Local Charge Transfer Unveils Antideactivation of Ru at High Potentials for the Alkaline Hydrogen Oxidation Reaction.

The activity of Ru-based alkaline hydrogen oxidation reaction (HOR) electrocatalysts usually decreases rapidly at potentials higher than 0.1 V (vs a reversible hydrogen electrode (RHE)), which significantly limits the lifetime of fuel cells. It is found that this phenomenon is caused by the overadsorption of the O species due to the overcharging of Ru nanoparticles at high potentials. Here, Mn1Ox(OH)y clusters-modified Ru nanoparticles (Mn1Ox(OH)y@Ru/C) were prepared to promote charge transfer from overcharged Ru nanoparticles to Mn1Ox(OH)y clusters. Mn1Ox(OH)y@Ru/C exhibits high HOR activity and stability over a wide potential range of 0-1.0 V. Moreover, a hydroxide exchange membrane fuel cell with a Mn1Ox(OH)y@Ru/C anode delivers a high peak power density of 1.731 W cm-2, much superior to that of a Pt/C anode. In situ X-ray absorption fine structure (XAFS) analysis and density functional theory (DFT) calculations reveal that Mn in Mn1Ox(OH)y clusters could receive more electrons from overcharged Ru at higher potentials and significantly decrease the overadsorption of the O species on Ru, thus permitting the HOR on Ru to proceed at high potentials. This study provides guidance for the design of alkaline HOR catalysts without activity decay at high potentials.

Enhancing Electrocatalytic CO2-to-CO Conversion by Weakening CO Binding through Nitrogen Integration in the Metallic Fe Catalyst.

Metallic iron (Fe) typically demonstrates the unfavorable catalytic activity for the CO2 reduction reaction (CO2RR), mainly attributed to the excessively strong binding of CO products on Fe sites. Toward this end, we employed an effective approach involving electronic structure modulation through nitrogen (N) integration to enhance the performance of the CO2RR. Here, an efficient catalyst has been developed, composed of N-doped metallic iron (Fe) nanoparticles encapsulated in a porous N-doped carbon framework. Notably, this N-integrated Fe catalyst displays significantly enhanced performance in the electrocatalytic reduction of CO2, yielding the highest CO Faradaic efficiency of 97.5% with a current density of 6.68 mA cm-2 at -0.7 V versus the reversible hydrogen electrode. The theoretical calculations, combined with the in situ attenuated total reflection surface-enhanced infrared absorption spectroscopy study, reveal that N integration modulates the electron density around Fe, resulting in the weakening of the binding strength between the Fe active sites and *CO intermediates, consequently promoting the desorption of CO and the overall CO2RR process.

Ultralow-Loading Ruthenium-Iridium Fuel Cell Catalysts Dispersed on Zn-N Species-Doped Carbon.

Developing low-loading platinum-group-metal (PGM) catalysts is one of the key challenges in commercializing anion-exchange-membrane-fuel-cells (AEMFCs), especially for hydrogen oxidation reaction (HOR). Here, ruthenium-iridium nanoparticles being deposited on a Zn-N species-doped carbon carrier (Ru6Ir/Zn-N-C) are synthesized and used as an anodic catalyst for AEMFCs. Ru6Ir/Zn-N-C shows extremely high mass activity (5.87 A mgPGM -1) and exchange current density (0.92 mA cm-2), which is 15.1 and 3.9 times that of commercial Pt/C, respectively. Based on the Ru6Ir/Zn-N-C AEMFCs achieve a peak power density of 1.50 W cm-2, surpassing the state-of-the-art commercial PtRu catalysts and the power ratio of the normalized loading is 14.01 W mgPGM anode -1 or 5.89 W mgPGM -1 after decreasing the anode loading (87.49 µg cm-2) or the total PGM loading (0.111 mg cm-2), satisfying the US Department of Energy's PGM loading target. Moreover, the solvent and solute isotope separation method is used for the first time to reveal the kinetic process of HOR, which shows the reaction is influenced by the adsorption of H2O and OH-. The improvement of the hydrogen bond network connectivity of the electric double layer by adjusting the interfacial H2O structure together with the optimized HBE and OHBE is proposed to be responsible for the high HOR activity of Ru6Ir/Zn-N-C.

Highly selective electrocatalytic reduction of CO2 to HCOOH over an in situ derived Ag-loaded Bi2O2CO3 electrocatalyst.

The electrochemical reduction of CO2 to HCOOH is considered one of the most appealing routes to alleviate the energy crisis and close the anthropogenic CO2 cycle. However, it remains challenging to develop electrocatalysts with high activity and selectivity towards HCOOH in a wide potential window. In this regard, Ag/Bi2O2CO3 was prepared by an in situ electrochemical transformation from Ag/Bi2O3. The Ag/Bi2O2CO3 catalyst achieves a faradaic efficiency (FE) of over 90% for HCOOH in a wide potential window between -0.8 V and -1.3 V versus the reversible hydrogen electrode (RHE). Moreover, a maximum FE of 95.8% and a current density of 15.3 mA cm-2 were achieved at a low applied potential of -1.1 V. Density functional theory (DFT) calculations prove that the high catalytic activity of Ag/Bi2O2CO3 is ascribed to the fact that Ag can regulate the electronic structure of Bi, thus facilitating the adsorption of *OCHO and hindering the adsorption of *COOH. This work expands the in situ electrochemical derivatization strategy for the preparation of electrocatalysts.

Optimizing Hydrogen and Hydroxyl Adsorption over Ru/WO2.9 Metal/Metalloid Heterostructure Electrocatalysts for Highly Efficient and Stable Hydrogen Oxidation Reactions in Alkaline Media.

The development of high-performance, stable and platinum-free electrocatalysts for the hydrogen oxidation reaction (HOR) in alkaline media is crucial for the commercial application of anion exchange membrane fuel cells (AEMFCs). Ruthenium, as an emerging HOR electrocatalyst with a price advantage over platinum, still needs to solve the problems of low intrinsic activity and easy oxidation. Herein, Ru nanoparticles are anchored on the oxygen-vacancy-rich metalloid WO2.9 by interfacial engineering to create abundant and efficient Ru and WO2.9 interfacial active sites for accelerated HOR in alkaline media. Ru/WO2.9/C displays excellent catalytic activity with mass activity (8.29 A mgNM -1) and specific activity (1.32 mA cmNM -2), which are 2.5/3.3 and 21.8/8.3 times that of PtRu/C and Pt/C, respectively. Moreover, Ru/WO2.9/C exhibits excellent CO tolerance and operational stability. Experimental and theoretical studies reveal that the improved charge transfer from Ru to WO2.9 in the metal/metalloid heterostructure significantly tune the electronic structure of Ru sites and optimize the hydrogen binding energy (HBE) of Ru. While, WO2.9 provides abundant hydroxyl adsorption sites. Therefore, the equilibrium adsorption of hydrogen and hydroxyl at the interface of Ru/WO2.9 will be realized, and the oxidation of metal Ru would be avoided, thereby achieving excellent HOR activity and durability.

V-O Species-Doped Carbon Frameworks Loaded with Ru Nanoparticles as Highly Efficient and CO-Tolerant Catalysts for Alkaline Hydrogen Oxidation.

Efficient and CO-tolerant catalysts for alkaline hydrogen oxidation (HOR) are vital to the commercial application of anion exchange membrane fuel cells (AEMFCs). Herein, a robust Ru-based catalyst (Ru/VOC) with ultrasmall Ru nanoparticles supported on carbon frameworks with atomically dispersed V-O species is prepared elaborately. The catalyst exhibits a remarkable mass activity of 3.44 mA µgPGM, which is 31.3 times that of Ru/C and even 4.7 times higher than that of Pt/C. Moreover, the Ru/VOC anode can achieve a peak power density (PPD) of 1.194 W cm-2, much superior to that of Ru/C anode and even better than that of Pt/C anode. In addition, the catalyst also exhibits superior stability and exceptional CO tolerance. Experimental results and density functional theory (DFT) calculations demonstrate that V-O species are ideal OH- adsorption sites, which allow Ru to release more sites for hydrogen adsorption. Furthermore, the electron transfer from Ru nanoparticles to the carbon substrate regulates the electronic structure of Ru, reducing the hydrogen binding energy (HBE) and the CO adsorption energy on Ru, thus boosting the alkaline HOR performance and CO tolerance of the catalyst. This is the first report that oxophilic single atoms distributed on carbon frameworks serve as OH- adsorption sites for efficient hydrogen oxidation, opening up new guidance for the elaborate design of high-activity catalysts for the alkaline HOR.

Microbial synthesis of Prussian blue for potentiating checkpoint blockade immunotherapy.

Cancer immunotherapy is revolutionizing oncology. The marriage of nanotechnology and immunotherapy offers a great opportunity to amplify antitumor immune response in a safe and effective manner. Here, electrochemically active Shewanella oneidensis MR-1 can be applied to produce FDA-approved Prussian blue nanoparticles on a large-scale. We present a mitochondria-targeting nanoplatform, MiBaMc, which consists of Prussian blue decorated bacteria membrane fragments having further modifications with chlorin e6 and triphenylphosphine. We find that MiBaMc specifically targets mitochondria and induces amplified photo-damages and immunogenic cell death of tumor cells under light irradiation. The released tumor antigens subsequently promote the maturation of dendritic cells in tumor-draining lymph nodes, eliciting T cell-mediated immune response. In two tumor-bearing mouse models using female mice, MiBaMc triggered phototherapy synergizes with anti-PDL1 blocking antibody for enhanced tumor inhibition. Collectively, the present study demonstrates biological precipitation synthetic strategy of targeted nanoparticles holds great potential for the preparation of microbial membrane-based nanoplatforms to boost antitumor immunity.

Creating interfaces of Cu0/Cu+ in oxide-derived copper catalysts for electrochemical CO2 reduction to multi-carbon products.

Electrochemical carbon dioxide reduction reaction (CO2RR) is an effective approach to capture CO2 and convert it into value-added chemicals and fuels, thereby reducing excess CO2 emissions. Recent reports have shown that copper-based catalysts exhibit excellent performance in converting CO2 into multi-carbon compounds and hydrocarbons. However, theselectivityto the couplingproductsispoor. Therefore, tuningCO2-reductionselectivitytoward C2+productsover Cu-based catalyst is one of the most important issues in CO2RR. Herein, we prepare a nanosheet catalyst with interfaces of Cu0/Cu+. The catalyst achieves Faraday efficiency (FE) of C2+ over 50% in a wide potential window between - 1.2 V to - 1.5 V versus reversible hydrogen electrode (vs. RHE). Moreover, the catalyst exhibits maximum FE of 44.5% and 58.9% towards C2H4 and C2+, with a partial current density of 10.5 mA cm-2 at - 1.4 V. Density functional theory (DFT) calculations show that the interface of Cu0/Cu+ facilitates CC coupling to form C2+ products, while inhibits CO2conversion toC1products.

Octahedral/Tetrahedral Vacancies in Fe3 O4 as K-Storage Sites: A Case of Anti-Spinel Structure Material Serving as High-Performance Anodes for PIBs.

Potassium-ion batteries (PIBs) have attracted more and more attention as viable alternatives to lithium-ion batteries (LIBs) due to the deficiency and uneven distribution of lithium resources. However, it is shown that potassium storage in some compounds through reaction or intercalation mechanisms cannot effectively improve the capacity and stability of anodes for PIBs. The unique anti-spinel structure of magnetite (Fe3 O4 ) is densely packed with thirty-two O atoms to form a face-centered cubic (fcc) unit cell with tetrahedral/octahedral vacancies in the O-closed packing structure, which can serve as K+ storage sites according to the density functional theory (DFT) calculation results. In this work, carbon-coated Fe3 O4 @C nanoparticles are prepared as high-performance anodes for PIBs, which exhibit high reversible capacity (638 mAh g-1 at 0.05 A g-1 ) and hyper stable cycling performance at ultrahigh current density (150 mAh g-1 after 9000 cycles at 10 A g-1 ). In situ XRD, ex-situ Fe K-edge XAFS, and DFT calculations confirm the storage of K+ in tetrahedral/octahedral vacancies.

Missing-Linker-Confined Single-Atomic Pt Nanozymes for Enzymatic Theranostics of Tumor.

Conventional nanozymes often possess low active site density. Pursuing effective strategies for constructing highly active single-atomic nanosystems with maximum atom utilization efficiency is exceptionally attractive. Herein, we develop a facile "missing-linker-confined coordination" strategy to fabricate two self-assembled nanozymes, i.e., conventional nanozyme (NE) and single-atomic nanozyme (SAE), which respectively consist of Pt nanoparticles and single Pt atoms as active catalytic sites anchored in metal-organic frameworks (MOFs) with encapsulated photosensitizers for catalase-mimicking enhanced photodynamic therapy. Compared to a Pt nanoparticle-based conventional nanozyme, a Pt single-atomic nanozyme shows enhanced catalase-mimicking activity in generating oxygen for overcoming tumor hypoxia, thus exhibiting a more efficient reactive oxygen species generation and high tumor inhibition rate.

Highly Flexible K-Intercalated MnO2 /Carbon Membrane for High-Performance Aqueous Zinc-Ion Battery Cathode.

The layered MnO2 is intensively investigated as one of the most promising cathode materials for aqueous zinc-ion batteries (AZIBs), but its commercialization is severely impeded by the challenging issues of the inferior intrinsic electronic conductivity and undesirable structural stability during the charge-discharge cycles. Herein, the lab-prepared flexible carbon membrane with highly electrical conductivity is first used as the matrix to generate ultrathin δ-MnO2 with an enlarged interlayer spacing induced by the K+ -intercalation to potentially alleviate the structural damage caused by H+ /Zn2+ co-intercalation, resulting in a high reversible capacity of 190 mAh g-1 at 3 A g-1 over 1000 cycles. The in situ/ex-situ characterizations and electrochemical analysis confirm that the enlarged interlayer spacing can provide free space for the reversible deintercalation/intercalation of H+ /Zn2+ in the structure of δ-MnO2 , and H+ /Zn2+ co-intercalation mechanism contributes to the enhanced charge storage in the layered K+ -intercalated δ-MnO2 . This work provides a plausible way to construct a flexible carbon membrane-based cathode for high-performance AZIBs.

Bidirectional Tandem Electrocatalysis Manipulated Sulfur Speciation Pathway for High-Capacity and Stable Na-S Battery.

The sluggish polysulfide redox kinetics and the uncontrollable sulfur speciation pathway, leading to serious shuttling effect and high activation barrier associated with sulfur cathode. We describe here the use of core-shell structured composite matrixes containing abundant catalytic sites for nearly fully reversible cycling of sulfur cathodes for Na-S batteries. The bidirectional tandem electrocatalysis provide successive reversible conversion of both long- and short-chain polysulfides, whereas Fe2 O3 accelerates Na2 S8 /Na2 S6 to Na2 S4 conversion and the redox-active Fe(CN)6 4- -doped polypyrrole shell catalyzes Na2 S4 reduction to Na2 S. The electrochemically reactive Na2 S can be readily charged back to sulfur with minimal overpotential. Simultaneously, stable cycling of Na-S pouch cell with a high reversible capacity of 696 mAh g-1 is also demonstrated. The bidirectional confined tandem catalysis renders the manipulation of sulfur redox electrochemistry for practical Na-S cells.

Activation of MoS2 monolayer electrocatalysts via reduction and phase control in molten sodium for selective hydrogenation of nitrogen to ammonia.

Electrochemical nitrogen fixation under ambient conditions is promising for sustainable ammonia production but is hampered by high reaction barrier and strong competition from hydrogen evolution, leading to low specificity and faradaic efficiency with existing catalysts. Here we describe the activation of MoS2 in molten sodium that leads to simultaneous formation of a sulfur vacancy-rich heterostructured 1T/2H-MoS x monolayer via reduction and phase transformation. The resultant catalyst exhibits intrinsic activities for electrocatalytic N2-to-NH3 conversion, delivering a faradaic efficiency of 20.5% and an average NH3 rate of 93.2 µg h-1 mgcat -1. The interfacial heterojunctions with sulfur vacancies function synergistically to increase electron localization for locking up nitrogen and suppressing proton recombination. The 1T phase facilitates H-OH dissociation, with S serving as H-shuttling sites and to stabilize . The subsequently couple with nearby N2 and NH x intermediates bound at Mo sites, thus greatly promoting the activity of the catalyst. First-principles calculations revealed that the heterojunction with sulfur vacancies effectively lowered the energy barrier in the potential-determining step for nitrogen reduction, and, in combination with operando spectroscopic analysis, validated the associative electrochemical nitrogen reduction pathway. This work provides new insights on manipulating chalcogenide vacancies and phase junctions for preparing monolayered MoS2 with unique catalytic properties.

NIR-II responsive PEGylated nickel nanoclusters for photothermal enhanced chemodynamic synergistic oncotherapy.

Rationale: All kinds of non-metal and metal-based nanozymes have been extensively explored as Fenton agents for Chemodynamic therapy (CDT). However, the low catalytic efficiency of non-metallic nanozymes and the susceptibility to oxidation and long-term toxicity of metallo-nanozymes limit their potential in CDT. Methods: In this study, we report a magneto-solvothermal method to tune the crystallinity and shape of polyethylene glycol (PEG)-ylated urchin-like nickel nanoclusters (named as 9T-PUNNC) at a high magnetic field with an intensity of 9 T for enhanced combined photothermal-chemodynamic therapy. Results: The needle-like protrusions on the surface of 9T-PUNNC can effectively increase the reception of NIR light in second NIR window (NIR-II) and transform it into local hyperthermia, achieving effective photothermal treatment. The light and heat generated by NIR-II further promotes the release of Ni2+ and improves the ability of Ni2+-mediated chemodynamic therapy (CDT). In addition, the surface coating of PEG on the surface of 9T-PUNNC improves its stability and biocompatibility of nanocrystals. In vitro and in vivo results indicate that the 9T-PUNNC could efficiently kill tumor cells (nearly 12 times more than control group) and inhibit tumor growth (nearly 9 times smaller than control group) under NIR-II irradiation through the synergistic effect of combined treatments. Conclusions: we developed a novel synthetic strategy to tune crystallinity and shape of PUNNC for enhanced NIR-II responsive photothermal conversion efficiency and accelerated acid-induced dissolution for improved ·OH generation. Such 9T-PUNNC enable a combined chemodynamic-photothermal treatment to provide superior therapeutic efficacy due to their highly synergistic effect.

Room-Temperature Sodium-Sulfur Batteries: Rules for Catalyst Selection and Electrode Design.

Seeking an optimal catalyst to accelerate conversion reaction kinetics of room-temperature sodium-sulfur (RT Na-S) batteries is crucial for improving their electrochemical performance and promoting the practical applications. Herein, theoretical calculations of interfacial interactions of catalysts and polysulfides in terms of the surface adsorption state, interfacial ions migration, and electronic concentration around the Fermi level are systematically proposed as guiding principles of catalyst selection for RT Na-S batteries. As a case, MoN catalyst is accurately selected from transition metal nitrides with different d orbital electrons, and for experiment, it is introduced into the carbon nanofibers as a dual-functioning host (MoN@CNFs). The MoN@CNFs can effectively anchor polysulfides and accelerate their conversion reaction. In addition, for the sodium anode, the MoN@CNFs can also induce uniform deposition of Na and inhibit dendrite growth, which are supported by in situ characterizations and finite element simulation technique. As a result, the as-prepared RT Na-S battery displays high reversible capacity of 990 mAh g-1 at 0.2 A g-1 after 100 cycles and long lifespan over 1500 cycles at 2 A g-1 . Even with high S loading of 5 mg cm-2 , the RT Na-S battery still exhibits a high areal capacity of 2.5 mAh cm-2 .

Electrocatalysis in Room Temperature Sodium-Sulfur Batteries: Tunable Pathway of Sulfur Speciation.

Benefiting from the merits of natural abundance, low cost, and ultrahigh theoretical energy density, the room temperature sodium-sulfur (RT NaS) batteries are regarded as one of the promising candidates for the next-generation scalable energy storage devices. However, the uncontrollable sulfur speciation pathways severely hinder its practical applications. Recently, various strategies have been employed to tune the conversion pathways of sulfur, such as physical confinement, chemical inhibition, and electrocatalysis. Herein, the recent advances in electrocatalytic effects manipulate sulfur speciation pathways in advanced RT NaS electrochemistry are reviewed, including the promotion of the nearly full conversion of long-chain polysulfides, short-chain polysulfides, and small sulfur molecules. The underlying catalytic modulation mechanism that fundamentally tunes the electrochemical pathway of sulfur species is comprehensively summarized along with the design strategies for catalytic active centers. Furthermore, the challenge and potential solutions to realize the quasi-solid conversion of sulfur are proposed to accelerate the real application of RT NaS batteries.

Simultaneous reversible tuning of H+ and Zn2+ coinsertion in MnO2 cathode for high-capacity aqueous Zn-ion battery.

Protons and zinc ions are generally regarded as charge carriers for rechargeable Zn/MnO2 batteries relying on cation coinsertion for their two-step redox energy storage. However, the irreversibility of H+ insertion and especially Zn2+ insertion unlocks the innate advantages of this scalable aqueous battery system such as high safety and low cost. Herein, an encapsulated structure with manganese hexacyanoferrate(II)-polypyrrole (MnHCF-PPy) composite thin films was in situ constructed within α-MnO2 nanofibers to modulate the interfacial charge transfer process and direct the consequent reversible H+ and Zn2+ insertion/extraction via a synergistic action. The PPy film promotes interfacial proton transfer for the fast conversion of MnO2 to MnOOH and suppresses cathode dissolution, whereas MnHCF with abundant interconnected open ion channels serves as a cation reservoir to facilitate continuous and reversible zinc ion transfer without the aggregation of ZnMn2O4 nanocrystals, leading to protected MnO2 cathodes with recorded high discharge capacity (263 mA h g-1 at 0.5 C), remarkable rate capability (179 mA h g-1 at 5 C), and long lifespan in ZnSO4 electrolyte. Moreover, a flexible solid-state Zn/MnO2 full cell was further demonstrated, which delivers a preferable energy density of 220 W h kgcathode-1, opening a new modus operandi towards advanced flexible batteries through interfacial engineering and device optimization.

Ultrasmall Cu Nanocrystals Dispersed in Nitrogen-Doped Carbon as Highly Efficient Catalysts for CO2 Electroreduction.

The electroreduction of carbon dioxide (CO2) to a liquid product is a viable method for establishing an artificial carbon cycle. Unfortunately, most electrocatalysts' low efficiency and instability prevent them from being used in practical applications. In the current study, we developed ultrasmall Cu nanocrystals embedded in nitrogen-doped carbon nanosheets (Cu/NC-NSs) for selective CO2 electroreduction by adjusting the potential. Cu/NC-NSs had 43.7 and 63.5% Faradaic efficiencies for the synthesis of ethanol and formate with applied potentials of -0.37 and -0.77 V vs reversible hydrogen electrode (RHE) using a flow cell architecture, respectively. Moreover, these Cu/NC-NSs show a steady catalytic performance up to 16 h. Density functional theory (DFT) calculations were performed to investigate the reaction mechanism. Furthermore, the synergistic effect formed by nitrogen-doped carbon and highly dispersed copper atoms led to their excellent performance in CO2 electroreduction.

Hollow Cuprous Oxide@Nitrogen-Doped Carbon Nanocapsules for Cascade Chemodynamic Therapy.

Cuprous-based nanozymes have demonstrated great potential for cascade chemodynamic therapy (CDT) due to their higher catalytic efficiency and simple reaction conditions. Here, hollow cuprous oxide@nitrogen-doped carbon (HCONC) dual-shell structures are designed as nanozymes for CDT oncotherapy. This HCONC with a size distribution of 130 nm is synthesized by a one-step hydrothermal method using cupric nitrate and dimethyl formamide as precursors. The thin-layer carbon (1.88 nm) of HCONC enhances the water-stability and reduces the systemic toxicity of cuprous oxide nanocrystals. The dissolved Cu+ of HCONC in acid solution induces a Fenton-like reaction and exhibits a fast reaction rate for catalyzing H2 O2 into highly toxic hydroxyl radicals (·OH). Meanwhile, the formed Cu+ consumes oversaturated glutathione (GSH) to avoid its destruction of ROS at the intracellular level. In general, both cellular and animal experiments show that HCONC demonstrates excellent antitumor ability without causing significant systemic toxicity, which may present tremendous potential for clinical cancer therapy.