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Hydrogen electrocatalytic reactions, including the hydrogen evolution reaction (HER) and the hydrogen oxidation reaction (HOR), play a crucial role in a wide range of energy conversion and storage technologies. However, the HER and HOR display anomalous non-Nernstian pH dependent kinetics, showing two to three orders of magnitude sluggish kinetics in alkaline media compared to that in acidic media. Fundamental understanding of the origins of the intrinsic pH effect has attracted substantial interest from the electrocatalysis community. More critically, a fundamental molecular level understanding of this effect is still debatable, but is essential for developing active, stable, and affordable fuel cells and water electrolysis technologies. Against this backdrop, in this review, we provide a comprehensive overview of the intrinsic pH effect on hydrogen electrocatalysis, covering the experimental observations, underlying principles, and strategies for catalyst design. We discuss the strengths and shortcomings of various activity descriptors, including hydrogen binding energy (HBE) theory, bifunctional theory, potential of zero free charge (pzfc) theory, 2B theory and other theories, across different electrolytes and catalyst surfaces, and outline their interrelations where possible. Additionally, we highlight the design principles and research progress in improving the alkaline HER/HOR kinetics by catalyst design and electrolyte optimization employing the aforementioned theories. Finally, the remaining controversies about the pH effects on HER/HOR kinetics as well as the challenges and possible research directions in this field are also put forward. This review aims to provide researchers with a comprehensive understanding of the intrinsic pH effect and inspire the development of more cost-effective and durable alkaline water electrolyzers (AWEs) and anion exchange membrane fuel cells (AMFCs) for a sustainable energy future.
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The specific capacity of Li- and Mn-rich layered oxide (LMROs) cathodes can be enhanced by the oxidation of lattice oxygen at high voltages. Nevertheless, an irreversible oxygen loss emerges with cycling, which triggers interlocking surface/interface issues and results in the fast deterioration of cycling performance. Herein, we prepare a surface modified LMRO electrode by one step doctor-blade casting and introducing a benzoquinone species DBBQ redox couple. The electrochemical test shows that the DBBQ-modified electrode has a high reversible capacity (>320 mAh g-1) and excellent rate performance, while the cyclic stability has been significantly improved as well. The capacity retention reaches as high as 93.3% after 500 cycles at 1 C. Mechanism analysis shows that DBBQ can not only play a redox couple in LMROs which achieves the adsorption and reduction of surface oxygen gas but also significantly enhance anionic redox in the bulk, thus realizing extraordinary capacity.
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Mn-based fluorophosphates have attracted much attention as cathodes for sodium-ion batteries owing to their high cost effectiveness, considerable capacity, and stable framework. However, the fascinating Mn3+/2+ redox couple suffers from inadequate activation due to the Mn-O covalent character and poor electronic conductivity, impeding its further applications. Herein, a local electronic structure regulation strategy is proposed to improve the Mn3+/2+ redox potential and reversible capacity simultaneously through introducing elements with low-energy 3d orbitals to expand the energy gap between the eg orbitals and Fermi energy of Na. Moreover, the 3d element substitution serves to narrow the band gap toward the improved intrinsic electronic conductivity. In comparison with pristine Na2Fe0.45Mn0.55PO4F, the as-prepared Na2Fe0.45Mn0.4V0.1PO4F cathode achieves an increase from 3.5 to 3.6 V in the high-voltage platform and an improvement in energy density from 330 to 361 Wh kg-1. This work inspires new ideas in adjusting the redox potential of polyanionic cathodes through deliberate regulation of the local electronic structure.
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Endowing conventional materials with specific functions that are hardly available is invariably of significant importance but greatly challenging. TiO2 is proven to be highly active for the photocatalytic hydrogen evolution while intrinsically inert for electrocatalytic hydrogen evolution reaction (HER) due to its poor electrical conductivity and unfavorable hydrogen adsorption/desorption behavior. Herein, the first activation of inert TiO2 for electrocatalytic HER is demonstrated by synergistically modulating the positions of d-band center and triggering hydrogen spillover through the dual doping-induced partial phase transition. The N, F co-doping-induced partial phase transition from anatase to rutile phase in TiO2 (AR-TiO2|(N,F)) exhibits extraordinary HER performance with overpotentials of 74, 80, and 142 mV at a current density of 10 mA cm-2 in 1.0 M KOH, 0.5 M H2SO4, and 1.0 M phosphate-buffered saline electrolytes, respectively, which are substantially better than pure TiO2, and even superior to the benchmark Pt/C catalysts. These findings may open a new avenue for the development of low-cost alternative to noble metal catalysts for electrocatalytic hydrogen production.
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Heterointerface engineering is presently considered a valuable strategy for enhancing the microwave absorption (MA) properties of materials via compositional modification and structural design. In this study, a sulfur-doped multi-interfacial composite (Fe7S8/NiS@C) coated with NiFe-layered double hydroxides (LDHs) is successfully prepared using a hydrothermal method and post-high-temperature vulcanization. When assembled into twisted surfaces, the NiFe-LDH nanosheets exhibit porous morphologies, improving impedance matching, and microwave scattering. Sulfur doping in composites generates heterointerfaces, numerous sulfur vacancies, and lattice defects, which facilitate the polarization process to enhance MA. Owing to the controllable heterointerface design, the unique porous structure induced multiple heterointerfaces, numerous vacancies, and defects, endowing the Fe7S8/NiS@C composite with an enhanced MA capability. In particular, the minimum reflection loss (RLmin) value reached -58.1 dB at 15.8 GHz at a thickness of 2.1 mm, and a broad effective absorption bandwidth (EAB) value of 7.3 GHz is achieved at 2.5 mm. Therefore, the Fe7S8/NiS@C composite exhibits remarkable potential as a high-efficiency MA material owing to the synergistic effects of the polarization processes, multiple scatterings, porous structures, and impedance matching.
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The energy transition to renewables necessitates innovative storage solutions beyond the capacities of lithium-ion batteries. Aluminum-ion batteries (AIBs), particularly their aqueous variants (AAIBs), have emerged as potential successors due to their abundant resources, electrochemical advantages, and eco-friendliness. However, they grapple with achieving their theoretical voltage potential, often yielding less than expected. This perspective article provides a comprehensive examination of the voltage challenges faced by AAIBs, attributing gaps to factors such as the aluminum reduction potential, hydrogen evolution reaction, and aluminum's inherent passivation. Through a critical exploration of methodologies, strategies, such as underpotential deposition, alloying, interface enhancements, tailored electrolyte compositions, and advanced cathode design, are proposed. This piece seeks to guide researchers in harnessing the full potential of AAIBs in the global energy storage landscape.
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A highly reversible zinc anode is crucial for the commercialization of zinc-ion batteries. However, the change in the microstructure of the electric double layer originated from the dynamic change in charge density on the electrode greatly impacts anode reversibility during charge/discharge, which is rarely considered in previous research. Herein, the zwitterion additive is employed to create an adaptive interface by coupling the transient zwitterion dynamics upon the change of interfacial charge density. Ab initio molecular dynamics simulations suggest the molecular orientation and adsorption groups of zwitterions will be determined by the charging state of the electrode. ZnSO4 electrolyte with zwitterion fulfills a highly reversible Zn anode with an average Coulombic efficiency of up to 99.85%. Zn/Zn symmetric cells achieve greatly enhanced cycling stability for 700 h with extremely small voltage hysteresis of 29 mV under 5 mA cm-2 with 5 mAh cm-2 . This study validates the adaptive interface based on transient dynamics of zwitterions, which sheds new light on developing highly reversible metal anodes with a high utilization rate.
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Rechargeable aprotic Li-CO2 batteries have aroused worldwide interest owing to their environmentally friendly CO2 fixation ability and ultra-high specific energy density. However, its practical applications are impeded by the sluggish reaction kinetics and discharge product accumulation during cycling. Herein, a flexible composite electrode comprising CoSe2 nanoparticles embedded in 3D carbonized melamine foam (CoSe2/CMF) for Li-CO2 batteries is reported. The abundant CoSe2 clusters can not only facilitate CO2 reduction/evolution kinetics but also serve as Li2CO3 nucleation sites for homogeneous discharge product growth. The CoSe2/CMF-based Li-CO2 battery exhibits a large initial discharge capacity as high as 5.62 mAh cm-2 at 0.05 mA cm-2, a remarkably small voltage gap of 0.72 V, and an ultrahigh energy efficiency of 85.9% at 0.01 mA cm-2, surpassing most of the noble metal-based catalysts. Meanwhile, the battery demonstrates excellent cycling stability of 1620 h (162 cycles) at 0.02 mA cm-2 with an average overpotential of 0.98 V and energy efficiency of 85.4%. Theoretical investigations suggest that this outstanding performance is attributed to the suitable CO2/Li adsorption and low Li2CO3 decomposition energy. Moreover, flexible Li-CO2 pouch cell with CoSe2/CMF cathode displays stable power output under different bending deformations, showing promising potential in wearable electronic devices.
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Nanostructured metal hydrides with unique morphology and improved hydrogen storage properties have attracted intense interests. However, the study of the growth process of highly active borohydrides remains challenging. Herein, for the first time the synthesis of LiBH4 nanorods through a hydrogen-assisted one-pot solvothermal reaction is reported. Reaction of n-butyl lithium with triethylamine borane in n-hexane under 50 bar of H2 at 40-100 °C gives rise to the formation of the [100]-oriented LiBH4 nanorods with 500-800 nm in diameter, whose growth is driven by orientated attachment and ligand adsorption. The unique morphology enables the LiBH4 nanorods to release hydrogen from ≈184 °C, 94 °C lower than the commercial sample (≈278 °C). Hydrogen release amounts to 13 wt% within 40 min at 450 °C with a stable cyclability, remarkably superior to the commercial LiBH4 (≈9.1 wt%). More importantly, up to 180 °C reduction in the onset temperature of hydrogenation is successfully attained by the nanorod sample with respect to the commercial counterpart. The LiBH4 nanorods show no foaming during dehydrogenation, which improves the hydrogen cycling performance. The new approach will shed light on the preparation of nanostructured metal borohydrides as advanced functional materials.
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Anionic redox chemistry enables extraordinary capacity for Li- and Mn-rich layered oxides (LMROs) cathodes. Unfortunately, irreversible surface oxygen evolution evokes the pernicious phase transition, structural deterioration, and severe electrode-electrolyte interface side reaction with element dissolution, resulting in fast capacity and voltage fading of LMROs during cycling and hindering its commercialization. Herein, a redox couple strategy is proposed by utilizing copper phthalocyanine (CuPc) to address the irreversibility of anionic redox. The Cu-N synergistic effect of CuPc could not only inhibit surface oxygen evolution by reducing the peroxide ion O2 2- back to lattice oxygen O2-, but also enhance the reaction activity and reversibility of anionic redox in bulk to achieve a higher capacity and cycling stability. Moreover, the CuPc strategy suppresses the interface side reaction and induces the forming of a uniform and robust LiF-rich cathode electrolyte, interphase (CEI) to significantly eliminate transition metal dissolution. As a result, the CuPc-enhanced LMRO cathode shows superb cycling performance with a capacity retention of 95.0% after 500 long-term cycles. This study sheds light on the great effect of N-based redox couple to regulate anionic redox behavior and promote the development of high energy density and high stability LMROs cathode.
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Singlet oxygen (term symbol 1Δg, hereafter 1O2), a reactive oxygen species, has recently attracted increasing interest in the field of rechargeable batteries and electrocatalysis and photocatalysis. These sustainable energy conversion and storage technologies are of vital significance to replace fossil fuels and promote carbon neutrality and finally tackle the energy crisis and climate change. Herein, the recent progresses of 1O2 for energy storage and conversion is summarized, including physical and chemical properties, formation mechanisms, detection technologies, side reactions in rechargeable batteries and corresponding inhibition strategies, and applications in electrocatalysis and photocatalysis. The formation mechanisms and inhibition strategies of 1O2 in particular aprotic lithium-oxygen (Li-O2) batteries are highlighted, and the applications of 1O2 in photocatalysis and electrocatalysis is also emphasized. Moreover, the confronting challenges and promising directions of 1O2 in energy conversion and storage systems are discussed.
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Strong metal-support interaction (SMSI) plays a vital role in tuning the geometric and electronic structures of metal species. Generally, a high-temperature treatment (>500 °C) in reducing atmosphere is required for constructing SMSI, which may induce the sintering of metal species. Herein, we use molten salts as the reaction media to trigger the formation of high-intensity SMSI at reduced temperatures. The strong ionic polarization of the molten salt promotes the breakage of Ti-O bonds in the TiO2 support, and hence decreases the energy barrier for the formation of interfacial bonds. Consequently, a high-intensity SMSI state is achieved in TiO2 supported Ir nanoclusters, evidenced by a large number of Ir-Ti bonds at the interface, at a low temperature of 350 °C. Moreover, this method is applicable for triggering SMSI in various supported metal catalysts with different oxide supports including CeO2 and SnO2. This newly developed SMSI construction methodology opens a new avenue and holds significant potential for engineering advanced supported metal catalysts toward a broad range of applications.
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Strong metal-support interaction (SMSI) is crucial to modulating the nature of metal species, yet the SMSI behaviors of sub-nanometer metal clusters remain unknown due to the difficulties in constructing SMSI at cluster scale. Herein, we achieve the successful construction of the SMSI between Pt clusters and amorphous TiO2 nanosheets by vacuum annealing, which requires a relatively low temperature that avoids the aggregation of small clusters. In situ scanning transmission electron microscopy observation is employed to explore the SMSI behaviors, and the results reveal the dynamic rearrangement of Pt atoms upon annealing for the first time. The originally disordered Pt atoms become ordered as the crystallizing of the amorphous TiO2 support, forming an epitaxial interface between Pt and TiO2. Such a SMSI state can remain stable in oxidation environment even at 400 °C. Further investigations prove that the electron transfer from TiO2 to Pt occupies the Pt 5d orbitals, which is responsible for the disappeared CO adsorption ability of Pt/TiO2 after forming SMSI. This work not only opens a new avenue for constructing SMSI at cluster scale but also provides in-depth understanding on the unique SMSI behavior, which would stimulate the development of supported metal clusters for catalysis applications.
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The rapid transport kinetics of divalent magnesium ions are crucial for achieving distinguished performance in aqueous magnesium-ion battery-based energy storage capacitors. However, the strong electrostatic interaction between Mg2+ with double charges and the host material significantly restricts Mg2+ diffusivity. In this study, a new composite material, EDA-Mn2O3, with double-energy storage mechanisms comprising an organic phase (ethylenediamine, EDA) and an inorganic phase (manganese sesquioxide) was successfully synthesized via an organic-inorganic coupling strategy. Inorganic-phase Mn2O3 serves as a scaffold structure, enabling the stable and reversible intercalation/deintercalation of magnesium ions. The organic phase EDA adsorbed onto the surface of Mn2O3 as an elastic matrix, works synergistically with Mn2O3, and utilizes bidentate chelating ligands to capture Mg2+. The robust coordination effect of terminal biprotonic amine in EDA enhances the structural diversity and specific capacity characteristics of the composite material, as further corroborated by density functional theory (DFT) calculations, ex situ XRD, XPS, and Raman spectroscopy. As expected, the EDA-Mn2O3 composite achieved an outstanding specific discharge capacity of 188.97â mAh/g at 0.1â A/g. Additionally, an aqueous magnesium ion capacitor with EDA-Mn2O3 serving as the cathode can reach 110.17â Wh/kg, which stands out among the aqueous magnesium ion capacitors that have been reported thus far. The abundant reversible redox sites are ensured by the strategic design concept based on the synergistic structure and composition advantages of organic and inorganic phases. This study aimed to explore the practical application value of organic-inorganic composite electrodes with double-energy storage mechanisms.
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Electrocatalysis is a highly promising technology widely used in clean energy conversion. There is a continuing need to develop advanced electrocatalysts to catalyze the critical electrochemical reactions. Integrating metal active species, including various metal nanostructures (NSs) and atomically dispersed metal sites (ADMSs), into metal-organic frameworks (MOFs) leads to the formation of promising heterogeneous electrocatalysts that take advantage of both components. Among them, MOFs can provide support and protection for the active sites on guest metals, and the resulting host-guest interactions can synergistically enhance the electrocatalytic performance. In this review, three key concerns on MOF-metal heterogeneous electrocatalysts regarding the catalytic sites, conductivity, and catalytic stability are first presented. Then, rational integration strategies of MOFs and metals, including the integration of metal NSs via surface anchoring, space confining, and MOF coating, as well as the integration of ADMSs either with the metal nodes/linkers or within the pores of MOFs, along with their recent progress on synergistic cooperation for specific electrochemical reactions are summarized. Finally, current challenges and possible solutions in applying these increasingly concerned electrocatalysts are also provided.
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Tin sulfide (SnS) is an attractive anode for sodium ion batteries (NIBs) because of its high theoretical capacity, while it seriously suffers from the inherently poor conductivity and huge volume variation during the cycling process, leading to inferior lifespan. To intrinsically maximize the sodium storage of SnS, herein, lithium azides (LiN3 )-induced SnS quantum dots (QDs) are first reported using a simple electrospinning strategy, where SnS QDs are uniformly distributed in the carbon fibers. Taking the advantage of LiN3 , which can effectively prevent the growth of crystal nuclei during the thermal treatment, the well-dispersed SnS QDs performs superior Na+ transfer kinetics and pseudocapacitive when used as an anode material for NIBs. The 3D SnS quantum dots embedded uniformly in N-doped nanofibers (SnS QDs@NCF) electrodes display superior long cycling life-span (484.6 mAh g-1 after 5800 cycles at 2 A g-1 and 430.9 mAh g-1 after 7880 cycles at 10 A g-1 ), as well as excellent rate capability (422.3 mAh g-1 at 20 A g-1 ). This fabrication of transition metal sulfides QDs composites provide a feasible strategy to develop NIBs with long life-span and superior rate capability to pave its practical implementation.
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The development of electric vehicles has received worldwide attention in the background of reducing carbon emissions, wherein lithium-ion batteries (LIBs) become the primary energy supply systems. However, commercial graphite-based anodes in LIBs currently confront significant difficulty in enduring ultrahigh power input due to the slow Li+ transport rate and the low intercalation potential. This will, in turn, cause dramatic capacity decay and lithium plating. The 2D layered materials (2DLMs) recently emerge as new fast-charging anodes and hold huge promise for resolving the problems owing to the synergistic effect of a lower Li+ diffusion barrier, a proper Li+ intercalation potential, and a higher theoretical specific capacity with using them. In this review, the background and fundamentals of fast-charging for LIBs are first introduced. Then the research progress recently made for 2DLMs used for fast-charging anodes are elaborated and discussed. Some emerging research directions in this field with a short outlook on future studies are further discussed.
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Sodium metal battery is supposed to be a propitious technology for high-energy storage application owing to the advantages of natural abundance and low cost. Unfortunately, the uncontrollable dendrite growth critically hampers its practical implementation. Herein, an inorganic/organic hybrid layer of NaF/CF/CC on the surface of Na foil (IOHL-Na) is designed and synthesized through the in situ reaction of polyvinylidene fluoride (PVDF) and metallic sodium. This protective layer possesses satisfactory Young's modulus, good kinetic property, and sodiophilicity, which can distinctly stabilize Na metal anode. As a result, the symmetric IOHL-Na cell achieves a lifespan of 770 h at 1 mAh cm-2 /1 mA cm-2 in carbonate electrolyte. The assembled full battery of IOHL-Na||Na3 V2 (PO4 )3 delivers a high discharge capacity of 85 mAh g-1 at 10 C after 600 cycles under ambient temperature. Furthermore, the IOHL-Na||Na3 V2 (PO4 )3 cell still can steadily operate at 10 C for 600 cycles at 55 °C. And when testing at an ultralow temperature of -40 °C, the full cell achieves 40 mAh g-1 at 0.5 C with a prolonged lifespan of 450 cycles. This work offers a new approach to protect the metal sodium anode without dendrite growth under wide temperatures.
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Metal-free 2D phosphorus-based materials are emerging catalysts for ammonia (NH3 ) production through a sustainable electrochemical nitrogen reduction reaction route under ambient conditions. However, their efficiency and stability remain challenging due to the surface oxidization. Herein, a stable phosphorus-based electrocatalyst, silicon phosphide (SiP), is explored. Density functional theory calculations certify that the N2 activation can be realized on the zigzag Si sites with a dimeric end-on coordinated mode. Such sites also allow the subsequent protonation process via the alternating associative mechanism. As the proof-of-concept demonstration, both the crystalline and amorphous SiP nanosheets (denoted as C-SiP NSs and A-SiP NSs, respectively) are obtained through ultrasonic exfoliation processes, but only the crystalline one enables effective and stable electrocatalytic nitrogen reduction reaction, in terms of an NH3 yield rate of 16.12 µg h-1 mgcat. -1 and a Faradaic efficiency of 22.48% at -0.3 V versus reversible hydrogen electrode. The resistance to oxidization plays the decisive role in guaranteeing the NH3 electrosynthesis activity for C-SiP NSs. This surface stability endows C-SiP NSs with the capability to serve as appealing electrocatalysts for nitrogen reduction reactions and other promising applications.
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Anion-exchange membrane (AEM) water electrolyzers (AEMWEs) and fuel cells (AEMFCs) are technologies that, respectively, achieve transformation and utilization of renewable resources in the form of green hydrogen (H2) energy. The significantly reduced cost of their key components (membranes, electrocatalysts, bipolar plates, etc.), quick reaction kinetics, and fewer corrosion problems endow AEM water electrolyzers and fuel cells with overwhelming superiority over their conventional counterparts (e.g., proton-exchange membrane water electrolyzer/fuel cells and alkaline water electrolyzer/fuel cells). Limitations in our fundamental understanding of AEM devices, however, specifically in key components, working management, and operation monitoring, restrict the improvement of cell performance, and they further impede the deployment of AEM water electrolyzers and fuel cells. Therefore, a panoramic view to outline the fundamentals, technological progress, and future perspectives on AEMWEs and AEMFCs is presented. The objective of this review is to (1) present a timely overview of the market development status of green hydrogen technology that is closely associated with AEMWEs (hydrogen production) and AEMFCs (hydrogen utilization); (2) provide an in-depth and comprehensive analysis of AEMWEs and AEMFCs from the viewpoint of all key components (e.g., membranes, ionomers, catalysts, gas diffusion layers, bipolar plates, and membrane electrode assembly (MEA)); (3) summarize the state-of-the-art technologies for working management of AEMWEs and AEMFCs, including electrolyte engineering (electrolyte selection and feeding), water management, gas and heat management, etc.; (4) outline the advances in monitoring the operations of AEMWEs and AEMFCs, which include microscopic and spectroscopic techniques and beyond; and (5) present key aspects that need to be further studied from the perspective of science and engineering to accelerate the deployment of AEMWEs and AEMFCs.