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The practical application of aqueous zinc ion batteries is still hampered by the side reactions and dendrite growth on Zn anode. Herein, the phase engineering of ZnSe coating layer by incorporating small molecules is developed to enhance the performance of Zn anode. The unique electronic structure of ZnSe⋅0.5N 2 H 4 promises strong adsorption for Zn atoms and enhanced ability to inhibit hydrogen evolution, thereby promoting uniform Zn deposition and preventing by-product and dendrite growth. Meanwhile, fast Zn 2+ transfer and deposition kinetics are also demonstrated by ZnSe⋅0.5N 2 H 4 . As a result, the ZnSe⋅0.5N 2 H 4 @Zn symmetric cell achieves long-term cycling stability up to 1900 h and 300 h at high current densities of 5 mA cm -2 and 20 mA cm -2 , respectively. The assembled ZnSe⋅0.5N 2 H 4 @Zn||NH 4 V 4 O 10 full cell presents outstanding cycling stability and rate capability. This work highlights the key role of crystal phase control of protective layer for high-performance zinc anode., (© 2024 Wiley-VCH GmbH.)

It is still challenging to develop an effective strategy to simultaneously enhance the activity and stability of electrocatalysts for electrocatalytic nitrate reduction reaction (eNO 3 RR). Herein, taking metallic cobalt as an example, it is demonstrated that the construction of low-coordinated cobalt nanosheets (L-Co NSs) by H 2 plasma etching of electrodeposited cobalt nanosheets (Co NSs) can greatly enhance the activity and stability of metallic cobalt for eNO 3 RR. Compared with Co NSs, at -0.4 V versus RHE, the nitrate removal rate, ammonia partial current density, and ammonia yield are increased by L-Co NSs from 82.14% to 98.57%, from 476 to 683 mA cm -2 , and from 2.11 to 2.54 mmol h -1 cm -2 , respectively. In addition, L-Co NSs demonstrate negligible activity decay after 30 cycles of stability test, while the Co NSs show significant activity decline. In situ electrochemical characterizations and theoretical calculations verify that the abundance of Co vacancies in L-Co NSs not only contribute to the optimized electronic structure and enhanced desorption of key intermediate to boost the activity but also facilitate the transformation of Co(OH) 2 to Co 0 to promote the stability. Furthermore, L-Co NSs exhibit favorable performance in removing nitrate from simulated wastewater and air plasma discharge-electrocatalytic reduction cascade system to produce ammonia., (© 2025 Wiley‐VCH GmbH.)

Electrochemical nitrate reduction reaction (NO 3 RR) is a promising approach to achieve remediation of nitrate-polluted wastewater and sustainable production of ammonia. However, it is still restricted by the low activity, selectivity and Faraday efficiency for ammonia synthesis. Herein, we propose an effective strategy to modulate the electrolyte microenvironment in electrical double layer (EDL) by mediating alkali metal cations in the electrolyte to enhance the NO 3 RR performance. Taking bulk Cu as a model catalyst, the experimental study reveals that the NO 3 - -to-NH 3 performance in different electrolytes follows the trend Li + + + + . Theoretical studies illustrate that the proton transport rate in NO 3 RR and the activity of the rate-determining step (NO 3 - to NO 2 - ) increase in the order Li + + + + . The cation effects are also general for two typical nanostructured catalysts including copper/cuprous oxide and nickel phosphides, achieving near-100 % Faradaic efficiency and over 99 % conversion of NO 3 - to NH 3 . Furthermore, we demonstrate that NO 3 - can be converted to high-purity NH 4 Cl by copper/cuprous oxide catalyst in K + -containing electrolyte., (© 2024 Wiley-VCH GmbH.)

Developing efficient oxygen evolution reaction (OER) electrocatalysts for seawater electrolysis is still a big challenge. Herein, a facile one-pot approach is reported to synthesize RuO 2 -incorporated NiFe-metal organic framework (RuO 2 /NiFe-MOF) with unique nanobrick-nanosheet heterostructure as precatalyst. Driven by electric field, the RuO 2 /NiFe-MOF dynamically reconstructs into RuO 2 nanoparticles-anchored NiFe oxy/hydroxide nanosheets (RuO 2 /NiFeOOH) with coherent interface, during which the dissolution and redeposition of RuO 2 are witnessed. Owing to the synergistic interaction between RuO 2 and NiFeOOH, the as-reconstructed RuO 2 /NiFeOOH exhibits outstanding alkaline OER activity with an ultralow overpotential of 187.6 mV at 10 mA cm -2 and a small Tafel slope of 31.9 mV dec -1 and excellent durability at high current densities of 840 and 1040 mA cm -2 in 1 m potassium hydroxide (KOH). When evaluated for seawater oxidation, the RuO 2 /NiFeOOH only needs a low overpotential of 326.2 mV to achieve 500 mA cm -2 and can continuously catalyze OER at 500 mA cm -2 for 100 h with negligible activity degradation. Density function theory calculations reveal that the presence of strong interaction and enhanced charge transfer along the coherent interface between RuO 2 and NiFeOOH ensures improved OER activity and stability., (© 2023 Wiley-VCH GmbH.)

With the development of clean hydrogen energy, the cost effective and high-performance hydrogen evolution reaction (HER) electrocatalysts are urgently required. Herein, a green, facile, and time-efficient Ru doping synergistic with air-plasma treatment strategy is reported to boost the HER performance of CoNi-layered double hydroxide (LDH) nanotube arrays (NTAs) derived from zeolitic imidazolate framework nanorods. The Ru doping and air-plasma treatment not only regulate the oxygen vacancy to optimize the electron structure but also increase the surface roughness to improve the hydrophilicity and hydrogen spillover efficiency. Therefore, the air plasma treated Ru doped CoNi-LDH (P-Ru-CoNi-LDH) nanotube arrays display superior HER performance with an overpotential of 29 mV at a current density of 10 mA cm -2 . Furthermore, by assembling P-Ru-CoNi-LDH as both cathode and anode for two-electrode urea-assisted water electrolysis, a small cell voltage of 1.36 V is needed at 10 mA cm -2 and can last for 100 h without any obvious activity attenuation that showing outstanding durability. In general, the P-Ru-CoNi-LDH can improve the HER performance from intrinsic electronic structure regulation cooperated with extrinsic surface wettability modification. These findings provide an effective intrinsic and extrinsic synergistic effect avenue to develop high performance HER electrocatalysts, which is potential to be applied to other research fields., (© 2021 Wiley-VCH GmbH.)

Metal sulfides with excellent redox reversibility and high capacity are very promising electrode materials for sodium-ion batteries. However, their practical application is still hindered by the poor rate capability and limited cycle life. Herein, a template-based strategy is developed to synthesize nitrogen-doped carbon-coated Cu 9 S 5 bullet-like hollow particles starting from bullet-like ZnO particles. With the structural and compositional advantages, these unique nitrogen-doped carbon-coated Cu 9 S 5 bullet-like hollow particles manifest excellent sodium storage properties with superior rate capability and ultra-stable cycling performance., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Hollow micro-/nanostructures have attracted tremendous interest owing to their intriguing structure-induced physicochemical properties and great potential for widespread applications. With the development of modern synthetic methodology and analytical instruments, a rapid structural/compositional evolution of hollow structures from simple to complex has occurred in recent decades. Here, an updated overview of research progress made in the synthesis of hollow structures is provided. After an introduction of definition and classification, achievements in synthetic approaches for these delicate hollow architectures are presented in detail. According to formation mechanisms, these strategies can be categorized into four different types, including hard-templating, soft-templating, self-templated, and template-free methods. In particular, the rationales and emerging innovations in conventional templating syntheses are in focus. The development of burgeoning self-templating strategies based on controlled etching, outward diffusion, and heterogeneous contraction is also summarized. In addition, a brief overview of template-free methods and recent advances on combined mechanisms is provided. Notably, the strengths and weaknesses of each category are discussed in detail. In conclusion, a perspective on future trends in the research of hollow micro-/nanostructures is given., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Antimony-based electrode materials with high specific capacity have aroused considerable interest as anode materials for sodium-ion batteries (SIBs). Herein, we develop a template-engaged ion-exchange method to synthesize Sb 2 Se 3 microclips, and the as-obtained Sb 2 Se 3 microclips are further in situ coated with polypyrrole (PPy). Benefiting from the structural and compositional merits, these PPy-coated Sb 2 Se 3 microclips exhibit enhanced sodium-storage properties in terms of high reversible capacity, superior rate capability, and stable cycling performance., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Electrode materials based on electrochemical conversion reactions have received considerable interest for high capacity anodes of sodium-ion batteries. However, their practical application is greatly hindered by the poor rate capability and rapid capacity fading. Tuning the structure at nanoscale and increasing the conductivity of these anode materials are two effective strategies to address these issues. Herein, a two-step ion-exchange method is developed to synthesize hierarchical Cu-doped CoSe 2 microboxes assembled by ultrathin nanosheets using Co-Co Prussian blue analogue microcubes as the starting material. Benefitting from the structural and compositional advantages, these Cu-doped CoSe 2 microboxes with improved conductivity exhibit enhanced sodium storage properties in terms of good rate capability and excellent cycling performance., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Metal-organic frameworks (MOFs) have drawn tremendous attention because of their abundant diversity in structure and composition. Recently, there has been growing research interest in deriving advanced nanomaterials with complex architectures and tailored chemical compositions from MOF-based precursors for electrochemical energy storage and conversion. Here, a comprehensive overview of the synthesis and energy-related applications of complex nanostructures derived from MOF-based precursors is provided. After a brief summary of synthetic methods of MOF-based templates and their conversion to desirable nanostructures, delicate designs and preparation of complex architectures from MOFs or their composites are described in detail, including porous structures, single-shelled hollow structures, and multishelled hollow structures, as well as other unusual complex structures. Afterward, their applications are discussed as electrode materials or catalysts for lithium-ion batteries, hybrid supercapacitors, water-splitting devices, and fuel cells. Lastly, the research challenges and possible development directions of complex nanostructures derived from MOF-based-templates for electrochemical energy storage and conversion applications are outlined., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Tin(II) sulfide (SnS) has been an attractive anode material for sodium ion batteries. Herein, an elegant templating method has been developed for the rational design and synthesis of hierarchical SnS nanotubes composed of ultrathin nanosheets. In order to enhance the electrochemical performance, carbon coated hierarchical SnS nanotubes (denoted as SnS@C nanotubes) have also been obtained by simply adding glucose into the reaction system. Benefiting from their unique structural merits, the SnS@C nanotubes exhibit enhanced sodium storage properties in terms of good cycling performance and superior rate capability., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Layered metal oxides have attracted increasing attention as cathode materials for sodium-ion batteries (SIBs). However, the application of such cathode materials is still hindered by their poor rate capability and cycling stability. Here, a facile self-templated strategy is developed to synthesize uniform P2-Na 0.7 CoO 2 microspheres. Due to the unique microsphere structure, the contact area of the active material with electrolyte is minimized. As expected, the P2-Na 0.7 CoO 2 microspheres exhibit enhanced electrochemical performance for sodium storage in terms of high reversible capacity (125 mAh g -1 at 5 mA g -1 ), superior rate capability and long cycle life (86 % capacity retention over 300 cycles). Importantly, the synthesis method can be easily extended to synthesize other layered metal oxide (P2-Na 0.7 MnO 2 and O3-NaFeO 2 ) microspheres., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Hollow nanostructures have attracted increasing research interest in electrochemical energy storage and conversion owing to their unique structural features. However, the synthesis of hollow nanostructured metal phosphides, especially nonspherical hollow nanostructures, is rarely reported. Herein, we develop a metal-organic framework (MOF)-based strategy to synthesize carbon incorporated Ni-Co mixed metal phosphide nanoboxes (denoted as NiCoP/C). The oxygen evolution reaction (OER) is selected as a demonstration to investigate the electrochemical performance of the NiCoP/C nanoboxes. For comparison, Ni-Co layered double hydroxide (Ni-Co LDH) and Ni-Co mixed metal phosphide (denoted as NiCoP) nanoboxes have also been synthesized. Benefiting from their structural and compositional merits, the as-synthesized NiCoP/C nanoboxes exhibit excellent electrocatalytic activity and long-term stability for OER., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Nickel and cobalt incorporated MoS 2 nanoboxes are synthesized via the reaction between Ni-Co Prussian blue analogue nanocubes and ammonium thiomolybdate. Due to the structural and compositional advantages, these well-defined nanoboxes manifest enhanced electrochemical activity as an electrocatalyst for hydrogen evolution reaction., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Novel Ni-Co-Prussian-blue-analog nano-cages consisting of pyramid-like walls were prepared via a facile chemical etching process with ammonia at room temperature. After annealing in air, the derived Ni-Co mixed oxide nanocages exhibit enhanced electrocatalytic activity and excellent stability toward the oxygen-evolution reaction., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Molybdenum disulfide (MoS2) has received considerable interest for electrochemical energy storage and conversion. In this work, we have designed and synthesized a unique hybrid hollow structure by growing ultrathin MoS2 nanosheets on N-doped carbon shells (denoted as C@MoS2 nanoboxes). The N-doped carbon shells can greatly improve the conductivity of the hybrid structure and effectively prevent the aggregation of MoS2 nanosheets. The ultrathin MoS2 nanosheets could provide more active sites for electrochemical reactions. When evaluated as an anode material for lithium-ion batteries, these C@MoS2 nanoboxes show high specific capacity of around 1000 mAh g(-1), excellent cycling stability up to 200 cycles, and superior rate performance. Moreover, they also show enhanced electrocatalytic activity for the electrochemical hydrogen evolution., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Nanoframe-like hollow structures with unique three-dimensional (3D) open architecture hold great promise for various applications. Current research efforts mainly focus on frame-like noble metals and metal oxides. However, metal sulfides with frame-like nanostructures have been rarely reported. Starting from metal-organic frameworks (MOFs), we demonstrate a novel structure-induced anisotropic chemical etching/anion exchange method to transform Ni-Co Prussian blue analogue (PBA) nanocubes into NiS nanoframes with tunable size. The reaction between Ni-Co PBA nanocube templates and Na2 S in solution leads to the formation of well-defined NiS nanoframes. The different reactivity between the edges and the plane surface of the Ni-Co PBA nanocubes is found to be the key factor for the formation of NiS nanoframes. Benefitting from their structural merits including 3D open structure, small size of primary nanoparticles, high specific surface area, and good structural robustness, the as-derived NiS nanoframes manifest excellent electrochemical performance for electrochemical capacitors and hydrogen evolution reaction in alkaline electrolyte., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Hollow structures of rutile TiO2 , and especially with non-spherical shape, have rarely been reported. Herein, high-quality rutile TiO2 submicroboxes have been synthesized by a facile templating method using Fe2 O3 submicrocubes as removable templates. Compared to other rutile TiO2 nanomaterials, the as-prepared rutile TiO2 submicroboxes manifest superior lithium storage properties in terms of high specific capacity, long-term cycling stability, and excellent rate capability., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Despite the significant advancement in preparing metal oxide hollow structures, most approaches rely on template-based multistep procedures for tailoring the interior structure. In this work, we develop a new generally applicable strategy toward the synthesis of mixed-metal-oxide complex hollow spheres. Starting with metal glycerate solid spheres, we show that subsequent thermal annealing in air leads to the formation of complex hollow spheres of the resulting metal oxide. We demonstrate the concept by synthesizing highly uniform NiCo2O4 hollow spheres with a complex interior structure. With the small primary building nanoparticles, high structural integrity, complex interior architectures, and enlarged surface area, these unique NiCo2O4 hollow spheres exhibit superior electrochemical performances as advanced electrode materials for both lithium-ion batteries and supercapacitors. This approach can be an efficient self-templated strategy for the preparation of mixed-metal-oxide hollow spheres with complex interior structures and functionalities., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Despite the great advantages of hollow structures as electrodes for lithium-ion batteries, one apparent common drawback which is often criticized is their compromised volumetric energy density due to the introduced hollow interior. Here, we design and synthesize bowl-like SnO2 @carbon hollow particles to reduce the excessive hollow interior space while retaining the general advantages of hollow structures. As a result, the tap density can be increased about 30 %. The as-prepared bowl-like SnO2 @carbon hollow particles with conformal carbon support exhibit excellent lithium storage properties in terms of high capacity, stable cyclability and excellent rate capability., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)