A liquid Li divertor is a promising alternative for future fusion devices.In this work a new divertor model is proposed,which is processed by 3D-printing technology to accurately control the size of the internal capil...A liquid Li divertor is a promising alternative for future fusion devices.In this work a new divertor model is proposed,which is processed by 3D-printing technology to accurately control the size of the internal capillary structure.At a steady-state heat load of 10 MW m^(-2),the thermal stress of the tungsten target is within the bearing range of tungsten by finite-element simulation.In order to evaluate the wicking ability of the capillary structure,the wicking process at 600℃ was simulated by FLUENT.The result was identical to that of the corresponding experiments.Within 1 s,liquid lithium was wicked to the target surface by the capillary structure of the target and quickly spread on the target surface.During the wicking process,the average wicking mass rate of lithium should reach 0.062 g s^(-1),which could even supplement the evaporation requirement of liquid lithium under an environment>950℃.Irradiation experiments under different plasma discharge currents were carried out in a linear plasma device(SCU-PSI),and the evolution of the vapor cloud during plasma irradiation was analyzed.It was found that the target temperature tends to plateau despite the gradually increased input current,indicating that the vapor shielding effect is gradually enhanced.The irradiation experiment also confirmed that the 3D-printed tungsten structure has better heat consumption performance than a tungsten mesh structure or multichannel structure.These results reveal the application potential and feasibility of a 3D-printed porous capillary structure in plasma-facing components and provide a reference for further liquid-solid combined target designs.展开更多
Metal-organic frameworks(MOFs)have been extensively considered as one of the most promising types of porous and crystalline organic-inorganic materials,thanks to their large specific surface area,high porosity,tailora...Metal-organic frameworks(MOFs)have been extensively considered as one of the most promising types of porous and crystalline organic-inorganic materials,thanks to their large specific surface area,high porosity,tailorable structures and compositions,diverse functionalities,and well-controlled pore/size distribution.However,most developed MOFs are in powder forms,which still have some technical challenges,including abrasion,dustiness,low packing densities,clogging,mass/heat transfer limitation,environmental pollution,and mechanical instability during the packing process,that restrict their applicability in industrial applications.Therefore,in recent years,attention has focused on techniques to convert MOF powders into macroscopic materials like beads,membranes,monoliths,gel/sponges,and nanofibers to overcome these challenges.Three-dimensional(3D)printing technology has achieved much interest because it can produce many high-resolution macroscopic frameworks with complex shapes and geometries from digital models.Therefore,this review summarizes the combination of different 3D printing strategies with MOFs and MOF-based materials for fabricating 3D-printed MOF monoliths and their environmental applications,emphasizing water treatment and gas adsorption/separation applications.Herein,the various strategies for the fabrication of 3D-printed MOF monoliths,such as direct ink writing,seed-assisted in-situ growth,coordination replication from solid precursors,matrix incorporation,selective laser sintering,and digital light processing,are described with the relevant examples.Finally,future directions and challenges of 3D-printed MOF monoliths are also presented to better plan future trajectories in the shaping of MOF materials with improved control over the structure,composition,and textural properties of 3D-printed MOF monoliths.展开更多
Direct air capture(DAC)of CO_(2)plays an indispensable role in achieving carbon-neutral goals as one of the key negative emission technologies.Since large air flows are required to capture the ultradilute CO_(2)from t...Direct air capture(DAC)of CO_(2)plays an indispensable role in achieving carbon-neutral goals as one of the key negative emission technologies.Since large air flows are required to capture the ultradilute CO_(2)from the air,lab-synthesized adsorbents in powder form may cause unacceptable gas pressure drops and poor heat and mass transfer efficiencies.A structured adsorbent is essential for the implementation of gas-solid contactors for cost-and energy-efficient DAC systems.In this study,efficient adsorbent poly(ethyleneimine)(PEI)-functionalized Mg-Al-CO_(3)layered double hydroxide(LDH)-derived mixed metal oxides(MMOs)are three-dimensional(3D)printed into monoliths for the first time with more than 90%adsorbent loadings.The printing process has been optimized by initially printing the LDH powder into monoliths followed by calcination into MMO monoliths.This structure exhibits a 32.7%higher specific surface area and a 46.1%higher pore volume,as compared to the direct printing of the MMO powder into a monolith.After impregnation of PEI,the monolith demonstrates a large adsorption capacity(1.82 mmol/g)and fast kinetics(0.7 mmol/g/h)using a CO_(2)feed gas at 400 ppm at 25℃,one of the highest values among the shaped DAC adsorbents.Smearing of the amino-polymers during the post-printing process affects the diffusion of CO_(2),resulting in slower adsorption kinetics of pre-impregnation monoliths compared to post-impregnation monoliths.The optimal PEI/MeOH ratio for the post-impregnation solution prevents pores clogging that would affect both adsorption capacity and kinetics.展开更多
Superconducting YBa_(2)Cu_(3)O_(7−x)(YBCO)bulks have promising applications in quasi-permanent magnets,levitation,etc.Recently,a new way of fabricating porous YBCO bulks,named direct-ink-writing(DIW)3D-printing method...Superconducting YBa_(2)Cu_(3)O_(7−x)(YBCO)bulks have promising applications in quasi-permanent magnets,levitation,etc.Recently,a new way of fabricating porous YBCO bulks,named direct-ink-writing(DIW)3D-printing method,has been reported.In this method,the customized precursor paste and programmable shape are two main advantages.Here,we have put forward a new way to customize the YBCO 3D-printing precursor paste which is doped with Al_(2)O_(3)nanoparticles to obtain YBCO with higher thermal conductivity.The great rheological properties of precursor paste after being doped with Al_(2)O_(3)nanoparticles can help the macroscopic YBCO samples with high thermal conductivity fabricated stably with high crystalline and lightweight properties.Test results show that the peak thermal conductivity of Al_(2)O_(3)-doped YBCO can reach twice as much as pure YBCO,which makes a great effort to reduce the quench propagation speed.Based on the microstructure analysis,one can find that the thermal conductivity of Al_(2)O_(3)-doped YBCO has been determined by its components and microstructures.In addition,a macroscopic theoretical model has been proposed to assess the thermal conductivity of different microstructures,whose calculated results take good agreement with the experimental results.Meanwhile,a microstructure with high thermal conductivity has been found.Finally,a macroscopic YBCO bulk with the presented high thermal conductivity microstructure has been fabricated by the Al_(2)O_(3)-doped method.Compared with YBCO fabricated by the traditional 3D-printed,the Al_(2)O_(3)-doped structural YBCO bulks present excellent heat transfer performances.Our customized design of 3D-printing precursor pastes and novel concept of structural design for enhancing the thermal conductivity of YBCO superconducting material can be widely used in other DIW 3D-printing materials.展开更多
The photocatalytic activity of catalysts depends on the energy-harvesting ability and the separation or transport of photogenerated carriers.The light absorption capacity of graphitic carbon nitride(g-C_(3)N_(4))-base...The photocatalytic activity of catalysts depends on the energy-harvesting ability and the separation or transport of photogenerated carriers.The light absorption capacity of graphitic carbon nitride(g-C_(3)N_(4))-based composites can be enhanced by adjusting the surface plasmon resonance(SPR)of noble metal nanoparticles(e.g.,Cu,Au,and Pd)in the entire visible region.Adjustments can be carried out by varying the nanocomponents of the materials.The SPR of noble metals can enhance the local electromagnetic field and improve interband transition,and resonant energy transfer occurs from plasmonic dipoles to electron-hole pairs via near-field electromagnetic interactions.Thus,noble metals have emerged as relevant nanocomponents for g-C_(3)N_(4) used in CO_(2) photoreduction and water splitting.Herein,recent key advances in noble metals(either in single atom,cluster,or nanoparticle forms)and composite photocatalysts based on inorganic or organic nanocomponent-incorporated g-C_(3)N_(4) nanosheets are systematically discussed,including the applications of these photocatalysts,which exhibit improved photoinduced charge mobility in CO_(2) photoconversion and H2 production.Issues related to the different types of multi-nanocomponent heterostructures(involving Schottky junctions,Z-/S-scheme heterostructures,noble metals,and additional semiconductor nanocomponents)and the adjustment of dimensionality of heterostructures(by incorporating noble metal nanoplates on g-C_(3)N_(4) forming 2D/2D heterostructures)are explored.The current prospects and possible challenges of g-C_(3)N_(4) composite photocatalysts incorporated with noble metals(e.g.,Au,Pt,Pd,and Cu),particularly in water splitting,CO_(2) reduction,pollution degradation,and chemical conversion applications,are summarized.展开更多
The uncontrolled dendrite growth of lithium metal anodes(LMAs)caused by unstable anode/electrolyte interface and uneven lithium deposition have impeded the practical applications of lithium metal batteries(LMBs).Const...The uncontrolled dendrite growth of lithium metal anodes(LMAs)caused by unstable anode/electrolyte interface and uneven lithium deposition have impeded the practical applications of lithium metal batteries(LMBs).Constructing a robust artificial solid electrolyte interphase(SEI)and regulating the lithium deposition behavior is an effective strategy to address these issues.Herein,a three-dimensional(3D)lithium anode with gradient Li_(3)N has been in-situ fabricated on carbon-based framework by thermal diffusion method(denoted as CC/Li/Li_(3)N).Density functional theory(DFT)calculations reveal that Li_(3)N can effectively promote the transport of Li^(+)due to the low energy barrier of Li^(+)diffusion.As expected,the Li_(3)N-rich conformal artificial SEI film can not only effectively stabilize the interface and avoid parasitic reactions,but also facilitate fast Li^(+)transport across the SEI layer.The anode matrix with uniformly distributed Li3N can enable homogenous deposition of Li,thus preventing Li dendrite propagation.Benefiting from these merits,the CC/Li/Li_(3)N anode achieves ultralong-term cycling for>1000 h at a current density of 2 m A cm^(-2)and dendrite-free Li deposition at an ultrahigh rate of 20 m A cm^(-2).Moreover,the full cells coupled with LiFePO4cathodes show extraordinary cycling stability for>300 cycles in liquidelectrolyte-based batteries and display a high-capacity retention of 96.7%after 100 cycles in solid-state cells,demonstrating the promising prospects for the practical applications of LMBs.展开更多
The ripple effect induced by uncontrollable Zn deposition is considered as the Achilles heel for developing high-performance aqueous Zn-ion batteries.For this problem,this work reports a design concept of 3D artificia...The ripple effect induced by uncontrollable Zn deposition is considered as the Achilles heel for developing high-performance aqueous Zn-ion batteries.For this problem,this work reports a design concept of 3D artificial array interface engineering to achieve volume stress elimination,preferred orientation growth and dendrite-free stable Zn metal anode.The mechanism of MXene array interface on modulating the growth kinetics and deposition behavior of Zn atoms were firstly disclosed on the multi-scale level,including the in-situ optical microscopy and transient simulation at the mesoscopic scale,in-situ Raman spectroscopy and in-situ X-ray diffraction at the microscopic scale,as well as density functional theory calculation at the atomic scale.As indicated by the electrochemical performance tests,such engineered electrode exhibits the comprehensive enhancements not only in the resistance of corrosion and hydrogen evolution,but also the rate capability and cyclic stability.High-rate performance(20 mA cm^(-2))and durable cycle lifespan(1350 h at 0.5 mA cm^(-2),1500 h at 1 mA cm^(-2)and 800 h at 5 mA cm^(-2))can be realized.Moreover,the improvement of rate capability(214.1 mAh g^(-1)obtained at 10 A g^(-1))and cyclic stability also can be demonstrated in the case of 3D MXene array@Zn/VO2battery.Beyond the previous 2D closed interface engineering,this research offers a unique 3D open array interface engineering to stabilize Zn metal anode,the controllable Zn deposition mechanism revealed is also expected to deepen the fundamental of rechargeable batteries including but not limited to aqueous Zn metal batteries.展开更多
Three-dimensional-structured metal oxides have myriad applications for optoelectronic devices.Comparing to conventional lithography-based manufacturing methods which face significant challenges for 3D device architect...Three-dimensional-structured metal oxides have myriad applications for optoelectronic devices.Comparing to conventional lithography-based manufacturing methods which face significant challenges for 3D device architectures,additive manufacturing approaches such as direct ink writing offer convenient,on-demand manufacturing of 3D oxides with high resolutions down to sub-micrometer scales.However,the lack of a universal ink design strategy greatly limits the choices of printable oxides.Here,a universal,facile synthetic strategy is developed for direct ink writable polymer precursor inks based on metal-polymer coordination effect.Specifically,polyethyleneimine functionalized by ethylenediaminetetraacetic acid is employed as the polymer matrix for adsorbing targeted metal ions.Next,glucose is introduced as a crosslinker for endowing the polymer precursor inks with a thermosetting property required for 3D printing via the Maillard reaction.For demonstrations,binary(i.e.,ZnO,CuO,In_(2)O_(3),Ga_(2)O_(3),TiO_(2),and Y_(2)O_(3)) and ternary metal oxides(i.e.,BaTiO_(3) and SrTiO_(3)) are printed into 3D architectures with sub-micrometer resolution by extruding the inks through ultrafine nozzles.Upon thermal crosslinking and pyrolysis,the 3D microarchitectures with woodpile geometries exhibit strong light-matter coupling in the mid-infrared region.The design strategy for printable inks opens a new pathway toward 3D-printed optoelectronic devices based on functional oxides.展开更多
The use of commercial products such as a cup and liner for total hip arthroplasty for patients with severe bone defects has a high probability of failure.In these patients the cup alone cannot cover the bone defect,an...The use of commercial products such as a cup and liner for total hip arthroplasty for patients with severe bone defects has a high probability of failure.In these patients the cup alone cannot cover the bone defect,and thus,an additional augment or cage is required.In this study,we designed three-dimensional(3D)printable bone augments as an alternative to surgeries using reinforcement cages.Thirty-five sharp-edged bone augments of various sizes were 3D printed.A biporous structure was designed to reduce the weight of the augment and to facilitate bone ingrowth.Two types of frames were used to prevent damage to the augment’s porous structure and maintain its stability during printing.Furthermore,two types of holes were provided for easy augment fixation at various angles.Fatigue tests were performed on a combination of worst-case sizes derived using finite element analysis.The test results confirmed the structural stability of the specimens at a load of 5340 N.Although the porosity of the specimens was measured to be 63.70%,it cannot be said that the porous nature was uniformly distributed because porosity tests were performed locally and randomly.In summary,3D-printable biporous bone augments capable of bonding from various angles and bidirectionally through angulation and bottom-plane screw holes are proposed.The mechanical results with bone augments indicate good structural safety in patients.However,further research is necessary to study the clinical applications of the proposed bone augment.展开更多
Electrocatalyst designs based on oxophilic foreign atoms are considered a promising approach for developing efficient pH-universal hydrogen evolution reaction(HER)electrocatalysts by overcoming the sluggish alkaline H...Electrocatalyst designs based on oxophilic foreign atoms are considered a promising approach for developing efficient pH-universal hydrogen evolution reaction(HER)electrocatalysts by overcoming the sluggish alkaline HER kinetics.Here,we design ternary transition metals-based nickel telluride(Mo WNi Te)catalysts consisting of high valence non-3d Mo and W metals and oxophilic Te as a first demonstration of non-precious heterogeneous electrocatalysts following the bifunctional mechanism.The Mo WNi Te showed excellent HER catalytic performance with overpotentials of 72,125,and 182 mV to reach the current densities of 10,100,and 1000 mA cm^(-2),respectively,and the corresponding Tafel slope of 47,52,and 58 mV dec-1in alkaline media,which is much superior to commercial Pt/C.Additionally,the HER performance of Mo WNi Te is well maintained up to 3000 h at the current density of 100 mA cm^(-2).It is further demonstrated that the Mo WNi Te exhibits remarkable HER activities with an overpotential of 45 mV(31 mV)and Tafel slope of 60 mV dec-1(34 mV dec-1)at 10 mA cm^(-2)in neutral(acid)media.The superior HER performance of Mo WNi Te is attributed to the electronic structure modulation,inducing highly active low valence states by the incorporation of high valence non-3d transition metals.It is also attributed to the oxophilic effect of Te,accelerating water dissociation kinetics through a bifunctional catalytic mechanism in alkaline media.Density functional theory calculations further reveal that such synergistic effects lead to reduced free energy for an efficient water dissociation process,resulting in remarkable HER catalytic performances within universal pH environments.展开更多
The poor contact and side reactions between Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)and lithium(Li)anode cause uneven Li plating and high interfacial impendence,which greatly hinder the practical application of LATP...The poor contact and side reactions between Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)and lithium(Li)anode cause uneven Li plating and high interfacial impendence,which greatly hinder the practical application of LATP in high-energy density solid-state Li metal batteries.In this work,a multifunctional ferroelectric BaTiO_(3)(BTO)/poly(vinylidene fluoride-co-trifluoroethylene-co-chlorotrifluoroethylene)(P[VDF-TrFE-CTFE])composite interlayer(B-TERB)is constructed between LATP and Li metal anode,which not only suppresses the Li dendrite growth,but also improves the interfacial stability and maintains the intimate interfacial contact to significantly decrease the interfacial resistance by two orders of magnitude.The B-TERB interlayer generates a uniform electric field to induce a uniform and lateral Li deposition,and therefore avoids the side reactions between Li metal and LATP achieving excellent interface stability.As a result,the Li/LATP@B-TERB/Li symmetrical batteries can stably cycle for 1800 h at 0.2 mA cm^(-2)and 1000 h at 0.5 mA cm^(-2).The solid-state LiFePO_(4)/LATP@B-TERB/Li full batteries also exhibit excellent cycle performance for 250 cycles at 0.5 C and room temperature.This work proposes a novel strategy to design multifunctional ferroelectric interlayer between ceramic electrolytes and Li metal to enable stable room-temperature cycling performance.展开更多
Improving the long-term cycling stability and energy density of all-solid-state lithium(Li)-metal batteries(ASSLMBs)at room temperature is a severe challenge because of the notorious solid–solid interfacial contact l...Improving the long-term cycling stability and energy density of all-solid-state lithium(Li)-metal batteries(ASSLMBs)at room temperature is a severe challenge because of the notorious solid–solid interfacial contact loss and sluggish ion transport.Solid electrolytes are generally studied as two-dimensional(2D)structures with planar interfaces,showing limited interfacial contact and further resulting in unstable Li/electrolyte and cathode/electrolyte interfaces.Herein,three-dimensional(3D)architecturally designed composite solid electrolytes are developed with independently controlled structural factors using 3D printing processing and post-curing treatment.Multiple-type electrolyte films with vertical-aligned micro-pillar(p-3DSE)and spiral(s-3DSE)structures are rationally designed and developed,which can be employed for both Li metal anode and cathode in terms of accelerating the Li+transport within electrodes and reinforcing the interfacial adhesion.The printed p-3DSE delivers robust long-term cycle life of up to 2600 cycles and a high critical current density of 1.92 mA cm^(−2).The optimized electrolyte structure could lead to ASSLMBs with a superior full-cell areal capacity of 2.75 mAh cm^(−2)(LFP)and 3.92 mAh cm^(−2)(NCM811).This unique design provides enhancements for both anode and cathode electrodes,thereby alleviating interfacial degradation induced by dendrite growth and contact loss.The approach in this study opens a new design strategy for advanced composite solid polymer electrolytes in ASSLMBs operating under high rates/capacities and room temperature.展开更多
This study presents a novel process for the fabrication of metal-intermetallic composites with a 3D bicontinuous structure, achieved through a combination of liquid metal dealloying(LMD) and subsequent alloying. Initi...This study presents a novel process for the fabrication of metal-intermetallic composites with a 3D bicontinuous structure, achieved through a combination of liquid metal dealloying(LMD) and subsequent alloying. Initially, porous Ti structures are produced using the LMD process, followed by immersion in a molten Mg-3Al(wt%) metal. Due to the higher thermodynamic miscibility of Al with Ti compared to Mg, the concentration of Al in the Ti matrix increases as the immersion time increases. This results in a sequential phase transition within the Ti matrix: α-Ti → Ti_(3)Al → Ti Al. The phase transition considerably affects the hardness and strength of the composite material,with the Mg-Ti_(3)Al-Ti Al composite exhibiting a maximum hardness nearly twice as high as that of the conventional Mg-Ti composite. This innovative process holds potential for the development of various bicontinuous metal-intermetallic composites.展开更多
Li metal with high-energy density is considered as the most promising anode for the next-generation rechargeable Li metal batteries;however,the growth of Li dendrites seriously hinders its practical application.Herein...Li metal with high-energy density is considered as the most promising anode for the next-generation rechargeable Li metal batteries;however,the growth of Li dendrites seriously hinders its practical application.Herein,3D free-standing carbon nanofibers modified by lithiophilic metal particles(CNF/Me,Me=Sn,Fe,Co)are obtained in situ by the electrospinning method.Benefiting from the lithophilicity,the CNF/Me composite may effectively prevent the formation of Li dendrites in the Li metal batteries.The optimized CNF/Sn–Li composite electrode exhibits a stable cycle life of over 2350 h during Li plating/stripping.When matched with typical commercial LiFePO_(4)(LFP)cathode,the LFP//CNF/Sn–Li full cell presents a high initial discharge specific capacity of 139 mAh g^(−1)at 1 C,which remains at 146 mAh g^(−1)after 400 cycles.When another state-of-the-art commercial LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM(811))cathode is used,the assembled NCM//CNF/Sn–Li full cell shows a large initial specific discharge capacity of 206 mAh g^(−1)at substantially enhanced 10 C,which keeps at the good capacity of 99 mAh g^(−1)after 300 cycles.These results are greatly superior to the counterparts with Li as the anodes,indicating the great potential for practical utilization of the advanced CNF/Sn–Li electrode.展开更多
Nonlinear flow behavior of fluids through three-dimensional(3D)discrete fracture networks(DFNs)considering effects of fracture number,surface roughness and fracture aperture was experimentally and numerically investig...Nonlinear flow behavior of fluids through three-dimensional(3D)discrete fracture networks(DFNs)considering effects of fracture number,surface roughness and fracture aperture was experimentally and numerically investigated.Three physical models of DFNs were 3D-printed and then computed tomography(CT)-scanned to obtain the specific geometry of fractures.The validity of numerically simulating the fluid flow through DFNs was verified via comparison with flow tests on the 3D-printed models.A parametric study was then implemented to establish quantitative relations between the coefficients/parameters in Forchheimer’s law and geometrical parameters.The results showed that the 3D-printing technique can well reproduce the geometry of single fractures with less precision when preparing complex fracture networks,numerical modeling precision of which can be improved via CT-scanning as evidenced by the well fitted results between fluid flow tests and numerical simulations using CT-scanned digital models.Streamlines in DFNs become increasingly tortuous as the fracture number and roughness increase,resulting in stronger inertial effects and greater curvatures of hydraulic pressure-low rate relations,which can be well characterized by the Forchheimer’s law.The critical hydraulic gradient for the onset of nonlinear flow decreases with the increasing aperture,fracture number and roughness,following a power function.The increases in fracture aperture and number provide more paths for fluid flow,increasing both the viscous and inertial permeabilities.The value of the inertial permeability is approximately four orders of magnitude greater than the viscous permeability,following a power function with an exponent a of 3,and a proportional coefficient b mathematically correlated with the geometrical parameters.展开更多
Metal derivative/graphitic carbon nitride(g-C_(3)N_(4))association is found promising in providing sustainable hydrogen production by photocatalytic water splitting process.Number of works reported on the synthesis an...Metal derivative/graphitic carbon nitride(g-C_(3)N_(4))association is found promising in providing sustainable hydrogen production by photocatalytic water splitting process.Number of works reported on the synthesis and application of various metal based g-C_(3)N_(4)composites are increasing day by day.Mechanism of charge separation varies according to the metal candidate that gets couple with g-C_(3)N_(4).The present article thus explores the interesting chemistry behind various metal based heterojunction and demonstrates the charge separation route.A thorough investigation has been done on the current research trend in the area.As many metal free g-C_(3)N_(4)composites are reported nowadays as an alternative to metal derivatives,here compares metallic and metal free derivatives of g-C_(3)N_(4)based on four critical requirements of an industrial catalyst,ie,activity,stability,cost and toxicity.Challenges and future direction in the area are also discussed with significance.The systematic discussion and schematic illustration of charge transfer process in different heterojunctions with reference to the reported systems,given in the article can definitely contribute to the design and development of more efficient g-C_(3)N_(4)based heterojunctions in future for hydrogen production application.展开更多
基金funded by the China Postdoctoral Science Foundation(No.2019M663487)the National Key Research and Development Program of China(No.2022YFE03130000)。
文摘A liquid Li divertor is a promising alternative for future fusion devices.In this work a new divertor model is proposed,which is processed by 3D-printing technology to accurately control the size of the internal capillary structure.At a steady-state heat load of 10 MW m^(-2),the thermal stress of the tungsten target is within the bearing range of tungsten by finite-element simulation.In order to evaluate the wicking ability of the capillary structure,the wicking process at 600℃ was simulated by FLUENT.The result was identical to that of the corresponding experiments.Within 1 s,liquid lithium was wicked to the target surface by the capillary structure of the target and quickly spread on the target surface.During the wicking process,the average wicking mass rate of lithium should reach 0.062 g s^(-1),which could even supplement the evaporation requirement of liquid lithium under an environment>950℃.Irradiation experiments under different plasma discharge currents were carried out in a linear plasma device(SCU-PSI),and the evolution of the vapor cloud during plasma irradiation was analyzed.It was found that the target temperature tends to plateau despite the gradually increased input current,indicating that the vapor shielding effect is gradually enhanced.The irradiation experiment also confirmed that the 3D-printed tungsten structure has better heat consumption performance than a tungsten mesh structure or multichannel structure.These results reveal the application potential and feasibility of a 3D-printed porous capillary structure in plasma-facing components and provide a reference for further liquid-solid combined target designs.
文摘Metal-organic frameworks(MOFs)have been extensively considered as one of the most promising types of porous and crystalline organic-inorganic materials,thanks to their large specific surface area,high porosity,tailorable structures and compositions,diverse functionalities,and well-controlled pore/size distribution.However,most developed MOFs are in powder forms,which still have some technical challenges,including abrasion,dustiness,low packing densities,clogging,mass/heat transfer limitation,environmental pollution,and mechanical instability during the packing process,that restrict their applicability in industrial applications.Therefore,in recent years,attention has focused on techniques to convert MOF powders into macroscopic materials like beads,membranes,monoliths,gel/sponges,and nanofibers to overcome these challenges.Three-dimensional(3D)printing technology has achieved much interest because it can produce many high-resolution macroscopic frameworks with complex shapes and geometries from digital models.Therefore,this review summarizes the combination of different 3D printing strategies with MOFs and MOF-based materials for fabricating 3D-printed MOF monoliths and their environmental applications,emphasizing water treatment and gas adsorption/separation applications.Herein,the various strategies for the fabrication of 3D-printed MOF monoliths,such as direct ink writing,seed-assisted in-situ growth,coordination replication from solid precursors,matrix incorporation,selective laser sintering,and digital light processing,are described with the relevant examples.Finally,future directions and challenges of 3D-printed MOF monoliths are also presented to better plan future trajectories in the shaping of MOF materials with improved control over the structure,composition,and textural properties of 3D-printed MOF monoliths.
基金supported by the Shanghai Agricultural Science and Technology Program (2022-02-08-00-12-F01176)he National Natural Science Foundation of China (52006135)
文摘Direct air capture(DAC)of CO_(2)plays an indispensable role in achieving carbon-neutral goals as one of the key negative emission technologies.Since large air flows are required to capture the ultradilute CO_(2)from the air,lab-synthesized adsorbents in powder form may cause unacceptable gas pressure drops and poor heat and mass transfer efficiencies.A structured adsorbent is essential for the implementation of gas-solid contactors for cost-and energy-efficient DAC systems.In this study,efficient adsorbent poly(ethyleneimine)(PEI)-functionalized Mg-Al-CO_(3)layered double hydroxide(LDH)-derived mixed metal oxides(MMOs)are three-dimensional(3D)printed into monoliths for the first time with more than 90%adsorbent loadings.The printing process has been optimized by initially printing the LDH powder into monoliths followed by calcination into MMO monoliths.This structure exhibits a 32.7%higher specific surface area and a 46.1%higher pore volume,as compared to the direct printing of the MMO powder into a monolith.After impregnation of PEI,the monolith demonstrates a large adsorption capacity(1.82 mmol/g)and fast kinetics(0.7 mmol/g/h)using a CO_(2)feed gas at 400 ppm at 25℃,one of the highest values among the shaped DAC adsorbents.Smearing of the amino-polymers during the post-printing process affects the diffusion of CO_(2),resulting in slower adsorption kinetics of pre-impregnation monoliths compared to post-impregnation monoliths.The optimal PEI/MeOH ratio for the post-impregnation solution prevents pores clogging that would affect both adsorption capacity and kinetics.
基金supported by the Fund of Natural Science Foundation of China(No.11872196,12232005)supported by the Outstanding Postgraduate‘Innovation Star’Fund for Distinguished of Gansu Province(No.2021CXZX-032).
文摘Superconducting YBa_(2)Cu_(3)O_(7−x)(YBCO)bulks have promising applications in quasi-permanent magnets,levitation,etc.Recently,a new way of fabricating porous YBCO bulks,named direct-ink-writing(DIW)3D-printing method,has been reported.In this method,the customized precursor paste and programmable shape are two main advantages.Here,we have put forward a new way to customize the YBCO 3D-printing precursor paste which is doped with Al_(2)O_(3)nanoparticles to obtain YBCO with higher thermal conductivity.The great rheological properties of precursor paste after being doped with Al_(2)O_(3)nanoparticles can help the macroscopic YBCO samples with high thermal conductivity fabricated stably with high crystalline and lightweight properties.Test results show that the peak thermal conductivity of Al_(2)O_(3)-doped YBCO can reach twice as much as pure YBCO,which makes a great effort to reduce the quench propagation speed.Based on the microstructure analysis,one can find that the thermal conductivity of Al_(2)O_(3)-doped YBCO has been determined by its components and microstructures.In addition,a macroscopic theoretical model has been proposed to assess the thermal conductivity of different microstructures,whose calculated results take good agreement with the experimental results.Meanwhile,a microstructure with high thermal conductivity has been found.Finally,a macroscopic YBCO bulk with the presented high thermal conductivity microstructure has been fabricated by the Al_(2)O_(3)-doped method.Compared with YBCO fabricated by the traditional 3D-printed,the Al_(2)O_(3)-doped structural YBCO bulks present excellent heat transfer performances.Our customized design of 3D-printing precursor pastes and novel concept of structural design for enhancing the thermal conductivity of YBCO superconducting material can be widely used in other DIW 3D-printing materials.
基金supported in part by the projects from the National Natural Science Foundation of China(No.51972145)Jinan Science&Technology Bureau,China(No.2021GXRC109)Science and Technology Program of the University of Jinan,China(No.XKY2118).
文摘The photocatalytic activity of catalysts depends on the energy-harvesting ability and the separation or transport of photogenerated carriers.The light absorption capacity of graphitic carbon nitride(g-C_(3)N_(4))-based composites can be enhanced by adjusting the surface plasmon resonance(SPR)of noble metal nanoparticles(e.g.,Cu,Au,and Pd)in the entire visible region.Adjustments can be carried out by varying the nanocomponents of the materials.The SPR of noble metals can enhance the local electromagnetic field and improve interband transition,and resonant energy transfer occurs from plasmonic dipoles to electron-hole pairs via near-field electromagnetic interactions.Thus,noble metals have emerged as relevant nanocomponents for g-C_(3)N_(4) used in CO_(2) photoreduction and water splitting.Herein,recent key advances in noble metals(either in single atom,cluster,or nanoparticle forms)and composite photocatalysts based on inorganic or organic nanocomponent-incorporated g-C_(3)N_(4) nanosheets are systematically discussed,including the applications of these photocatalysts,which exhibit improved photoinduced charge mobility in CO_(2) photoconversion and H2 production.Issues related to the different types of multi-nanocomponent heterostructures(involving Schottky junctions,Z-/S-scheme heterostructures,noble metals,and additional semiconductor nanocomponents)and the adjustment of dimensionality of heterostructures(by incorporating noble metal nanoplates on g-C_(3)N_(4) forming 2D/2D heterostructures)are explored.The current prospects and possible challenges of g-C_(3)N_(4) composite photocatalysts incorporated with noble metals(e.g.,Au,Pt,Pd,and Cu),particularly in water splitting,CO_(2) reduction,pollution degradation,and chemical conversion applications,are summarized.
基金supported by the National Natural Science Foundation of China(22078251)the National Key R&D Program of China(2021YFB2012000)+1 种基金the Opening Project of Key Laboratory of Optoelectronic Chemical Materials and Devices of Ministry of Education,Jianghan University(JDGD-202211)the Graduate Innovation Fund of Wuhan Institute of Technology(CX2021014)。
文摘The uncontrolled dendrite growth of lithium metal anodes(LMAs)caused by unstable anode/electrolyte interface and uneven lithium deposition have impeded the practical applications of lithium metal batteries(LMBs).Constructing a robust artificial solid electrolyte interphase(SEI)and regulating the lithium deposition behavior is an effective strategy to address these issues.Herein,a three-dimensional(3D)lithium anode with gradient Li_(3)N has been in-situ fabricated on carbon-based framework by thermal diffusion method(denoted as CC/Li/Li_(3)N).Density functional theory(DFT)calculations reveal that Li_(3)N can effectively promote the transport of Li^(+)due to the low energy barrier of Li^(+)diffusion.As expected,the Li_(3)N-rich conformal artificial SEI film can not only effectively stabilize the interface and avoid parasitic reactions,but also facilitate fast Li^(+)transport across the SEI layer.The anode matrix with uniformly distributed Li3N can enable homogenous deposition of Li,thus preventing Li dendrite propagation.Benefiting from these merits,the CC/Li/Li_(3)N anode achieves ultralong-term cycling for>1000 h at a current density of 2 m A cm^(-2)and dendrite-free Li deposition at an ultrahigh rate of 20 m A cm^(-2).Moreover,the full cells coupled with LiFePO4cathodes show extraordinary cycling stability for>300 cycles in liquidelectrolyte-based batteries and display a high-capacity retention of 96.7%after 100 cycles in solid-state cells,demonstrating the promising prospects for the practical applications of LMBs.
基金financially the National Natural Science Foundation of China(Nos.22178221,22208221)Shenzhen Science and Technology Program(Nos.JCYJ20200109105805902)+1 种基金Natural Science Foundation of Guangdong Province(Nos.2021A1515110751)China Postdoctoral Science Foundation(Nos.2021M702255)。
文摘The ripple effect induced by uncontrollable Zn deposition is considered as the Achilles heel for developing high-performance aqueous Zn-ion batteries.For this problem,this work reports a design concept of 3D artificial array interface engineering to achieve volume stress elimination,preferred orientation growth and dendrite-free stable Zn metal anode.The mechanism of MXene array interface on modulating the growth kinetics and deposition behavior of Zn atoms were firstly disclosed on the multi-scale level,including the in-situ optical microscopy and transient simulation at the mesoscopic scale,in-situ Raman spectroscopy and in-situ X-ray diffraction at the microscopic scale,as well as density functional theory calculation at the atomic scale.As indicated by the electrochemical performance tests,such engineered electrode exhibits the comprehensive enhancements not only in the resistance of corrosion and hydrogen evolution,but also the rate capability and cyclic stability.High-rate performance(20 mA cm^(-2))and durable cycle lifespan(1350 h at 0.5 mA cm^(-2),1500 h at 1 mA cm^(-2)and 800 h at 5 mA cm^(-2))can be realized.Moreover,the improvement of rate capability(214.1 mAh g^(-1)obtained at 10 A g^(-1))and cyclic stability also can be demonstrated in the case of 3D MXene array@Zn/VO2battery.Beyond the previous 2D closed interface engineering,this research offers a unique 3D open array interface engineering to stabilize Zn metal anode,the controllable Zn deposition mechanism revealed is also expected to deepen the fundamental of rechargeable batteries including but not limited to aqueous Zn metal batteries.
基金financial support of this research by the National Natural Science Foundation of China (No. 51905446)the Research Center for Industries of the Future (RCIF) at Westlake University for partially supporting this work。
文摘Three-dimensional-structured metal oxides have myriad applications for optoelectronic devices.Comparing to conventional lithography-based manufacturing methods which face significant challenges for 3D device architectures,additive manufacturing approaches such as direct ink writing offer convenient,on-demand manufacturing of 3D oxides with high resolutions down to sub-micrometer scales.However,the lack of a universal ink design strategy greatly limits the choices of printable oxides.Here,a universal,facile synthetic strategy is developed for direct ink writable polymer precursor inks based on metal-polymer coordination effect.Specifically,polyethyleneimine functionalized by ethylenediaminetetraacetic acid is employed as the polymer matrix for adsorbing targeted metal ions.Next,glucose is introduced as a crosslinker for endowing the polymer precursor inks with a thermosetting property required for 3D printing via the Maillard reaction.For demonstrations,binary(i.e.,ZnO,CuO,In_(2)O_(3),Ga_(2)O_(3),TiO_(2),and Y_(2)O_(3)) and ternary metal oxides(i.e.,BaTiO_(3) and SrTiO_(3)) are printed into 3D architectures with sub-micrometer resolution by extruding the inks through ultrafine nozzles.Upon thermal crosslinking and pyrolysis,the 3D microarchitectures with woodpile geometries exhibit strong light-matter coupling in the mid-infrared region.The design strategy for printable inks opens a new pathway toward 3D-printed optoelectronic devices based on functional oxides.
基金supported by the Technology Development Program(P0011350)funded by the Ministry of SMEs and Startups(MSS,Korea)。
文摘The use of commercial products such as a cup and liner for total hip arthroplasty for patients with severe bone defects has a high probability of failure.In these patients the cup alone cannot cover the bone defect,and thus,an additional augment or cage is required.In this study,we designed three-dimensional(3D)printable bone augments as an alternative to surgeries using reinforcement cages.Thirty-five sharp-edged bone augments of various sizes were 3D printed.A biporous structure was designed to reduce the weight of the augment and to facilitate bone ingrowth.Two types of frames were used to prevent damage to the augment’s porous structure and maintain its stability during printing.Furthermore,two types of holes were provided for easy augment fixation at various angles.Fatigue tests were performed on a combination of worst-case sizes derived using finite element analysis.The test results confirmed the structural stability of the specimens at a load of 5340 N.Although the porosity of the specimens was measured to be 63.70%,it cannot be said that the porous nature was uniformly distributed because porosity tests were performed locally and randomly.In summary,3D-printable biporous bone augments capable of bonding from various angles and bidirectionally through angulation and bottom-plane screw holes are proposed.The mechanical results with bone augments indicate good structural safety in patients.However,further research is necessary to study the clinical applications of the proposed bone augment.
基金supported through the National Research Foundation of Korea(NRF)funded by the Ministry of Science and ICT(2022M3H4A1A04096478)the support from the Supercomputing Center of Wuhan University。
文摘Electrocatalyst designs based on oxophilic foreign atoms are considered a promising approach for developing efficient pH-universal hydrogen evolution reaction(HER)electrocatalysts by overcoming the sluggish alkaline HER kinetics.Here,we design ternary transition metals-based nickel telluride(Mo WNi Te)catalysts consisting of high valence non-3d Mo and W metals and oxophilic Te as a first demonstration of non-precious heterogeneous electrocatalysts following the bifunctional mechanism.The Mo WNi Te showed excellent HER catalytic performance with overpotentials of 72,125,and 182 mV to reach the current densities of 10,100,and 1000 mA cm^(-2),respectively,and the corresponding Tafel slope of 47,52,and 58 mV dec-1in alkaline media,which is much superior to commercial Pt/C.Additionally,the HER performance of Mo WNi Te is well maintained up to 3000 h at the current density of 100 mA cm^(-2).It is further demonstrated that the Mo WNi Te exhibits remarkable HER activities with an overpotential of 45 mV(31 mV)and Tafel slope of 60 mV dec-1(34 mV dec-1)at 10 mA cm^(-2)in neutral(acid)media.The superior HER performance of Mo WNi Te is attributed to the electronic structure modulation,inducing highly active low valence states by the incorporation of high valence non-3d transition metals.It is also attributed to the oxophilic effect of Te,accelerating water dissociation kinetics through a bifunctional catalytic mechanism in alkaline media.Density functional theory calculations further reveal that such synergistic effects lead to reduced free energy for an efficient water dissociation process,resulting in remarkable HER catalytic performances within universal pH environments.
基金supported by National Natural Science Foundation of China(No.U2001220)Local Innovative Research Teams Project of Guangdong Pearl River Talents Program(No.2017BT01N111)+1 种基金Shenzhen All-Solid-State Lithium Battery Electrolyte Engineering Research Center(XMHT20200203006)Shenzhen Technical Plan Project(Nos.RCJC20200714114436091,JCYJ20180508152210821,and JCYJ20180508152135822).
文摘The poor contact and side reactions between Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)and lithium(Li)anode cause uneven Li plating and high interfacial impendence,which greatly hinder the practical application of LATP in high-energy density solid-state Li metal batteries.In this work,a multifunctional ferroelectric BaTiO_(3)(BTO)/poly(vinylidene fluoride-co-trifluoroethylene-co-chlorotrifluoroethylene)(P[VDF-TrFE-CTFE])composite interlayer(B-TERB)is constructed between LATP and Li metal anode,which not only suppresses the Li dendrite growth,but also improves the interfacial stability and maintains the intimate interfacial contact to significantly decrease the interfacial resistance by two orders of magnitude.The B-TERB interlayer generates a uniform electric field to induce a uniform and lateral Li deposition,and therefore avoids the side reactions between Li metal and LATP achieving excellent interface stability.As a result,the Li/LATP@B-TERB/Li symmetrical batteries can stably cycle for 1800 h at 0.2 mA cm^(-2)and 1000 h at 0.5 mA cm^(-2).The solid-state LiFePO_(4)/LATP@B-TERB/Li full batteries also exhibit excellent cycle performance for 250 cycles at 0.5 C and room temperature.This work proposes a novel strategy to design multifunctional ferroelectric interlayer between ceramic electrolytes and Li metal to enable stable room-temperature cycling performance.
基金This work was financially supported by Stable Support Plan Program for Higher Education Institutions(20220815094504001)Shenzhen Key Laboratory of Advanced Energy Storage(ZDSYS20220401141000001)+1 种基金This work was also financially supported by the Shenzhen Science and Technology Innovation Commission(GJHZ20200731095606021,20200925155544005)the Project of Hetao Shenzhen-Hong Kong Science and Technology Innovation Cooperation Zone(HZQB-KCZYB-2020083)。
文摘Improving the long-term cycling stability and energy density of all-solid-state lithium(Li)-metal batteries(ASSLMBs)at room temperature is a severe challenge because of the notorious solid–solid interfacial contact loss and sluggish ion transport.Solid electrolytes are generally studied as two-dimensional(2D)structures with planar interfaces,showing limited interfacial contact and further resulting in unstable Li/electrolyte and cathode/electrolyte interfaces.Herein,three-dimensional(3D)architecturally designed composite solid electrolytes are developed with independently controlled structural factors using 3D printing processing and post-curing treatment.Multiple-type electrolyte films with vertical-aligned micro-pillar(p-3DSE)and spiral(s-3DSE)structures are rationally designed and developed,which can be employed for both Li metal anode and cathode in terms of accelerating the Li+transport within electrodes and reinforcing the interfacial adhesion.The printed p-3DSE delivers robust long-term cycle life of up to 2600 cycles and a high critical current density of 1.92 mA cm^(−2).The optimized electrolyte structure could lead to ASSLMBs with a superior full-cell areal capacity of 2.75 mAh cm^(−2)(LFP)and 3.92 mAh cm^(−2)(NCM811).This unique design provides enhancements for both anode and cathode electrodes,thereby alleviating interfacial degradation induced by dendrite growth and contact loss.The approach in this study opens a new design strategy for advanced composite solid polymer electrolytes in ASSLMBs operating under high rates/capacities and room temperature.
基金supported by the National Research Council of Science & Technology (NST) grant by the Korea Government (MSIT) (grant no.CRC23011-000)by the National Research Foundation of Korea (NRF) funded by the Ministry of Science,ICT,and Future Planning (MSIP,South Korea) (grant no.NRF-2021R1C1C1007645)。
文摘This study presents a novel process for the fabrication of metal-intermetallic composites with a 3D bicontinuous structure, achieved through a combination of liquid metal dealloying(LMD) and subsequent alloying. Initially, porous Ti structures are produced using the LMD process, followed by immersion in a molten Mg-3Al(wt%) metal. Due to the higher thermodynamic miscibility of Al with Ti compared to Mg, the concentration of Al in the Ti matrix increases as the immersion time increases. This results in a sequential phase transition within the Ti matrix: α-Ti → Ti_(3)Al → Ti Al. The phase transition considerably affects the hardness and strength of the composite material,with the Mg-Ti_(3)Al-Ti Al composite exhibiting a maximum hardness nearly twice as high as that of the conventional Mg-Ti composite. This innovative process holds potential for the development of various bicontinuous metal-intermetallic composites.
基金supported by the Chinese National Natural Science Foundation(No.22075008,21571010,U0734002)National Basic Research Programs of China(973 Program,No.2014CB931800,2011CB935700)+1 种基金Chinese Aeronautic Project(No.2013ZF51069)111 Project(No.B14009).
文摘Li metal with high-energy density is considered as the most promising anode for the next-generation rechargeable Li metal batteries;however,the growth of Li dendrites seriously hinders its practical application.Herein,3D free-standing carbon nanofibers modified by lithiophilic metal particles(CNF/Me,Me=Sn,Fe,Co)are obtained in situ by the electrospinning method.Benefiting from the lithophilicity,the CNF/Me composite may effectively prevent the formation of Li dendrites in the Li metal batteries.The optimized CNF/Sn–Li composite electrode exhibits a stable cycle life of over 2350 h during Li plating/stripping.When matched with typical commercial LiFePO_(4)(LFP)cathode,the LFP//CNF/Sn–Li full cell presents a high initial discharge specific capacity of 139 mAh g^(−1)at 1 C,which remains at 146 mAh g^(−1)after 400 cycles.When another state-of-the-art commercial LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM(811))cathode is used,the assembled NCM//CNF/Sn–Li full cell shows a large initial specific discharge capacity of 206 mAh g^(−1)at substantially enhanced 10 C,which keeps at the good capacity of 99 mAh g^(−1)after 300 cycles.These results are greatly superior to the counterparts with Li as the anodes,indicating the great potential for practical utilization of the advanced CNF/Sn–Li electrode.
基金the Natural Science Foundation of Zhejiang Province(Grant No.LR19E090001)the Natural Science Foundation of China(Grant Nos.42077252,42011530122,and 51979272).
文摘Nonlinear flow behavior of fluids through three-dimensional(3D)discrete fracture networks(DFNs)considering effects of fracture number,surface roughness and fracture aperture was experimentally and numerically investigated.Three physical models of DFNs were 3D-printed and then computed tomography(CT)-scanned to obtain the specific geometry of fractures.The validity of numerically simulating the fluid flow through DFNs was verified via comparison with flow tests on the 3D-printed models.A parametric study was then implemented to establish quantitative relations between the coefficients/parameters in Forchheimer’s law and geometrical parameters.The results showed that the 3D-printing technique can well reproduce the geometry of single fractures with less precision when preparing complex fracture networks,numerical modeling precision of which can be improved via CT-scanning as evidenced by the well fitted results between fluid flow tests and numerical simulations using CT-scanned digital models.Streamlines in DFNs become increasingly tortuous as the fracture number and roughness increase,resulting in stronger inertial effects and greater curvatures of hydraulic pressure-low rate relations,which can be well characterized by the Forchheimer’s law.The critical hydraulic gradient for the onset of nonlinear flow decreases with the increasing aperture,fracture number and roughness,following a power function.The increases in fracture aperture and number provide more paths for fluid flow,increasing both the viscous and inertial permeabilities.The value of the inertial permeability is approximately four orders of magnitude greater than the viscous permeability,following a power function with an exponent a of 3,and a proportional coefficient b mathematically correlated with the geometrical parameters.
文摘Metal derivative/graphitic carbon nitride(g-C_(3)N_(4))association is found promising in providing sustainable hydrogen production by photocatalytic water splitting process.Number of works reported on the synthesis and application of various metal based g-C_(3)N_(4)composites are increasing day by day.Mechanism of charge separation varies according to the metal candidate that gets couple with g-C_(3)N_(4).The present article thus explores the interesting chemistry behind various metal based heterojunction and demonstrates the charge separation route.A thorough investigation has been done on the current research trend in the area.As many metal free g-C_(3)N_(4)composites are reported nowadays as an alternative to metal derivatives,here compares metallic and metal free derivatives of g-C_(3)N_(4)based on four critical requirements of an industrial catalyst,ie,activity,stability,cost and toxicity.Challenges and future direction in the area are also discussed with significance.The systematic discussion and schematic illustration of charge transfer process in different heterojunctions with reference to the reported systems,given in the article can definitely contribute to the design and development of more efficient g-C_(3)N_(4)based heterojunctions in future for hydrogen production application.