Surface reconstruction of pyrite-type transition metal sulfides during oxygen evolution reaction.

Reconstruction universally occurs over non-layered transition metal sulfides (TMSs) during oxygen evolution reaction (OER), leading to the formation of active species metal (oxy)hydroxide and thus significantly influences the OER performance. However, the reconstruction process and underlying mechanism quantitatively remain largely unexplored. Herein, we proposed an electrochemical reaction mechanism, namely sulfide oxidation reaction (SOR), to elucidate the reconstruction process of pyrite-type TMSs. Based on this mechanism, we evaluated the reconstruction capability of NiS2 doped with transition metals V, Cr, Mn, Fe, Co, Cu, Mo, Ru, Rh, and Ir within different doped systems. Two key descriptors were thus proposed to describe the reconstruction abilities of TMSs: USOR (the theoretical electric potential of SOR) and ΔU (the difference between the theoretical electric potential of SOR and OER), representing the initiation electric potential of reconstruction and the intrinsic reconstruction abilities of TMSs, respectively. Our finding shows that a lower USOR readily initiate reconstruction at a lower potential and a larger ΔU indicating a poorer reconstruction ability of the catalyst during OER. Furthermore, Fe-doped CoS2 was used to validate the rationality of our proposed descriptors, being consistent with the experiment findings. Our work provides a new perspective on understanding the reconstruction mechanism and quantifying the reconstruction of TMSs.

Favoring CO Intermediate Stabilization and Protonation by Crown Ether for CO2 Electromethanation in Acidic Media.

The large-scale deployment of CO2 electroreduction is hampered by deficient carbon utilization in neutral and alkaline electrolytes due to CO2 loss into (bi)carbonates. Switching to acidic media mitigates carbonation, but suffers from low product selectivity because of hydrogen evolution. Here we report a crown ether decoration strategy on a Cu catalyst to enhance carbon utilization and selectivity of CO2 methanation under acidic conditions. Macrocyclic 18-Crown-6 is found to enrich potassium cations near the Cu electrode surface, simultaneously enhancing the interfacial electric field to stabilize the *CO intermediate and accelerate water dissociation to boost *CO protonation. Remarkably, the mixture of 18-Crown-6 and Cu nanoparticles affords a CH4 Faradaic efficiency of 51.2 % and a single pass carbon efficiency of 43.0 % toward CO2 electroreduction in electrolyte with pH=2. This study provides a facile strategy to promote CH4 selectivity and carbon utilization by modifying Cu catalysts with supramolecules.

Directional electronic tuning of Ni nanoparticles by interfacial oxygen bridging of support for catalyzing alkaline hydrogen oxidation.

Metallic nickel (Ni) is a promising candidate to substitute Pt-based catalysts for hydrogen oxidation reaction (HOR), but huge challenges still exist in precise modulation of the electronic structure to boost the electrocatalytic performances. Herein, we present the use of single-layer Ti3C2Tx MXene to deliberately tailor the electronic structure of Ni nanoparticles via interfacial oxygen bridges, which affords Ni/Ti3C2Tx electrocatalyst with exceptional performances for HOR in an alkaline medium. Remarkably, it shows a high kinetic current of 16.39 mA cmdisk-2 at the overpotential of 50 mV for HOR [78 and 2.7 times higher than that of metallic Ni and Pt/C (20%), respectively], also with good durability and CO antipoisoning ability (1,000 ppm) that are not available for conventional Pt/C (20%) catalyst. The ultrahigh conductivity of single-layer Ti3C2Tx provides fast transmission of electrons for Ni nanoparticles, of which the uniform and small sizes endow them with high-density active sites. Further, the terminated -O/-OH functional groups on Ti3C2Tx directionally capture electrons from Ni nanoparticles via interfacial Ni-O bridges, leading to obvious electronic polarization. This could enhance the Nids-O2p interaction and weaken Nids-H1s interaction of Ni sites in Ni/Ti3C2Txenabling a suitable H-/OH-binding energy and thus enhancing the HOR activity.

The influence of COVID-19 pandemic on PM2.5 air quality in Northern Taiwan from Q1 2020 to Q2 2021.

The study aimed to investigate the PM2.5 variations in different periods of COVID-19 control measures in Northern Taiwan from Quarter 1 (Q1) 2020 to Quarter 2 (Q2) 2021. PM2.5 sources were classified based on long-range transport (LRT) or local pollution (LP) in three study periods: one China lockdown (P1), and two restrictions in Taiwan (P2 and P3). During P1 the average PM2.5 concentrations from LRT (LRT-PM2.5-P1) were higher at Fuguei background station by 27.9% and in the range of 4.9-24.3% at other inland stations compared to before P1. The PM2.5 from LRT/LP mix or pure LP (Mix/LP-PM2.5-P1) was also higher by 14.2-39.9%. This increase was due to higher secondary particle formation represented by the increase in secondary ions (SI) and organic matter in PM2.5-P1 with the largest proportion of 42.17% in PM2.5 from positive matrix factorization (PMF) analysis. A similar increasing trend of Mix/LP-PM2.5 was found in P2 when China was still locked down and Taiwan was under an early control period but the rapidly increasing infected cases were confirmed. The shift of transportation patterns from public to private to avoid virus infection explicated the high correlation of the increasing infected cases with the increasing PM2.5. In contrast, the decreasing trend of LP-PM2.5-P3 was observed in P3 with the PM2.5 biases of ∼45% at all the stations when China was not locked down but Taiwan implemented a semi-lockdown. The contribution of gasoline vehicle sources in PM2.5 was reduced from 20.3% before P3 to 10% in P3 by chemical signatures and source identification using PMF implying the strong impact of strict control measures on vehicle emissions. In summary, PM2.5 concentrations in Northern Taiwan were either increased (P1 and P2) or decreased (P3) during the COVID-19 pandemic depending on control measures, source patterns and meteorological conditions.

Realizing High Capacity and Zero Strain in Layered Oxide Cathodes via Lithium Dual-Site Substitution for Sodium-Ion Batteries.

Sodium-ion batteries have garnered unprecedented attention as an electrochemical energy storage technology, but it remains challenging to design high-energy-density cathode materials with low structural strain during the dynamic (de)sodiation processes. Herein, we report a P2-layered lithium dual-site-substituted Na0.7Li0.03[Mg0.15Li0.07Mn0.75]O2 (NMLMO) cathode material, in which Li ions occupy both transition-metal (TM) and alkali-metal (AM) sites. The combination of theoretical calculations and experimental characterizations reveals that LiTM creates Na-O-Li electronic configurations to boost the capacity derived from the oxygen anionic redox, while LiAM serves as LiO6 prismatic pillars to stabilize the layered structure through suppressing the detrimental phase transitions. As a result, NMLMO delivers a high specific capacity of 266 mAh g-1 and simultaneously exhibits the nearly zero-strain characteristic within a wide voltage range of 1.5-4.6 V. Our findings highlight the effective way of dual-site substitution to break the capacity-stability trade-off in cathode materials for advanced rechargeable batteries.

Hollow Hierarchical Cu2 O-Derived Electrocatalysts Steering CO2 Reduction to Multi-Carbon Chemicals at Low Overpotentials.

The electrochemical reduction of carbon dioxide into multi-carbon products (C2+ ) using renewably generated electricity provides a promising pathway for energy and environmental sustainability. Various oxide-derived copper (OD-Cu) catalysts have been showcased, but still require high overpotential to drive C2+ production owing to sluggish carbon-carbon bond formation and low CO intermediate (*CO) coverage. Here, the dilemma is circumvented by elaborately devising the OD-Cu morphology. First, computational studies propose a hollow and hierarchical OD-Cu microstructure that can generate a core-shell microenvironment to inhibit CO evolution and accelerate *CO dimerization via intermediate confinement and electric field enhancement, thereby boosting C2+ generation. Experimentally, the designed nanoarchitectures are synthesized through a heteroseed-induced approach followed by electrochemical activation. In situ spectroscopic studies further elaborate correlation between *CO dimerization and designed architectures. Remarkably, the hierarchical OD-Cu manifests morphology-dependent selectivity of CO2 reduction, giving a C2+ Faradaic efficiency of 75.6% at a considerably positive potential of -0.55 V versus reversible hydrogen electrode.

Dual-Function Presodiation with Sodium Diphenyl Ketone towards Ultra-stable Hard Carbon Anodes for Sodium-Ion Batteries.

Hard carbon (HC) is a promising anode material for sodium-ion batteries, yet still suffers from low initial Coulombic efficiency (ICE) and unstable solid electrolyte interphase (SEI). Herein, sodium diphenyl ketone (Na-DK) is applied to realize dual-function presodiation for HC anodes. It compensates the irreversible Na uptake at the oxygen-containing functional groups and reacts with carbon defects of five/seven-membered rings for quasi-metallic sodium in HC. The as-formed sodium induces robust NaF-rich SEI on HC in 1.0 M NaPF6 in diglyme, favoring the interfacial reaction kinetics and stable Na+ insertion and extraction. This renders the presodiated HC (pHC) with high ICE of ≈100 % and capacity retention of 82.4 % after 6800 cycles. It is demonstrated to couple with Na3 V2 (PO4 )3 cathodes in full cells to show high capacity retention of ≈100 % after 700 cycles. This work provides in-depth understanding of chemical presodiation and a new strategy for highly stable sodium-ion batteries.

Non-flammable, dilute, and hydrous organic electrolytes for reversible Zn batteries.

Rechargeable Zn batteries hold great practicability for cost-effective sustainable energy storage but suffer from irreversibility of the Zn anode in aqueous electrolytes due to parasitic H2 evolution, corrosion, and dendrite growth. Herein, we report a non-flammable, dilute, and hydrous organic electrolyte by dissolving low-cost hydrated Zn(ClO4)2·6H2O in trimethyl phosphate (TMP), which homogenizes plating/stripping and enables in situ formation of a Zn3(PO4)2-ZnCl2-rich interphase to stabilize the Zn anode. A dilute 0.5 m Zn(ClO4)2·6H2O/TMP electrolyte featuring a H2O-poor Zn2+-solvation sheath and low water activity enables significantly enhanced Zn reversibility and a wider electrochemical window than the concentrated counterpart. In this formulated electrolyte, the Zn anode exhibits a high efficiency of 99.5% over 500 cycles, long-term cycling for 1200 h (5 mA h cm-2 at 5 mA cm-2) and stable operation at 50 °C. The results would guide the design of hydrous organic electrolytes for practical rechargeable batteries employing metallic electrode materials.

Clinical Performance of Rapid Antigen Tests for the Detection of SARS-CoV-2 Infection in the Emergency Department and Community: A Retrospective Study.

Background: Rapid antigen tests for severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) detection have been authorized for emergency use (EUA); however, the performance has not been fully evaluated in clinical contexts. This study aimed to provide evidence regarding the diagnostic performance of SARS-CoV-2 rapid antigen tests compared with the real-time reverse transcription-polymerase chain reaction (RT-PCR) test in the emergency department (ED) and community. Methods: Patients who underwent SARS-CoV-2 rapid antigen tests using the VTRUST COVID-19 Antigen Rapid Test (TD-4531) and real-time RT-PCR on the same day in the ED or community from May 24, 2021, to June 24, 2021, were examined. Results: Paired nasopharyngeal swabs were collected from 4022 suspected COVID-19 patients: 800 in the ED and 3222 in the community. Overall, 62 (1.54%) tested positive, 13 tested indeterminate, and 3947 tested negative by real-time RT-PCR. The sensitivity and specificity of the antigen test were 51.61% and 99.44% (overall), 62.50% and 99.61% (ED), and 31.82% and 99.40% (community), respectively. There were 30 false negatives and 22 false positives. Among the false negatives, 16.67% had a cycle threshold (Ct) value of <25. Conclusion: The VTRUST COVID-19 Antigen Rapid Test showed comparable specificity as real-time RT-PCR for the ED and community, but the sensitivity was relatively low, especially when the Ct value was >25. This test can be useful for the rapid identification of infected subjects in an epidemic situation.

Tuning Interphase Chemistry to Stabilize High-Voltage LiCoO2 Cathode Material via Spinel Coating.

Cathode electrolyte interphases (CEIs) are critical to the cycling stability of high-voltage cathodes for batteries, yet their formation mechanism and properties remain elusive. Here we report that the compositions of CEIs are largely controlled by abundant species in the inner Helmholtz layer (IHL) and can be tuned from material aspects. The IHL of LiCoO2 (LCO) was found to alter after charging, with a solvent-rich environment that results in fragile organic-rich CEIs. By passivated spinel Li4 Mn5 O12 coating, we achieve an anion-rich IHL after charging, thus enabling robust LiF-rich CEIs. In situ microscopy reveals that LiF-rich CEIs maintain mechanical integrity at 500 °C, in sharp contrast to organic-rich CEIs which undergo severe expansion and subsequent voids/cracks in the cathode. As a result, the spinel-coated LCO exhibits a high specific capacity of 194 mAh g-1 at 0.05 C and a capacity retention of 83 % after 300 cycles at 0.5 C. Our work sheds new light on modulating CEIs for advanced lithium-ion batteries.

Boosting the Kinetics and Stability of Zn Anodes in Aqueous Electrolytes with Supramolecular Cyclodextrin Additives.

The hydrophobic internal cavity and hydrophilic external surface of cyclodextrins (CDs) render promising electrochemical applications. Here, we report a comparative and mechanistic study on the use of CD molecules (α-, ß-, and γ-CD) as electrolyte additives for rechargeable Zn batteries. The addition of α-CD in aqueous ZnSO4 solution reduces nucleation overpotential and activation energy of Zn plating and suppresses H2 generation. Computational, spectroscopic, and electrochemical studies reveal that α-CD preferentially adsorbs in parallel on the Zn surface via secondary hydroxyl groups, suppressing water-induced side reactions of hydrogen evolution and hydroxide sulfate formation. Additionally, the hydrophilic exterior surface of α-CD with intense electron density simultaneously facilitates Zn2+ deposition and alleviates Zn dendrite formation. A formulated 3 M ZnSO4 + 10 mM α-CD electrolyte enables homogenous Zn plating/stripping (average Coulombic efficiency ∼ 99.90%) at 1 mA cm-2 in Zn|Cu cells and a considerable capacity retention of 84.20% after 800 cycles in Zn|V2O5 full batteries. This study provides insight into the use of supramolecular macrocycles to modulate and enhance the interface stability and kinetics of metallic anodes for aqueous battery chemistry.

Galvanic-Cell Deposition Enables the Exposure of Bismuth Grain Boundary for Efficient Electroreduction of Carbon Dioxide.

Metallic bismuth (Bi) holds great promise in efficient conversion of carbon dioxide (CO2 ) into formate, yet the complicated synthetic routes and unobtrusive performance hinder the practical application. Herein, a facile galvanic-cell deposition method is proposed for the rapid and one-step synthesis of Bi nanodendrites. Compared to the traditional deposition method, it is found that the special galvanic-cell configuration can promote the exposure of low-angle grain boundaries. X-ray absorption spectroscopy, in situ characterizations and theoretical calculations indicate the electronical structures can be greatly tailored by the grain boundaries, which can facilitate the CO2 adsorption and intermediate formation. Consequently, the grain boundary-enriched Bi nanodendrites exhibit a high selectivity toward formate with an impressively high production rate of 557.2 µmol h-1 cm-2 at -0.94 V versus reversible hydrogen electrode, which outperforms most of the state-of-the-art Bi-based electrocatalysts with longer synthesis time. This work provides a straightforward method for rapidly fabricating active Bi electrocatalysts, and explicitly reveals the critical effect of grain boundary in Bi nanostructures on CO2 reduction.

Building Homogenous Li2 TiO3 Coating Layer on Primary Particles to Stabilize Li-Rich Mn-Based Cathode Materials.

Li-rich Mn-based oxides (LRMOs) are promising cathode materials for next-generation lithium-ion batteries (LIBs) with high specific energy (≈900 Wh kg-1 ) because of anionic redox contribution. However, LRMOs suffer from issues such as irreversible release of lattice oxygen, transition metal (TM) dissolution, and parasitic cathode-electrolyte reactions. Herein, a facile, scalable route to build homogenous and ultrathin Li2 TiO3 (LTO) coating layer on the primary particles of LRMO through molten salt (LiCl) assisted solid-liquid reaction between TiO2 and Li1.08 Mn0.54 Co0.13 Ni0.13 O2 is reported. The prepared LTO-coated Li1.08 Mn0.54 Co0.13 Ni0.13 O2 (LTO@LRMO) exhibits 99.7% capacity retention and 95.3% voltage retention over 125 cycles at 0.2 C, significantly outperforming uncoated LRMO. Combined characterizations of differential electrochemical mass spectrometry, in situ X-ray diffraction, and ex situ X-ray photoelectron spectroscopy evidence significantly suppressed oxygen release, phase transition, and interfacial reactions. Further analysis of cycled electrodes reveals that the LTO coating layer inhibits TM dissolution and prevents the lithium anode from TM crossover effect. This study expands the primary particle coating strategy to upgrade LRMO cathode materials for advanced LIBs.

Stabilizing Zinc Electrodes with a Vanillin Additive in Mild Aqueous Electrolytes.

Metallic zinc (Zn) is an attractive anode material to use for building an aqueous battery but suffers from dendritic growth and water-induced corrosion. Herein, we report the use of vanillin as a bifunctional additive in aqueous electrolyte to stabilize the Zn electrochemistry. Computational, spectroscopic, and electrochemical studies suggest that vanillin molecules preferentially absorb in parallel on the Zn surface to homogenize the Zn2+ plating and favorably coordinate with Zn2+ to weaken the solvation interaction between H2O and Zn2+, resulting in a compact, dendrite-free Zn deposition and a stable electrode-electrolyte interface with suppressed hydrogen evolution and hydroxide sulfate formation. In the formulated 2 M ZnSO4 electrolyte with 5 mM vanillin, the Zn anode sustains high areal capacity (10 mAh cm-2 at 1 mA cm-2) and remarkable cycling stability (1 mAh cm-2 for 1000 h) in a Zn|Zn cell and high average Coulombic efficiency (99.8%) in a Zn|Cu cell, significantly outperforming the cells without vanillin. Furthermore, the vanillin additive supports stable operation of full Zn|V2O5 batteries and is readily generalized to a Zn(CF3SO3)2-based electrolyte. This work offers a facile and cost-effective strategy of electrolyte design to enable high-performance aqueous Zn batteries.

Nanoporous NiSb to Enhance Nitrogen Electroreduction via Tailoring Competitive Adsorption Sites.

Ambient nitrogen reduction reaction (NRR) is attracting extensive interest but still suffers from sluggish kinetics owing to competitive rapid hydrogen evolution and difficult nitrogen activation. Herein, nanoporous NiSb alloy is reported as an efficient electrocatalyst for N2 fixation, achieving a high ammonia yield rate of 56.9 µg h-1 mg-1 with a Faradaic efficiency of 48.0%. Density functional theory calculations reveal that in NiSb alloy, Ni favors N2 hydrogenation while the neighboring Sb separates active sites for proton and N2 adsorption, which optimizes the adsorption/desorption of intermediates and enables an energetically favorable NRR pathway. This work indicates promising electrocatalytic application of the alloys of 3d and p block metals toward the NRR and provides an intriguing strategy to enhance the reduction of inert molecules by restraining the competitive hydrogen adsorption.

Regulating Electrocatalytic Oxygen Reduction Activity of a Metal Coordination Polymer via d-π Conjugation.

Non-noble transition metal complexes have attracted growing interest as efficient electrocatalysts for oxygen reduction reaction (ORR) while their activities still lack rational and effective regulation. Herein, we propose a d-π conjugation strategy for rough and fine tuning of ORR activity of TM-BTA (TM=Mn/Fe/Co/Ni/Cu, BTA=1,2,4,5-benzenetetramine) coordination polymers. By first-principle calculations, we elucidate that the strong d-π conjugation elevates the dxz /dyz orbitals of TM centers to enhance intermediate adsorption and strengthens the electronic modulation effect from substitute groups on ligands. Based on this strategy, Co-TABQ (tetramino benzoquinone) is found to approach the top of ORR activity volcano. The synthesized Co-TABQ with atomically distributed Co on carbon nanotubes exhibits a half-wave potential of 0.85 V and a specific current of 127 mA mgmetal -1 at 0.8 V, outperforming the benchmark Pt/C. The high activity, low peroxide yield, and considerable durability of Co-BTA and Co-TABQ promise their application in oxygen electrocatalysis. This study provides mechanistic insight into the rational design of transition metal complex catalysts.

Electroless Formation of a Fluorinated Li/Na Hybrid Interphase for Robust Lithium Anodes.

Engineering a stable solid electrolyte interphase (SEI) is one of the critical maneuvers in improving the performance of a lithium anode for high-energy-density rechargeable lithium batteries. Herein, we build a fluorinated lithium/sodium hybrid interphase via a facile electroless electrolyte-soaking approach to stabilize the repeated plating/stripping of lithium metal. Jointed experimental and computational characterizations reveal that the fluorinated hybrid SEI mainly consisting of NaF, LiF, LixPOyFz, and organic components features a mosaic polycrystalline structure with enriched grain boundaries and superior interfacial properties toward Li. This LiF/NaF hybrid SEI exhibits improved ionic conductivity and mechanical strength in comparison to the SEI without NaF. Remarkably, the fluorinated hybrid SEI enables an extended dendrite-free cycling of metallic Li over 1300 h at a high areal capacity of 10 mAh cm-2 in symmetrical cells. Furthermore, full cells based on the LiFePO4 cathode and hybrid SEI-protected Li anode sustain long-term stability and good capacity retention (96.70% after 200 cycles) at 0.5 C. This work could provide a new avenue for designing robust multifunctional SEI to upgrade the metallic lithium anode.

Growing Nanostructured CuO on Copper Foil via Chemical Etching to Upgrade Metallic Lithium Anode.

Metallic lithium is one of the most promising anode materials to build next generation electrochemical power sources such as Li-air, Li-sulfur, and solid-state lithium batteries. The implementation of rechargeable Li-based batteries is plagued by issues including dendrites, pulverization, and an unstable solid electrolyte interface (SEI). Herein, we report the use of nanostructured CuO in situ grown on commercial copper foil (CuO@Cu) via chemical etching as a Li-reservoir substrate to stabilize SEI formation and Li stripping/plating. The lithiophilic interconnected CuO layer enhances electrolyte wettability. Besides, a mechanically stable Li2O- and LiF-rich SEI is generated on CuO@Cu during initial discharge, which permits dense and uniform lithium deposition upon subsequent cycling. Compared with bare Cu, the CuO@Cu electrode exhibits superior performance in terms of Coulombic efficiency, discharge/charge overpotentials, and cyclability. By pairing with the Li-CuO@Cu anodes, full cells with LiFePO4 and LiNi1/3Mn1/3Co1/3O2 cathodes sustain 300 cycles with 98.8% capacity retention at 1 C and deliver a specific capacity of 80 mAh g-1 at 10 C, respectively. This work would shed light on the design of advanced current collectors with SEI modulation to upgrade lithium anodes.

Isolated diatomic Zn-Fe in N-doped carbon for electrocatalytic nitrogen reduction to ammonia.

Isolated diatomic Zn-Fe anchored on nitrogen-doped carbon is explored as an efficient and robust electrocatalyst for N2 reduction in a neutral aqueous electrolyte, delivering a high NH3 yield rate (30.5 µg h-1 mgcat.-1) and considerable faradaic efficiency (26.5%) at a low overpotential of -300 mV. Density functional theory calculations reveal that the Zn-Fe atomic pairs synergistically favor N2 activation and reduce the reaction barrier for the rate-limiting step of intermediate *NNH formation.

Materials chemistry for rechargeable zinc-ion batteries.

Rechargeable zinc-ion batteries (ZIBs) are promising for large scale energy storage and portable electronic applications due to their low cost, material abundance, high safety, acceptable energy density and environmental friendliness. This tutorial review presents an introduction to the fundamentals, challenges, recent advances and prospects related to ZIBs. Firstly, the intrinsic chemical properties, challenges and strategies of metallic zinc anodes are underscored. Then, the multiple types of cathode materials are classified and comparatively discussed in terms of their structural and electrochemical properties, issues and remedies. Specific attention is paid to the mechanistic understanding and structural transformation of cathode materials based on Zn ion-(de)intercalation chemistry. After that, the widely investigated electrolytes are elaborated by discussing their effect on Zn plating/stripping behaviours, reaction kinetics, electrode/electrolyte interface chemistries, and cell performances. Finally, the remaining challenges and future perspectives are outlined for the development of ZIBs.