustained‐release additives for practical challenges. The intrinsic uniformity of SEI and the constant supplements of building blocks of SEI jointly afford to sustainable SEI. Specific spatial distributions and abundant heterogeneous grain boundaries of LiF, LiNxOy, and Li2O effectively regulate uniformity of Li deposition. In a Li metal battery with an ultrathin Li anode (33 μm), a high‐loading LiNi0.5Co0.2Mn0.3O2 cathode (4.4 mAh cm−2), and lean electrolytes (6.1 g Ah−1), 83 % of initial capacity retains after 150 cycles. A pouch cell (3.5 Ah) demonstrated a specific energy of 340 Wh kg−1 for 60 cycles with lean electrolytes (2.3 g Ah−1).
A solid electrolyte interphase (SEI) was proposed for practical high‐energy‐density Li batteries. The intrinsic uniformity and the constant supplements of building blocks of SEI jointly afford a sustainable SEI. A pouch cell with a specific energy of 340 Wh kg−1 underwent 60 cycles with a retention of 90 %.
Supported platinum intermetallic compound catalysts have attracted considerable attention owing to their remarkable activities and durability for the oxygen reduction reaction in proton-exchange ...membrane fuel cells. However, the synthesis of highly ordered intermetallic compound catalysts remains a challenge owing to the limited understanding of their formation mechanism under high-temperature conditions. In this study, we perform in-situ high-temperature X-ray diffraction studies to investigate the structural evolution in the impregnation synthesis of carbon-supported intermetallic catalysts. We identify the phase-transition-temperature (T
)-dependent evolution process that involve concurrent (for alloys with high T
) or separate (for alloys with low T
) alloying/ordering stages. Accordingly, we realize the synthesis of highly ordered intermetallic catalysts by adopting a separate annealing protocol with a high-temperature alloying stage and a low-temperature ordering stage, which display a high mass activity of 0.96 A mg
at 0.9 V in H
-O
fuel cells and a remarkable durability.
Lithium (Li) metal is the most promising electrode for next‐generation rechargeable batteries. However, the challenges induced by Li dendrites on a working Li metal anode hinder the practical ...applications of Li metal batteries. Herein, nitrogen (N) doped graphene was adopted as the Li plating matrix to regulate Li metal nucleation and suppress dendrite growth. The N‐containing functional groups, such as pyridinic and pyrrolic nitrogen in the N‐doped graphene, are lithiophilic, which guide the metallic Li nucleation causing the metal to distribute uniformly on the anode surface. As a result, the N‐doped graphene modified Li metal anode exhibits a dendrite‐free morphology during repeated Li plating and demonstrates a high Coulombic efficiency of 98 % for near 200 cycles.
The matrix: Nitrogen‐doped graphene is used as the Li plating matrix to regulate Li metal nucleation and suppress dendrite growth. The N‐containing functional groups in the N‐doped graphene are lithiophilic, which guide the Li nucleation and give a uniform distribution of Li on the anode surface. The dendrite‐free lithium‐metal anodes exhibit an impressive electrochemical performance.
The outstanding efficiency of Fe‐based metallic glass powders in degrading organic water contaminants is reported. While the glassy alloy contains 24% chemically inactive metalloid elements, the ...powders are capable to completely decompose the C32H20N6Na4O14S4 azo dye in aqueous solution in short time, about 200 times faster than the conventional Fe powders. The metastable thermodynamic nature and the particle surface topography are the major factors controlling the chemical performance of the metallic glass. Our findings may open a new opportunity for functional applications of metallic glasses.
Fe‐based metallic glass powders show outstanding efficiency in degrading organic contaminants due to their far‐from‐equilibrium thermodynamic nature. The –N=N– bond of the dye can be completely decomposed in a short time. Higher degradation efficiency can be achieved by tailoring the particle morphology. The findings are expected to open new areas for the applications of metallic glasses.
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