Controllable and large-area growth of ZnO nanosheet arrays under ambient condition as superior anodes for scalable aqueous batteries

Two-dimensional(2D)oxides have been the focus of substantial research interest recently,owing to their fascinating physico-chemical properties.However,fabrication of large-area 2D oxide materials in a controlled manner under mild conditions still remains a formidable challenge.Herein,we develop a facile and universal strategy based on the sonochemistry approach for controllable and large-area growth of quasi-aligned single-crystalline ZnO nanosheets on a Zn substrate(Zn@SC-ZnO)under ambient conditions.The obtained ZnO nanosheets possess the desired exclusively exposed(001)facets,which have been confirmed to play a critical role in significantly reducing the activation energy and facilitating the stripping/plating processes of Zn.Accordingly,the constructed Zn@SC-ZnO||Zn@SC-ZnO symmetric cell has very low polarization overpotential down to~20 mV,with limited dendrite growth and side reactions for Zn anodes.The developed Zn@SC-ZnO//MnO_(2)aqueous Zn-ion batteries(ZIBs)show a voltage efficiency of 88.2%under 500 mA g^(-1)at the stage of 50%depth of discharge,which is state of the art for ZIBs reported to date.Furthermore,the as-assembled large-size cell(5 cm×5 cm)delivers an open circuit potential of 1.648 V,and can be robustly operated under a high current of 20 mA,showing excellent potential for future scalable applications.

Highly Enhanced Visible-Light-Driven Photoelectrochemical Performance of ZnO-Modified In_2S_3 Nanosheet Arrays by Atomic Layer Deposition

Photoanodes based on In_2S_3/ZnO heterojunction nanosheet arrays(NSAs) have been fabricated by atomic layer deposition of ZnO over In_2S_3 NSAs, which were in situ grown on fluorine-doped tin oxide glasses via a facile solvothermal process. The as-prepared photoanodes show dramatically enhanced performance for photoelectrochemical(PEC) water splitting, compared to single semiconductor counterparts. The optical and PEC properties of In_2S_3/ZnO NSAs have been optimized by modulating the thickness of the Zn O overlayer. After pairing with ZnO, the NSAs exhibit a broadened absorption range and an increased light absorptance over a wide wavelength region of 250–850 nm. The optimized sample of In_2S_3/ZnO-50 NSAs shows a photocurrent density of 1.642 m A cm^(-2)(1.5 V vs. RHE) and an incident photonto-current efficiency of 27.64% at 380 nm(1.23 V vs.RHE), which are 70 and 116 times higher than those of the pristine In_2S_3 NSAs, respectively. A detailed energy band edge analysis reveals the type-II band alignment of the In_2S_3/ZnO heterojunction, which enables efficient separation and collection of photogenerated carriers,especially with the assistance of positive bias potential, and then results in the significantly increased PEC activity.

Rapid and reversible Na deposition onto Al nanosheet arrays

Sodium metal battery(SMB)is regarded as a promising candidate for next-generation high-energy battery due to high theoretical capacity and abundant natural resources.However,the growth of sodium dendrites and large volume expansion during the processes of sodium plating and stripping seriously restrict the practical application of SMBs.Here,a three-dimensional skeleton of aluminum nanosheet arrays(Al NSARs)is constructed by a facile etching approach to achieve rapid and reversible Na plating/stripping.The Al NSARs with large geometric specific surface and plentiful cavities can provide rich active nucleation sites,reduce local current density and accommodate Na volume change,which lead to uniform deposition of sodium with dendrite-free morphology.As a result,Na plating/stripping on Al NSARs can stably operate over 650 cycles at 2 mA cm^(-2)/2 mAh cm^(-2)with average Coulombic efficiency(CE)of 100.0%and low potential polarization of 27 mV.Moreover,the full cell of Na_(s)V_(2)(PO_(4))_(3)||Al NSARs@Na can run for over 1800 cycles at a high rate of 20C.These superior properties,combined with relatively low cost and weight of Al,enable our AlNSARs to begreat prospect for practical applications.

Tuning electronic configuration of WP_(2) nanosheet arrays via nickel doping for high-efficiency hydrogen evolution reaction

Modulate the electronic structure and surface energy by nanostructure and heteroatom doping is an efficient strategy to improve electrocatalytic activity of hydrogen evolution reaction(HER).Herein,nickel incorporated WP_(2) self-supporting nanosheet arrays cathode was synthesized on carbon cloth(Ni-WP_(2) NS/CC)by in-situ phosphating reduction of the Ni-doped WO3.It shows that heteroatom doping and the three-dimensional(3D)nanosheet arrays morphology both facilitate to reduce the interfacial transfer resistance and increase electrochemical-active surface areas,which effectively improve electrocatalytic hydrogen evolution reaction(HER)activity.The optimized catalyst,1%Ni-WP_(2) NS/CC,exhibits an outstanding electrocatalytic performance with an overpotential of 110 m V at 10 m A cm^(-2) and a Tafel slope of 65 m V dec^(-1) in the acid solution.DFT calculations further demonstrate the nickel doping can adjust the intrinsic structure of electronics,lower the Gibbs free energy of adsorption of hydrogen(DGH*),and effectively improve the HER performance.

A Wire-Shaped Supercapacitor in Micrometer Size Based on Fe_3O_4 Nanosheet Arrays on Fe Wire

One-dimensional(1D, wire-and fiber-shaped)supercapacitors have recently attracted interest due to their roll-up, micrometer size and potential applications in portable or wearable electronics. Herein, a 1D wireshaped electrode was developed based on Fe_3O_4 nanosheet arrays connected on the Fe wire, which was prepared via oxidation of Fe wire in 0.1 M KCl solution(pH 3) with O2-rich environment under 70 °C. The obtained Fe_3O_4 nanosheet arrays displayed a high specific capacitance(20.8 m F cm^(-1) at 10 mV s^(-1)) and long cycling lifespan(91.7% retention after 2500 cycles). Theexcellent performance may attribute to the connected nanosheet structure with abundant open spaces and the intimate contact between the Fe_3O_4 and iron substrate. In addition, a wire-shaped asymmetric supercapacitor was fabricated and had excellent capacitive properties with a high energy density(9 l Wh cm^(-2)) at power density of 532.7 l W cm^(-2) and remarkable long-term cycling performance(99% capacitance retention after 2000 cycles).Considering low cost and earth-abundant electrode material, as well as outstanding electrochemical properties, the assembled supercapacitor will possess enormous potential for practical applications in portable electronic device.

Synchronous regulation of morphology and electronic structure of FeNi-P nanosheet arrays by Zn implantation for robust overall water splitting

FeNi-based phosphides are one of the most hopeful electrocatalysts,whereas the significant challenge is to achieve prominent bifunctional catalytic activity with low voltage for water splitting.The morphology and electronic structure of FeNi-based phosphides can intensively dominate effective catalysis,therefore their simultaneous regulating is extremely meaningful.Herein,a robust bifunctional catalyst of Zn-implanted FeNi-P nanosheet arrays(Zn-FeNi-P)vertically well-aligned on Ni foam is successfully fabricated by Zn implanting strategy.The Zn fulfills the role of electronic donor due to its low electronegativity to enhance the electronic density of FeNi-P for optimized water dissociation kinetics.Meanwhile,the implantation of Zn into FeNi-P can effectively regulate morphology of the catalyst from thick and irregular nanosheets to ultrathin lamellar structure,which generates enriched catalytic active sites,leading to accelerating electron/mass transport ability.Accordingly,the designed Zn-FeNi-P catalyst manifests remarkable hydrogen evolution reaction(HER)activity with low overpotentials of 55 and 225 mV at 10 and 200 mA·cm^(−2),which is superior to the FeNi-P(82 mV@10 mA·cm^(−2)and 301 mV@200 mA·cm^(−2)),and even out-performing the Pt/C catalyst at a high current density>200 mA·cm^(−2).Moreover,the oxygen evolution reaction(OER)activity of Zn-FeNi-P also has dramatically improved(207 mV@10 mA·cm^(−2))comparable to FeNi-P(221 mV@10 mA·cm^(−2))and RuO_(2)(239 mV@10 mA·cm^(−2)).Noticeably,an electrolyzer based on Zn-FeNi-P electrodes requires a low cell voltage of 1.47 V to achieve 10 mA·cm^(−2),far beyond the catalytic activities of FeNi-P||FeNi-P(1.51 V@10 mA·cm^(−2))and the benchmark RuO_(2)||Pt/C couples(1.56 V@10 mA·cm^(−2)).This Zn-implanting strategy paves a new perspective for the development of admirable bifunctional catalysts.

Self-transforming ultrathin α-Co(OH)2 nanosheet arrays from metal-organic framework modified graphene oxide with sandwichlike structure for efficient electrocatalytic oxygen evolution

Developing efficient and low-cost electrocatalysts for oxygen evolution reaction(OER)with high electrochemical activity and durability for diverse renewable and sustainable energy technologies remains challenging.Herein,an ultrasonic-assisted and coordination modulation strategy is developed to construct sandwich-like metal-organic framework(MOF)derived hydroxide nanosheet(NS)arrays/graphene oxide(GO)composite via one-step self-transformation route.Inducing from unsteady state,the dodecahedral ZIF-67 with Co^2+in tetrahedral coordination auto-converts into defect-rich ultrathin layered hydroxides with the interlayered ion NO3-.The self-transforming a-Co(OH)2/GO nanosheet arrays from ZIF-67(Co(OH)2-GNS)change the coordination mode of Co^2+and bring about the exposure of more metal active sites,thereby enhancing the spatial utilization ratio within the framework.As monometal-based electrocatalyst,the optimized Co(OH)2-GNS exhibits remarkable OER catalytic performance evidenced by a low overpotential of 259 mV to achieve a current density of 10 mA·cm-2 in alkaline medium,even exceeding commercial RuO2.During the oxygen evolution process,electron migration can be accelerated by the interfacial/in-plane charge polarization and local electric field,corroborated by the off-axis electron holography.Density functional theory(DFT)calculations further studied the collaboration between ultrathin Co(OH)2 NS and GO,which leads to lower energy barriers of intermediate products and greatly promotes electrocatalytic property.

NiS_(2) nanosheet arrays on stainless steel foil as binder-free anode for high-power sodium-ion batteries

Owing to the wide range and low cost of sodium resources,sodium-ion batteries(SIBs)have received extensive attention and research.Metal sulfides with high theoretical capacity are used as promising anode materials for SIBs.This paper presents the electrochemical performance of the binder-free NiS_(2)nanosheet arrays grown on stainless steel(SS)substrate(NiS_(2)/SS)using an in situ growth and sulfidation strategy as anode for sodium ion batteries.Owing to the close connection between the NiS_(2)nanosheet arrays and the SS current collector,the NiS_(2)/SS anode demonstrates high rate capability with a reversible capacity of 492.5 mAh·g^(-1)at 5.0C rate.Such rate capability is superior to that of NiS_(2)nanoparticles(NiS_(2)/CMC:41.7 mAh·g^(-1)at 5.0C,NiS_(2)/PVDF:7.3 mAh·g^(-1)at 5.0C)and other Ni sulfides(100–450 mAh·g^(-1)at 5.0C)reported.Furthermore,the initial reversible specific capacity and Coulombic efficiency of NiS_(2)/SS are 786.5 mAh·g^(-1)and 81%,respec-tively,demonstrating a better sodium storage ability than those of most NiS_(2)anodes reported for SIBs.In addition,the amorphization and conversion mechanism during the sodiation/desodiation process of NiS_(2)are proposed after investigation by in situ X-ray diffraction(XRD)measurements of intermediate products at successive charge/discharge stages.

Coupling of NiFe-Based Metal-Organic Framework Nanosheet Arrays with Embedded Fe-Ni_(3)S_(2) Clusters as Efficient Bifunctional Electrocatalysts for Overall Water Splitting

Developing highly efficient,easy-to-make and cost-effective bifunctional electrocatalysts for water splitting with lower cell voltages is crucial to producing massive hydrogen fuel.In response,the coupled hierarchical Ni/Fe-based MOF nanosheet arrays with embedded metal sulfide nanoclusters onto nickel foam skeleton(denoted as Fe-Ni_(3)S_(2)@NiFe-MOF/NF)are fabricated,in which the Fe-Ni_(3)S_(2) clusters could effectively restrain the aggregation of the layer metal-organic frameworks(MOF)nanosheets and adjust the local electronic structures of MOFs nanosheets.Benefiting from the rapid charge transfer and the exposure of abundant active sites,the well-designed Fe-Ni_(3)S_(2)@NiFe-MOF/NF displays excellent oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)performance.More importantly,when equipped in the alkaline water electrolyzer,the Fe-Ni_(3)S_(2)@Ni Fe-MOF/NF enables the system with a mere 1.6 V for achieving the current density of 10 mA cm^(-2).This work offers a paradigm for designing efficient bifunctional HER/OER electrocatalysts based on the hybrid materials of nanostructured metal sulfide and MOF.

Carbon-based nanoarrays embedded with Ce-doped ultrasmall Co_(2)P nanoparticles enable efficient electrooxidation of 5-hydroxymethylfurfural coupled with hydrogen production

The electrooxidation of 5-hydroxymethylfurfural(HMFOR)not only offers a green route to attain high-value 2,5-furandicarboxylic acid(FDCA)from biomass,but also is considered as a promising approach to replace the kinetically sluggish OER for future hydrogen production.Herein,we report the construction and structural optimization of Ce-doped ultrasmall Co_(2)P nanoparticles(NPs)in carbon-based nanoarrays to boost HER-coupled HMFOR.We demonstrate that the electronic structure of Co-based electrocatalysts can be positively regulated by Ce doping and the optimized Ce-Co_(2)P-based electrocatalyst only require a low voltage of 1.20 V vs.RHE to achieve 10 m A cm^(-2)for HMFOR with an excellent FDCA Faraday efficiency(FEFDCA)of 98.5%,which are superior to its Ce-free counterpart(1.29 V vs.RHE;FEFDCA=83.9%).When being assembled into a HERcoupled HMFOR system,this bifunctional electrocatalyst can achieve 50 m A cm^(-2)with an ultralow voltage of 1.46 V,which is reduced by 210 m Vas compared with that of its Ce-free counterpart(1.67 V).Quasi-operando experiments and DFTcalculations further reveal the significant roles of Ce doping in promoting the charge transfer between active sites and HMF,and reducing the free energy barrier of intermediate(^(*)HMFCA)dehydrogenation.This study provides new insights into the underlying mechanisms of Ce doping into metal phosphides for boosting HER-coupled HMFOR,developing a facile methodology to construct efficient electrocatalysts for energy storage/conversion systems.

A 3D porous WP2 nanosheets@carbon cloth flexible electrode for efficient electrocatalytic hydrogen evolution

Self-standing porous WP2 nanosheet arrays on carbon fiber cloth （WP2 NSs/CC） were synthesized and used as a 3D flexible hydrogen evolution electrode. Because of its 3D porous nanoarray structure, the WP2 NSs/CC exhibits a remarkable catalytic activity and a high stability. By using the experimental measurements and first-principle calculations, the underlying reasons for the excellent catalytic activity were further explored. Our work makes the present WPz NSs as a promising electrocatalyst for hydrogen evolution and provides a way to design and fabricate efficient hydrogen evolution electrodes through 3D porous nano-arrays architecture.

兼具异质结构和锰掺杂的Ni_(2)P纳米片阵列用于高效电催化水分解

目前,开发低成本、稳定的电解水催化剂变得十分紧迫.本工作通过简单的水热反应,磷化及硫化处理,将三维Ni_(2)P纳米片阵列通过异质结工程和锰掺杂进行修饰.受益于锰掺杂,异质结构内部的协同作用以及三维纳米片阵列所暴露的丰富活性位点,Mn掺杂Ni_(2)O_(3)/Ni_(2)P和Mn掺杂Ni_(x)S_(y)/Ni_(2)P分别表现出优异的析氢和析氧催化性能.其中,它们分别在104和290 mV的过电位下获得-10和100 mA cm^(-2)电流密度.此外,Mn掺杂Ni_(x)S_(y)/Ni_(2)P在50 mA cm^(-2)的电流密度下能稳定运行160 h.以Mn掺杂Ni_(2)O_(3)/Ni_(2)P和Mn掺杂Ni_(x)S_(y)/Ni_(2)P分别作为阴极和阳极组成的全水分解电解池,不仅在1.65 V的电池电压下获得10 mA cm^(-2)的电流密度,而且在50 mA cm^(-2)的电流密度下仍能稳定运行120 h.本研究工作不仅提供了一种同时利用异质结工程、锰掺杂和三维纳米结构阵列的策略来设计和制备高活性的电解水催化剂,还提出了大规模制备应用于可再生能源器件的非贵金属电催化剂的新方向.

Improving Na^(+)transport kinetics and Na^(+)storage of hierarchical rhenium-nickel sulfide(ReS_(2)@NiS_(2))hollow architecture by assembling layered 2D-3D heterostructures

Mixed metal sulfides have been widely used as anode material of sodium-ion batteries(SIBs)because of their excellent conductivity and sodium ion storage performance.Herein,ReS_(2)@NiS_(2)heterostructures have been triumphantly designed and prepared through anchoring ReS_(2)nanosheet arrays on the surface of NiS_(2)hollow nanosphere.Specifically,the carbon nanospheres was used as hard template to synthesize NiS_(2)hollow spheres as the substrate and then the ultrathin two-dimensional ReS_(2)nanosheet arrays were uniformly grown on the surface of NiS_(2).The internal hollow property provides sufficient space to relieve the volume expansion,and the outer two-dimensional nanosheet realizes the rapid electron transport and insertion/extraction of Na^(+).Owing to the great improvement of the transport kinetics of Na^(+),NiS_(2)@ReS_(2)heterostructure electrode can achieve a high specific capacity of 400 mAh/g at the high current density of 1 A/g and still maintain a stable cycle stability even after 220 cycles.This hard template method not only paves a new way for the design and construct binary metal sulfide heterostructure electrode materials with outstanding electrochemical performance for Na^(+)batteries but also open up the potential applications of anode materials of SIBs.

Synergistic tuning of electrochemical surface area and surface Co^(3+)by oxygen plasma enhances the capacities of Co_(3)O_(4)lithium-oxygen battery cathodes

Modifying electrochemical surface area(ECSA)and surface chemistry are promising approaches to enhance the capacities of oxygen cathodes for lithium-oxygen(Li-O_(2))batteries.Although various chemical approaches have been successfully used to tune the cathode surface,versatile physical techniques including plasma etching etc.could be more effortless and effective than arduous chemical treatments.Herein,for the first time,we propose a facile oxygen plasma treatment to simultaneously etch and modify the surface of Co_(3)O_(4)nanosheet arrays(NAs)cathode for Li-O_(2)batteries.The oxygen plasma not only etches Co_(3)O_(4)nanosheets to enhance the ECSA but also lowers the oxygen vacancy concentration to enable a Co^(3+)-rich surface.In addition,the NA architecture enables the full exposure of oxygen vacancies and surface Co^(3+)that function as the catalytically active sites.Thus,the synergistic effects of enhanced ECSA,modest oxygen vacancy and high surface Co^(3+)achieve a significantly enhanced reversible capacity of 3.45 mAh/cm^(2)for Co_(3)O_(4)NAs.This work not only develops a promising high-capacity cathode for Li-O_(2)batteries,but also provides a facile physical method to simultaneously tune the nanostructure and surface chemistry of energy storage materials.