查看更多>>摘要：Photothermal catalytic CO2 conversion provides an effective solution targeting carbon neutrality by syn-ergistic utilization of photon and heat.However,the C-C coupling initiated by photothermal catalysis is still a big challenge.Herein,a three-dimensional(3D)hierarchical W18O49/WTe2 hollow nanosphere is constructed through in-situ embodying of oxygen vacancy and tellurium on the scaffold of WO3.The light absorption towards near-infrared spectral region and CO2 adsorption are enhanced by the formation of half-metal WTe2 and the unique hierarchical hollow architecture.Combining with the generation of oxy-gen vacancy with strengthened CO2 capture,the photothermal effect on the samples can be sufficiently exploited for activating the CO2 molecules.In particular,the close contact between W18O49 and WTe2 lar-gely promotes the photoinduced charge separation and mass transfer,and thus the*CHO intermediate formation and fixedness are facilitated.As a result,the C-C coupling can be evoked between tungsten and tellurium atoms on WTe2.The ethylene production by optimized W18O49/WTe2 reaches 147.6 μmol g-1 with the selectivity of 80％.The in-situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)and density functional theory(DFT)calculations are performed to unveil the presence and sig-nificance of aldehyde intermediate groups in C-C coupling.The half-metallic WTe2 cocatalyst proposes a new approach for efficient CO2 conversion with solar energy,and may especially create a new platform for the generation of multi-carbon products.
查看更多>>摘要：Compared to conventional electrocatalytic water splitting,electrocatalytic ethanol oxidation reaction(EOR)along with hydrogen production is considered a more energy-efficient strategy.Herein,we pre-pared a type of novel quaternary alloy catalyst(PtAuCuNi@NF)that exhibits excellent activity for EOR(0.215 V at 10 mA cm-2)and hydrogen evolution reaction(HER)(7 mV at 10 mA cm-2).Experimental results demonstrated that both Cu and Ni modulated the electronic environment around Pt and Au.The electron-rich active center facilitates the rapid adsorption and dissociation of reactants and interme-diates for both EOR and HER.Impressively,in the ethanol-assisted overall water splitting(E-OWS),a cur-rent density of 10 mA cm-2 was achieved at 0.28 V.Moreover,an advanced acid-base self-powered system(A-Bsps)that can achieve a self-powered voltage of 0.59 V was assembled.Accordingly,the self-driven hydrogen production with zero external power supply was realized by integrating A-Bsps with the E-OWS equipment.The interesting results can provide a feasible strategy for designing and developing advanced nanoalloy-based materials for clean energy integration and use in various fields.
查看更多>>摘要：Transition metal chalcogenides(TMCs)are recognized as pre-catalysts,and their(oxy)hydroxides derived from electrochemical reconstruction are the active species in the water oxidation.However,understand-ing the role of the residual chalcogen in the reconstructed layer is lacking in detail,and the corresponding catalytic mechanism remains controversial.Here,taking Cu1-xCoxS as a platform,we explore the regulat-ing effect and existence form of the residual S doped into the reconstructive layer for oxygen evolution reaction(OER),where a dual-path OER mechanism is proposed.First-principles calculations and oper-ando 18O isotopic labeling experiments jointly reveal that the residual S in the reconstructive layer of Cu1-xCoxS can wisely balance the adsorbate evolution mechanism(AEM)and lattice oxygen oxidation mechanism(LOM)by activating lattice oxygen and optimizing the adsorption/desorption behaviors at metal active sites,rather than change the reaction mechanism from AEM to LOM.Following such a dual-path OER mechanism,Cu0.4Co0.6S-derived Cu0.4Co0.6OSH not only overcomes the restriction of linear scaling relationship in AEM,but also avoids the structural collapse caused by lattice oxygen migration in LOM,so as to greatly reduce the OER potential and improved stability.
查看更多>>摘要：Silicon-based materials have demonstrated remarkable potential in high-energy-density batteries owing to their high theoretical capacity.However,the significant volume expansion of silicon seriously hinders its utilization as a lithium-ion anode.Herein,a functionalized high-toughness polyimide(PDMI)is syn-thesized by copolymerizing the 4,4'-Oxydiphthalic anhydride(ODPA)with 4,4'-oxydianiline(ODA),2,3-diaminobenzoic acid(DABA),and 1,3-bis(3-aminopropyl)-tetramethyl disiloxane(DMS).The combi-nation of rigid benzene rings and flexible oxygen groups(-O-)in the PDMI molecular chain via a rigidness/softness coupling mechanism contributes to high toughness.The plentiful polar carboxyl(-COOH)groups establish robust bonding strength.Rapid ionic transport is achieved by incorporating the flexible siloxane segment(Si-O-Si),which imparts high molecular chain motility and augments free volume holes to facilitate lithium-ion transport(9.8×10-10 cm2 s-1 vs.16×10-10 cm2 s-1).As expected,the SiOx@PDMI-1.5 electrode delivers brilliant long-term cycle performance with a remarkable capacity retention of 85％over 500 cycles at 1.3 A g-1.The well-designed functionalized polyimide also signifi-cantly enhances the electrochemical properties of Si nanoparticles electrode.Meanwhile,the assembled SiOx@PDMI-1.5/NCM811 full cell delivers a high retention of 80％after 100 cycles.The perspective of the binder design strategy based on polyimide modification delivers a novel path toward high-capacity elec-trodes for high-energy-density batteries.
查看更多>>摘要：Precisely refining the electronic structure of electrocatalysts represents a powerful approach to further optimize the electrocatalytic performance.Herein,we demonstrate an ingenious d-d orbital hybridization concept to construct Mo-doped Co9S8 nanorod arrays aligned on carbon cloth(CC)substrate(abbreviated as Mo-Co9S8@CC hereafter)as a high-efficiency bifunctional electrocatalyst toward water electrolysis.It has experimentally and theoretically validated that the 4d-3d orbital coupling between Mo dopant and Co site can effectively optimize the H2O activation energy and lower H*adsorption energy barrier,thereby leading to enhanced hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)activities.Thanks to the unique electronic and geometrical advantages,the optimized Mo-Co9S8@CC with appropriate Mo content exhibits outstanding bifunctional performance in alkaline solution,with the overpotentials of 75 and 234 mV for the delivery of a current density of 10 mA cm-2,small Tafel slopes of 53.8 and 39.9 mV dec-1 and long-term stabilities for at least 32 and 30 h for HER and OER,respectively.More impressively,a water splitting electrolylzer assembled by the self-supported Mo-Co9S8@CC elec-trode requires a low cell voltage of 1.53 V at 10 mA cm-2 and shows excellent stability and splendid reversibility,demonstrating a huge potential for affordable and scalable electrochemical H2 production.The innovational orbital hybridization strategy for electronic regulation herein provides an inspirable avenue for developing progressive electrocatalysts toward new energy systems.
查看更多>>摘要：Design and synthesis of superior cost-effective non-fullerene acceptors(NFAs)are still big challenges for facilitating the commercialization of organic solar cells(OSCs),yet to be realized.Herein,two medium bandgap fully non-fused ring electron acceptors(NFREAs,medium bandgap,i.e.,1.3-1.8 eV),namely PTR-2C1 and PTR-4C1 are synthesized with only four steps by using intramolecular noncovalent interac-tion central core,structured alkyl side chain orientation linking units and flanking with different electron-withdrawing end group.Among them,PTR-4C1 exhibits increased average electrostatic potential(ESP)difference with polymer donor,enhanced crystallinity and compact π-π stacking compared with the control molecule PTR-2Cl.As a result,the PTR-4CI-based OSC achieved an impressive power conver-sion efficiency(PCE)of 14.72％,with a much higher open-circuit voltage(Voc)of 0.953 V and significantly improved fill factor(FF)of 0.758,demonstrating one of the best acceptor material in the top-performing fully NFREA-based OSCs with both high PCE and Voc.Notably,PTR-4Cl-based cells maintain a good T80 lifetime of its initial PCE after over 936 h under a continuous thermal annealing treatment and over 1300 h T80 lifetime without encapsulation.This work provides a cost-effective design strategy for NFREAs on obtaining high Voc,efficient exciton dissociation,and ordered molecular packing and thus high-efficiency and stable OSCs.
查看更多>>摘要：Aqueous Zn metal batteries(AZMBs)with intrinsic safety,high energy density and low cost have been regarded as promising electrochemical energy storage devices.However,the parasitic reaction on metal-lic Zn anode and the incompatibility between electrode and electrolytes lead to the deterioration of elec-trochemical performance of AZMBs during the cycling.The critical point to achieve the stable cycling of AZMBs is to properly regulate the zinc ion solvated structure and transfer behavior between metallic Zn anode and electrolyte.In recent years,numerous achievements have been made to resolve the formation of Zn dendrite and interface incompatible issues faced by AZMBs via optimizing the sheath structure and transport capability of zinc ions at electrode-electrolyte interface.In this review,the challenges for metallic Zn anode and electrode-electrolyte interface in AZMBs including dendrite formation and inter-face characteristics are presented.Following the influences of different strategies involving designing advanced electrode structure,artificial solid electrolyte interphase(SEI)on Zn anode and electrolyte engi-neering to regulate zinc ion solvated sheath structure and transport behavior are summarized and dis-cussed.Finally,the perspectives for the future development of design strategies for dendrite-free Zn metal anode and long lifespan AZMBs are also given.
查看更多>>摘要：In this review,we discuss the electrochemical properties of Prussian blue(PB)for Na+storage by combin-ing structural engineering and electrolyte modifications.We integrated experimental data and density functional theory(DFT)in sodium-ion battery(SIB)research to refine the atomic arrangements and crys-tal lattices and introduce substitutions and dopants.These changes affect the lattice stability,intercala-tion,electronic and ionic conductivities,and electrochemical performance.We unraveled the intricate structure-electrochemical behavior relationship by combining experimental data with computational models,including first-principles calculations.This holistic approach identified techniques for optimizing PB and Prussian blue analog(PBA)structural properties for SIBs.We also discuss the tuning of electrolytes by systematically adjusting their composition,concentration,and additives using a combination of molecular dynamics(MD)simulations and DFT computations.Our review offers a comprehensive assess-ment of strategies for enhancing the electrochemical properties of PB and PBAs through structural engi-neering and electrolyte modifications,combining experimental insights with advanced computational simulations,and paving the way for next-generation energy storage systems.
查看更多>>摘要：Expediting redox kinetics of sulfur species on conductive scaffolds with limited charge accessible surface is considered as an imperative approach to realize energy-dense and power-intensive lithium-sulfur(Li-S)batteries.In this work,the concept of concurrent hetero-/homo-geneous electrocatalysts is pro-posed to simultaneously mediate liquid-solid conversion of lithium polysulfides(LiPSs)and solid lithium disulfide/sulfide(Li2S2/Li2S)propagation,the latter of which suffers from sluggish reduction kinetics due to buried conductive scaffold surface by extensive deposition of Li2S2/Li2S.The selected model material to verify this concept is a two-in-one catalyst:carbon nanotube(CNT)scaffold supported iron-cobalt(Fe-Co)alloy nanoparticles and partially carbonized selenium(C-Se)component.The Fe-Co alloy serves as a heterogeneous electrocatalyst to seed Li2S2/Li2S through sulphifilic active sites,while the C-Se sustainably releases soluble lithium polyselenides and functions as a homogeneous electrocatalyst to propagate Li2S2/Li2S via solution pathways.Such bi-phasic mediation of the sulfur species benefits reduction kinetics of LiPS conversion,especially for the massive Li2S2/Li2S growth scenario by affording an additional solution directed route in case of conductive surface being largely buried.This strategy endows the Li-S batteries with improved cycling stability(836 mA h g-1 after 180 cycles),rate capability(547 mA h g-1 at 4 C)and high sulfur loading superiority(2.96 mA h cm-2 at 2.4 mg cm-2).This work hopes to enlighten the employment of bi-phasic electrocatalysts to dictate liquid-solid transformation of intermediates for conversion chemistry batteries.
Kakali MaitiMatthew T.CurnanHyung Jun KimKyeounghak Kim...
669-681页
查看更多>>摘要：As a noble metal substitute,two-dimensional(2D)hierarchical nano-frame structures have attracted great interest as candidate catalysts due to their remarkable advantages-high intrinsic activity,high electron mobility,and straightforward surface functionalization.Therefore,they may replace Pt-based catalysts in oxygen reduction reaction(ORR)applications.Herein,a simple method is developed to design hierarchical nano-frame structures assembled via 2D NiO and N-doped graphene(NG)nanosheets.This procedure can yield nanostructures that satisfy the criteria correlated with improved electrocatalytic per-formance,such as large surface area,numerous undercoordinated atoms,and high defect densities.Further,porous NG nanosheet architectures,featuring NiO nanosheets densely coordinated with accessi-ble holey Fe2O3 moieties,can enhance mesoporosity and balance hydrophilicity.Such improvements can facilitate charge transport and expose formerly inaccessible reaction sites,maximizing active site density utilization.Density functional theory(DFT)calculations reveal favored O2 adsorption and dissociation on Fe2O3 hybrid structures when supported by 2D NiO and NG nanomaterials,given 2D materials donated charge to Fe2O3 active sites.Our systematic studies reveal that synergistic contributions are responsible for enriching the catalytic activity of Fe2O3@NiO/NG in alkaline media-encompassing internal voids and pores,unique hierarchical support structures,and concentrated N-dopant and bimetallic atomic interac-tions.Ultimately,this work expands the toolbox for designing and synthesizing highly efficient 2D/2D shelled functional nanomaterials with transition metals,endeavoring to benefit energy conversion and related ORR applications.
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