Advance in 3D self-supported amorphous nanomaterials for energy storage and conversion

The advancement of next-generation energy technologies calls for rationally designed and fabricated electrode materials that have desirable structures and satisfactory performance.Three-dimensional(3D)self-supported amorphous nanomaterials have attracted great enthusiasm as the cornerstone for building high-performance nanodevices.In particular,tremendous efforts have been devoted to the design,fabrication,and evaluation of self-supported amorphous nanomaterials as electrodes for energy storage and conversion devices in the past decade.However,the electrochemical performance of devices assembled with 3D self-supported amorphous nanomaterials still remains to be dramatically promoted to satisfy the demands for more practical applications.In this review,we aim to outline the achievements made in recent years in the development of 3D self-supported amorphous nanomaterials for a broad range of energy storage and conversion processes.We firstly summarize different synthetic strategies employed to synthesize 3D nanomaterials and to tailor their composition,morphology,and structure.Then,the performance of these 3D self-supported amorphous nanomaterials in their corresponding energy-related reactions is highlighted.Finally,we draw out our comprehensive understanding towards both challenges and prospects of this promising field,where valuable guidance and inspiration will surely facilitate further development of 3D self-supported amorphous nanomaterials,thus enabling more highly efficient energy storage and conversion devices that play a key role in embracing a sustainable energy future.

Wet-chemical synthesis and applications of amorphous metalcontaining nanomaterials

In the past decades,metal-containing nanomaterials have attracted increasing interests owing to their intriguing physicochemical properties and various promising applications.Recent research has revealed that the phase of metal-containing nanomaterials could significantly affect their properties and functions.In particular,nanomaterials with amorphous phase,which possess long-range disordered atomic arrangements,and the amorphous/crystalline heterophase nanostructures comprised of both amorphous and crystalline phases,have exhibited superior performance in various applications,e.g.,catalysis and energy storage.In this review,a brief overview of the recent progress on the wet-chemical synthesis and applications of amorphous and amorphous/crystalline heterophase metal-containing nanomaterials has been provided.Subsequently,on the basis of different categories of metal-containing nanomaterials,including metals,metal alloys,and metal compounds,their synthetic routes and promising applications will be highlighted.Finally,current challenges and some personal perspectives in this emerging research field will be proposed.

Amorphous hybrid tungsten oxide–nickel hydroxide nanosheets used as a highly efficient electrocatalyst for hydrogen evolution reaction

There are more challenges for alkaline hydrogen evolution reaction(HER)via simultaneously expediting the electron-coupled water dissociation process(Volmer step)and the following electrochemical H_(2) desorption(Heyrovsky step).Hybrid amorphous electrocatalysts are highly desirable for efficient hydrogen evolution from water-alkali electrolyzers due to the bifunctionality for the different elementary steps of HER and optimal interactions with water molecules and the reactive hydrogen intermediates(Had).Herein,the synthesis of amorphous hybrid ultrathin(tungsten oxide/nickel hydroxide)hydrate(a-[WO_(3)/Ni(OH)_(2)]·0.2H_(2)O)nanosheets on nickel foam(NF)for efficient alkaline HER is described.The structural and composition features of a-[WO_(3)/Ni(OH)_(2)]·0.2H_(2)O are characterized in detailed.The resulting a-[WO_(3)/Ni(OH)_(2)]·0.2H_(2)O/NF electrocatalyst with the synergistic effect of both hybrid components for the HER elementary steps shows greatly improved the activity and durability for the HER with a low overpotential of-41 and-163 mV at-10 and-500 mA·cm^(-2),respectively,a Tafel slope as low as-72.9 mV·dec^(-1),and long-term stability of continuous electrolysis for at least 150 h accompanying by inappreciable overpotential change in 1 M KOH.In the hybrid a-[WO_(3)/Ni(OH)_(2)]·0.2H_(2)O,Ni(OH)_(2) and WO_(3) moieties are separately responsible for accelerating dissociative adsorption of water and weakening Had adsorption strength,which is beneficial to the improvement of the alkaline HER activity.

Synthesis of amorphous Pd-based nanocatalysts for efficient alcoholysis of styrene oxide and electrochemical hydrogen evolution

Amorphous nanomaterials with long-range disordered structures could possess distinct properties and promising applications,especially in catalysis,as compared with their conventional crystalline counterparts.It is imperative to achieve the controlled preparation of amorphous noble metal-based nanomaterials for the exploration of their phase-dependent applications.Here,we report a facile wet-chemical reduction strategy to synthesize various amorphous multimetallic Pd-based nanomaterials,including PdRu,PdRh,and PdRuRh.The phase-dependent catalytic performances of distinct Pd-based nanomaterials towards diverse catalytic applications have been demonstrated.Specifically,the usage of PdRu nanocatalysts with amorphous and crystalline face-centered cubic(fcc)phases can efficiently switch the ring-opening route of styrene oxide to obtain different products with high selectivity through alcoholysis reaction and hydrogenation reaction,respectively.Moreover,when used as an electrocatalyst for hydrogen evolution reaction(HER),the synthesized amorphous PdRh nanocatalyst exhibits low overpotential and high turnover frequency values,outperforming its crystalline fcc counterpart and most of the reported Pd-based HER electrocatalysts.

Morphological and structural engineering in amorphous Cu2MoS4 nanocages for remarkable electrocatalytic hydrogen evolution

Morphological and structural control of amorphous nanomaterials is challenging due to the long-range disordered atomic arrangements. Herein, we firstly propose a controllable self-hydrolyzing etching-precipitating (SHEP) method to fabricate the regular-shaped amorphous Cu2MoS4 nanocages (a-Cu2MoS4 NCs) with hollow porous structures under ambient conditions. Benefitting from the hollow porous structures and the amorphous characteristics with copious sulfur vacancies, the a-Cu2MoS4 NCs possess more enhanced activity toward hydrogen evolution reaction (HER) than their crystalline counterparts. The octahedral a-Cu2MoS4 NCs with a shell thickness of 20 nm, which balance the appropriate surface porosity and good structural stability, exhibit the best HER activity with a low overpotential of 96 mV at 10 mA cm^-2 and a small tafel slope of 61 mV decade^-1 in alkaline environment. Moreover, this method is very versatile and can be extended to synthesize other ternary nanocages. Our current work may shed light on the precise controllable synthesis of various ternary nanocages and open a new frontier for developing highly active amorphous catalysts.