Tumor microenvironment-responsive drug self-delivery systems utilize tumor microenvironment-responsive chemical bonds to link anti-tumor drugs,exploiting the hydrophilic and hydrophobic properties of different drugs to form amphiphilic prodrug molecules with self-assembly characteristics.Upon stimulation by specific factors in the tumor microenvironment,these amphiphilic prodrug molecules can release drugs at precise sites within the tumor.These strategies significantly increase the drug concentration at the tumor site while effectively reducing the damage of anti-cancer drugs to normal tissues.Owing to the advanced delivery strategies such as synergistic administration and controlled drug release,tumor microenvironment-responsive drug self-delivery systems hold great potential for treating malignant tumors with multidrug resistance(MDR).At the same time,the stimulus-reactivity of metal complexes provides an important opportunity to design site-specific prodrugs that can maximize therapeutic efficacy while minimizing adverse side effects of metal drugs.This innovative drug design complements the tumor microenvironment-responsive self-delivery system,providing more feasible therapeutic strategies and possibilities in the field of cancer therapy and drug delivery.This work provides a comprehensive review of recent advancements in drug self-delivery systems,offering insights into their potential applications in cancer therapy and MDR reversal.

With the rapid development of new energy and the high proportion of new energy connected to the grid,energy storage has become the leading technology driving significant adjustments in the global energy landscape.Electrochemical energy storage,as the most popular and promising energy storage method,has received extensive attention.Currently,the most widely used energy storage method is metal-ion secondary batteries,whose performance mainly depends on the cathode material.Prussian blue analogues(PBAs)have a unique open framework structures that allow quick and reversible insertion/extraction of metal ions such as Na⁺,K⁺,Zn²⁺,Li⁺etc.,thus attracting widespread attention.The advantages of simple synthesis process,abundant resources,and low cost also distinguish it from its counterparts.Unfortunately,the crystal water and structural defects in the PBAs lattice that is generated during the synthesis process,as well as the low Na content,significantly affect their electrochemical performance.This paper focuses on PBAs’synthesis methods,crystal structure,modification strategies,and their potential applications as cathode materials for various metal ion secondary batteries and looks forward to their future development direction.

Electrocatalytic CO₂reduction reaction(CO₂RR)has been developed as a promising and attractive strategy to close the anthropogenic carbon cycle.Among various reduction products,multi-carbon(C2+)oxygenate and hydrocarbon compounds are desirable value-added fuels or chemicals.Extensive researches have revealed the crucial role of local CO₂and H₂O concentrations(or the adsorption of*CO and*H)close to the electrode/catalyst surface in manipulating multi-carbon generation pathways.In this mini reviews,we mainly summarized the recent progress of this field over the past five years.The modulating strategies for the hydrogen and carbon species ratio can be divided into three categories,i.e.,catalyst morphology,electrolyte composition and mass transfer.The effectiveness of the aforementioned strategies in promoting multi-carbon product selectivity was discussed in detail from the perspectives of tuning the local CO₂and H₂O concentrations and the subsequent thermodynamic-and kinetic-controlled*CO and*H ratios.Finally,the critical challenges remaining in balancing the ratio of CO₂and H₂O as well as potential upgrading directions for future research are addressed.

Lithium metal,with its exceptionally high theoretical capacity,emerges as the optimal anode choice for high-energy-density rechargeable batteries.Nevertheless,the practical application of lithium metal batteries(LMBs)is constrained by issues such as lithium dendrite growth and low Coulombic efficiency(CE).Herein,a roll-to-roll approach is adopted to prepare meter-scale,lithiophilic Sn-modified Cu mesh(Sn@Cu mesh)as the current collector for long-cycle lithium metal batteries.The two-dimensional(2D)nucleation mechanism on Sn@Cu mesh electrodes promotes a uniform Li flux,facilitating the deposition of Li metal in a large granular morphology.Simultaneously,experimental and computational analyses revealed that the distribution of the electric field in the Cu mesh skeleton induces Li inward growth,thereby generating a uniform,dense composite Li anode.Moreover,the Sn@Cu mesh-Li symmetrical cell demonstrates stable cycling for over 2000 h with an ultra-low 10 mV voltage polarization.In Li||Cu half-cells,the Sn@Cu mesh electrode demonstrates stable cycling for 100 cycles at a high areal capacity of 5 mAh·cm-2,achieving a CE of 99.2%.This study introduces a simple and large-scale approach for the production of lithiophilic three-dimensional(3D)current collectors,providing more possibilities for the scalable application of Li metal batteries.

Recently,hollow carbon nanospheres(HCSs)have garnered significant attention as potential Li metal hosts owing to their unique large voids and ease of fabrication.However,similar to other nanoscale hosts,their practical performance is limited by inhomogeneous agglomeration,increased binder requirements,and high tortuosity within the electrode.To overcome these problems and high tortuosity within the electrode,this study introduces a pomegranate-like carbon microcluster composed of primary HCSs(P-CMs)as a novel Li metal host.This unique nanostructure can be easily prepared using the spray-drying technique,enabling its mass production.Comprehensive analyses with various tools demonstrate that compared with HCS hosts,the P-CM host requires a smaller amount of binder to fabricate a sufficiently robust and even surface electrode.Furthermore,owing to reduced tortuosity,the well-designed P-CM electrode can provide continuous and shortened pathways for electron/ion transport,accelerating the Li-ion transfer kinetics and prohibiting preferential Li plating at the upper region of the electrode.Due to these characteristics,Li metal can be effectively encapsulated in the large inner voids of the primary HCSs constituting the P-CM,thereby enhancing the electrochemical performance of P-CM hosts in Li metal batteries.Specifically,the Coulombic efficiency of the P-CM host can be maintained at 97%over 100 cycles,with a high Li deposition areal capacity of 3 mAh·cm^-2and long cycle life(1000 h,1 mA·cm^-2,and 1.0 mAh·cm^-2).Furthermore,a full cell incorporating a LiFePO4 cathode exhibits excellent cycle life.

Lithium/fluorinated carbon(Li/CF_x)batteries are greatly limited in their applications mostly due to poor rate performances.In this study,N,P co-doped biomass carbon was synthesized using melamine and phytic acid as doping sources,and the resulting product was then utilized as a precursor for CF_x.The resulting fluorinated biomass carbon has a high degree of fluorination,exceeding the specific capacity of commercial fluorinated graphite while also demonstrating exceptional performance at high discharge rates.During the fluorination process,N,P-containing functional groups were removed from the crystalline lattice in the basal plane.This facilitates the formation of a defect-rich carbon matrix,enhancing the F/C ratio by improving the fluorinated active sites and obtaining more highly active semi-ionic bonds.Additionally,the abundant defects and porous structure promote Li⁺diffusion.Density functional theory calculations indicated that doping modification effectively reduces the energy barrier for Li+migration,enhancing Li+transport efficiency.The prepared CF_xdelivers material with a maximum specific capacity of 919 mAh·g^-1,while maintaining a specific capacity of 702 mAh·g^-1at a high discharge current density of 20C(with a capacity retention rate of 76.4%).In this study,fluorinated N,P co-doped biomass carbon,exhibiting ultrahigh capacity and high-rate performance,was prepared for the first time,which can potentially advance the commercialization of CF_x.

Ultrathin Li-rich Li-Cu binary alloy has become a competitive anode material for Li metal batteries of high energy density.However,due to the poor-lithiophilicity of the single skeleton structure of Li-Cu alloy,it has limitations in inducing Li nucleation and improving electrochemical performance.Hence,we introduced Ag species to Li-Cu alloy to form a 30μm thick Li-rich Li-Cu-Ag ternary alloy(LCA)anode,with Li-Ag infinite solid solution as the active phase,and Cu-based finite solid solutions as three-dimensional(3D)skeleton.Such nano-wire networks with LiCu4 and CuxAgy finite solid solution phases were prepared through a facile melt coating technique,where Ag element can act as lithiophilic specie to enhance the lithiophilicity of built-in skeleton,and regulate the deposition behavior of Li effectively.Notably,the formation of CuxAgy solid solution can strengthen the structural stability of the skeleton,ensuring the geometrical integrity of Li anode,even at the fully delithiated state.Meanwhile,the Li-Ag infinite solid solution phase can promote the Li plating/stripping reversibility of the LCA anode with an improved coulombic efficiency(CE).The synergistic effect between infinite and finite solid solutions could render an enhanced electrochemical performance of Li metal batteries.The LCA|LCA symmetric cells showed a long lifespan of over 600 h with stable polarization voltage of 40 mV,in 1 mA·cm^-2/1 mAh·cm^-2.In addition,the full cells matching our ultrathin LCA anode with 17.2 mg·cm^-2mass loading of LiFePO4 cathode,can continuously operate beyond 110 cycles at 0.5C,with a high capacity retention of 91.5%.Kindly check and confirm the edit made in the article title.

The design and development of high-performance anodes pose significant challenges in the construction of next-generation rechargeable lithium-ion batteries(LIBs).Sodium molybdate dihydrate(Na₂MoO₄·2H₂O)has garnered increasing attention due to its cost-effectiveness,non-toxicity and earth abundance.To enhance the Li storage performance of Na₂MoO₄·2H₂O,a crystallographic orientation regulation strategy is proposed in this work.Initially,density functional theory calculations are carried out to demonstrate that the(020)crystal plane of Na₂MoO₄·2H₂O offers the lowest energy barrier for Li⁺migration.Subsequently,the preferred crystallographic orientation of Na₂MoO₄·2H₂O crystal is tuned through a low-temperature recrystallization method.Furthermore,the microstructure and phase changes of Na₂MoO₄·2H₂O during the lithiation/de-lithiation process are studied using in situ and ex situ XRD tests,ex situ XPS and cyclic voltammetry to unravel its Li⁺storage mechanism.Upon application as LIBs anode,the Na₂MoO₄·2H₂O single-crystal particles with a preferred(020)surface exhibit superior reversible capacity,high-capacity retention and high cycling stability.The enhanced Li storage performance should be attributed to the regulated crystallographic orientation and small changes in the crystal microstructure during the charge/discharge process,which facilitates Li⁺migration and bolsters structural stability.Notably,this study introduces a novel concept and a simple synthesis method for the advancement of electrodes in rechargeable batteries.

LiMnxFe1-xPO4 is a promising cathode candidate due to its high security and the availability of a high 4.1 V operating voltage and high energy density.However,the poor electrochemical kinetics and structural instability currently hinder its broader application.Herein,inspired by the hydrogen-bonded cross-linking and steric hindrance effect between short-chain polymer molecules(polyethylene glycol-400,PEG-400),the pomegranate-type LiMn_0.5Fe_0.5PO₄-0.5@C(P-LMFP@C)cathode materials with 3D ion/electron dual-conductive network structure were constructed through ball mill-assisted spray-drying method.The intermolecular effects of PEG-400 promote the spheroidization and uniform PEG coating of LMFP precursor,which prevents agglomeration during sintering.The 3D ion/electron dual-conductive network structure in P-LMFP@C accelerates the Li⁺transport kinetics,improving the rate performance and cycling stability.As a result,the designed P-LMFP@C has remarkable electrochemical behavior,boasting excellent capacity retention(98%after 100 cycles at the 1C rate)and rate capability(91 mAh·g^-1at 20C).Such strategy introduces a novel window for designing high-performance olivine cathodes and offers compatibility with a range of energy storage materials for diverse applications.

Tin-based metal organic complexes with breakable coordination bonds,multiple active sites,and high theoretical capacity have attracted wide attentiorials for lithium-ion batteries(LIBs).However,the inferior electrical conductivity and significant volume changes have limited their electrochemical stability and practical application performance.This work proposes a universal doping strategy for the preparation of tin-phthalic acid complexes(Sn-MOF)doped with metal atoms(Al,Cr,Mn,Fe,Co,Ni,Cu,Zn).Metal atoms are uniformly dispersed within Sn-MOF for enhancing electrical conductivity and accommodating appropriate volume expansion,resulting in improved rate capability and cycling stability.Additionally,compared to a series of doped Sn-MOF,Zn-doped Sn-MOF exhibits the most exceptional electrochemical performance with a high reversible capacity of 1131 mAh·g^-1and stable cycling performance at a current density of 0.5 A·g^-1,delivering a capacity of 1065 mAh·g^-1after 500 cycles.Zn-doping catalyzes the lithiation reaction between Sn-MOF and Li⁺,promoting their reaction kinetics during the first cycle.Furthermore,the Zn-doped Sn-MOF is inclined to form a thin and stable solid electrolyte interface film to maintain cyclic stability.