Deformable Catalytic Material Derived from Mechanical Flexibility for Hydrogen Evolution Reaction

Deformable catalytic material with excellent flexible structure is a new type of catalyst that has been applied in various chemical reactions,especially electrocatalytic hydrogen evolution reaction(HER).In recent years,deformable catalysts for HER have made great progress and would become a research hotspot.The catalytic activities of deformable catalysts could be adjustable by the strain engineering and surface reconfiguration.The surface curvature of flexible catalytic materials is closely related to the electrocatalytic HER properties.Here,firstly,we systematically summarized self-adaptive catalytic performance of deformable catalysts and various micro–nanostructures evolution in catalytic HER process.Secondly,a series of strategies to design highly active catalysts based on the mechanical flexibility of lowdimensional nanomaterials were summarized.Last but not least,we presented the challenges and prospects of the study of flexible and deformable micro–nanostructures of electrocatalysts,which would further deepen the understanding of catalytic mechanisms of deformable HER catalyst.

Advanced development of grain boundaries in TMDs from fundamentals to hydrogen evolution application

Grain boundary(GB),as a kind of lattice defect,widely exists in two-dimensional transition metal dichalcogenides(2D TMDs),which has complex and diverse influences on the physical/chemical properties of 2D TMDs.GBs are universally considered to be a double-edged sword,although some electrical and mechanical properties of 2D TMDs would be adversely affected leading to the reduced overall quality,certain structure-oriented applications could be realized based on its unique properties.In this review,we first detailed the atomic structure characteristics of GBs and the corresponding techniques,then we systematically summarized the methods of introducing GBs into 2D TMDs.Next,we expounded unique electrical,mechanical,and chemical properties of the GBs in 2D TMDs and clarified its internal relationship with the atomic structure.Moreover,the application of GB structure in hydrogen evolution reaction(HER)is also discussed.In the end,we make a conclusion and put forward outlooks,hoping to further promote the basic research of GB and boost the wide application of 2D TMDs.

Recent advances on liquid intercalation and exfoliation of transition metal dichalcogenides: From fundamentals to applications

The weak van der Waals gap endows two dimensional transition metal dichalcogenides(2D TMDs)with the potential to realize guest intercalation and host exfoliation.Intriguingly,the liquid intercalation and exfoliation is a facile,low-cost,versatile and scalable strategy to modulate the structure and physiochemical property of TMDs via introducing foreign species into interlayer.In this review,firstly,we briefly introduce the resultant hybrid superlattice and disperse nanosheets with tailored properties fabricated via liquid intercalation and exfoliation.Subsequently,we systematically analyze the intercalation phenomenon and limitations of various intercalants in chemical or electrochemical methods.Afterwards,we intensely discuss diverse functionalities of resultant materials,focusing on their potential applications in energy conversion,energy storage,water purification,electronics,thermoelectrics and superconductor.Finally,we highlight the challenges and outlooks for precise and mass production of 2D TMDs-based materials via liquid intercalation and exfoliation.This review enriches the overview of liquid intercalation and exfoliation strategy,and paves the path for relevant high-performance devices.

MoS_(x) nanowire networks derived from[Mo_(3)S_(13)]^(2−) clusters for efficient electrocatalytic hydrogen evolution

Precise design and synthesis of sub-nano scale catalysts with controllable electronic and geometric structures are pivotal for enhancing the hydrogen evolution reaction(HER)performance of molybdenum sulfide(MoS_(2))and unraveling its structure−activity relationship.By leveraging transition molybdenum polysulfide clusters as functional units for multi-level ordering,we successfully designed and synthesized MoS_(x)nanowire networks derived from[Mo_(3)S_(13)]^(2−) clusters via evaporationinduced self-assembly,which exhibit enhanced HER activity attributed to a high density of active sites and dynamic evolution behavior under cathodic potentials.MoS_(x) nanowire networks electrode yields a current density of 100 mA·cm^(−2) at 142 mV in 0.5 M H_(2)SO_(4).This work provides an attractive prospect for optimizing catalysts at the sub-nano scale and offers insights into a strategy for designing catalysts in various gas evolution reactions.

Revisited electrochemical gas evolution reactions from the perspective of gas bubbles

Electrochemical gas evolution reactions are common but essential in many electrochemical processes including water electrolysis.During these processes,gas bubbles are constantly nucleating on reaction interfaces in electrolyte and consequently exert an impact on catalysts and the performance.In the past few decades,extensive studies have been conducted to characterize bubbles with emerging advanced technologies,manage behaviors of bubbles,and apply bubbles to various domains.In this review,we summarize representative discoveries as well as recent advancements in electrochemical gas evolution reactions from the perspective of gas bubbles.Finally,we end up this review with a profound outlook on future research topics from the combination of experiments and theoretical techniques,non-negligible bubble effects,gravity-free situation,and reactions under practical industrial conditions.

Amorphous molybdenum sulfide and its Mo-S motifs:Structural characteristics,synthetic strategies,and comprehensive applications

Amorphous materials are one kind of nonequilibrium materials and have become one of the most active research fields.Compared with crystalline solids,the theory of amorphous materials is still in infancy because their characteristic of atomic arrangement is more like liquid and has no long-range periodicity.Recently,as the representative of amorphous materials,amorphous molybdenum sulfide(a-MoS_(x))with unique physical and chemical properties has been studied extensively.However,considerable debate surrounds the structure–property relationships of a-MoS_(x)owing to its diverse Mo-S motifs.Herein,we summarize recent discoveries and research results regarding a-MoS_(x),whose structural characteristics,synthetic strategies,formation criteria,and comprehensive applications are discussed in detail.Finally,this review is ended with our personal insights and critical outlooks over the development of a-MoS_(x).

Dislocation-strained MoS_(2)nanosheets for high-efficiency hydrogen evolution reaction

Defect engineering is one of the effective strategies to optimize the physical and chemical properties of molybdenum disulfide(MoS_(2))to improve catalytic hydrogen evolution reaction(HER)performance.Dislocations,as a typical defect structure,are worthy of further investigation due to the versatility and sophistication of structures and the influence of local strain effects on the catalytic performance.Herein,this study adopted a low-temperature hydrothermal synthesis strategy to introduce numerous dislocation-strained structures into the in-plane and out-of-plane of MoS_(2)nanosheets.Superior HER catalytic activity of 5.85 mmol·g^(−1)·h^(−1)under visible light was achieved based on the high-density dislocations and the corresponding strain field.This work paves a new pathway for improving the catalytic activity of MoS_(2)via a dislocation-strained synergistic modulation strategy.

Tailoring activation sites of metastable distorted 1T′-phase MoS_(2) by Ni doping for enhanced hydrogen evolution

Heteroatom doping is a promising approach to enhance catalytic activity by modulating physical properties,electronic structure,and reaction pathway.Herein,we demonstrate that appropriate Ni-doping could trigger a preferential transition of the basal plane from 2H(trigonal prismatic)to 1T′(clustered Mo)by inducing lattice distortion and S vacancy(SV)and thus dramatically facilitate its catalytic hydrogen evolution activity.It is noteworthy that the unique catalysts did possess superior catalytic performance of hydrogen evolution reaction(HER).The rate of photocatalytic hydrogen evolution could reach 20.45 mmol·g^(−1)·h^(−1) and reduced only slightly in the long period of the photocatalytic process.First-principles calculations reveal that the distorted Ni-1T′-MoS_(2) with SV could generate favorable water adsorption energy(Ead(H_(2)O))and Gibbs free energy of hydrogen adsorption(∆GH).This work exhibits a facile and promising pathway for synergistically regulating physical properties,electronic structure,or wettability based on the doping strategy for designing HER electrocatalysts.

Revisiting lithium-storage mechanisms of molybdenum disulfide

Molybdenum disulfide(MoS_(2)),a typical two-dimensional transition metallic layered material,attracts tremendous attentions in the electrochemical energy storage due to its excellent physicochemical properties.However,with the deepening of the research and exploration of the lithium storage mechanism of these advanced MoS_(2)-based anode materials,the complex reaction process influenced by internal and external factors hinders the exhaustive understanding of the lithium storage process.To design stable anode material with high performance,it is urgent to review the mechanisms of reported anode materials and summarize the related factors that influence the reaction processes.This review aims to dissect all possible side reactions during charging and discharging process,uncover internal and external factors inducing various anode reactions and finally put forward strategies of controlling high cycling capacity and super-stable lithium storage capability of MoS_(2).This review will be helpful to the design of MoS_(2)-based lithium-ion batteries(LIBs) with excellent cycle performance to enlarge the application fields of these advanced electrochemical energy storage devices.

Ingeniously designed Ni-Mo-S/ZnIn_(2)S_(4) composite for multi-photocatalytic reaction systems

Molybdenum disulfide (MoS_(2)) with low cost, high activity and high earth abundance has been found to be a promising catalyst for the hydrogen evolution reaction (HER), but its catalytic activity is considerably limited due to its inert basal planes. Here, through the combination of theory and experiment, we propose that doping Ni in MoS_(2) as catalyst can make it have excellent catalytic activity in different reaction systems. In the EY/TEOA system, the maximum hydrogen production rate of EY/Ni-Mo-S is 2.72 times higher than that of pure EY, which confirms the strong hydrogen evolution activity of Ni-Mo-S nanosheets as catalysts. In the lactic acid and Na_(2)S/Na_(2)SO_(3) systems, when Ni-Mo-S is used as co-catalyst to compound with ZnIn_(2)S_(4) (termed as Ni-Mo-S/ZnIn_(2)S_(4)), the maximum hydrogen evolution rates in the two systems are 5.28 and 2.33 times higher than those of pure ZnIn_(2)S_(4), respectively. The difference in HER enhancement is because different systems lead to different sources of protons, thus affecting hydrogen evolution activity. Theoretically, we further demonstrate that the Ni-Mo-S nanosheets have a narrower band gap than MoS_(2), which is conducive to the rapid transfer of charge carriers and thus result in multi-photocatalytic reaction systems with excellent activity. The proposed atomic doping strategy provides a simple and promising approach for the design of photocatalysts with high activity and stability in multi-reaction systems.