Microneedles(MNs)offer a precise and minimally invasive platform for delivering vaccines and therapeutic agents directly into the skin,leveraging the abundance of tissue-resident immune cells to elicit robust and dura...Microneedles(MNs)offer a precise and minimally invasive platform for delivering vaccines and therapeutic agents directly into the skin,leveraging the abundance of tissue-resident immune cells to elicit robust and durable immune responses.Compared to traditional intramuscular or subcutaneous vaccination methods,MNbased vaccines demonstrate superior patient compliance,enhanced antigen stability,and heightened immunogenicity,positioning them as a promising tool in biomedical applications.This review provides a comprehensive overview of the materials and fabrication techniques used in MN preparation,explores their structural classifications,and examines the role of antigens and adjuvants in optimizing vaccine efficacy.Furthermore,the diverse applications of MN delivery systems in preventing infectious diseases,advancing tumor immunotherapy,and addressing other immune-related conditions are discussed.展开更多
The semi-hydrogenation of alkynes to alkenes is of great significance in the industrial production of pharmaceutical and fine chemicals.Electrochemical semi-hydrogenation(ECSH)has emerged as a promising alternative to...The semi-hydrogenation of alkynes to alkenes is of great significance in the industrial production of pharmaceutical and fine chemicals.Electrochemical semi-hydrogenation(ECSH)has emerged as a promising alternative to conventional thermochemical hydrogenation.However,its practical application is hindered by low reaction rate and competing hydrogen evolution reaction(HER).In this work,the controllable incorporation of sulfur into the lattice of Pd nanostructures is proposed to develop disordered and electron-deficient Pd-based nanosheets on Ni foam and enhance their ECSH performance of alkynes.Mechanistic investigations demonstrate that the electronic and geometric structures of Pd sites are optimized by lattice sulfur,which tunes the competitive adsorption of H*and alkynes,inherently inhibits the H*coupling and weakens alkene adsorption,thereby promotes the semi-hydrogenation of alkynes and prevents the over-hydrogenation of alkenes.The optimized Pd-based nanosheets exhibit efficient electrocatalytic semi-hydrogenation performance in an H-cell,achieving 97%alkene selectivity,94%Faradaic efficiency,and a reaction rate of 303.7μmol mgcatal.^(-1) h^(-1) using 4-methoxyphenylacetylene as the model substrate.Even in a membrane electrode assembly(MEA)configuration,the optimized Pd-based nanosheets achieves a single-cycle alkyne conversion of 96%and an alkene selectivity of 97%,with continuous production of alkene at a rate of 1901.1μmol mgcatal.^(-1) h^(-1).The potential-and time-independent selectivity,good substrate universality with excellent tolerance to active groups(C–Br/Cl/C]O,etc.)further highlight the potential of this strategy for advanced catalysts design and green chemistry.展开更多
The rare earth elements(REEs)extraction by chemical leaching from ion-adsorption type rare earth ores(IAREO)has led to serious ecological and environmental risks.Conversely,demand for bioleaching is on the rise with t...The rare earth elements(REEs)extraction by chemical leaching from ion-adsorption type rare earth ores(IAREO)has led to serious ecological and environmental risks.Conversely,demand for bioleaching is on the rise with the advantage of being environmental-friendly.As one of the organic acids produced by biological metabolism,citric acid was used to leach REEs and explore the performance and process.The results demonstrate that citric acid exhibits higher leaching efficiency(96.00%)for REEs at a relatively low concentration of 0.01 mol/L compared with(NH_(4))_(2)SO_(4)(84.29%,0.1 mol/L)and MgSO_(4)(83.99%,0.1 mol/L).Citric acid shows a preference for leaching heavy rare earth elements,with 99%leaching efficiency in IAREO,which shows higher capacity than(NH_(4))_(2)SO_(4)and MgSO_(4)(as inorganic leaching agents).Kinetic analysis indicates that the leaching process of REEs with citric acid is controlled by both the internal diffusion kinetics and chemical reaction kinetics,which is different from inorganic leaching agents.Visual Minteq calculations confirm that RE-Citrate is the main constituent of the extract solution in the leaching process of the IAREO,thereby enhancing the leaching efficiency of REEs from the IAREO.It suggests that citric acid may be used as a promising organic leaching agent for the environmentalfriendly extraction of REEs from IAREO.展开更多
The structural modulation of metal-based heterostructure plays a vital role in achieving enhanced performances for highly efficient electrocatalysis.Here we design submonolayered Ru-modified Pd mesoporous nanosheets(P...The structural modulation of metal-based heterostructure plays a vital role in achieving enhanced performances for highly efficient electrocatalysis.Here we design submonolayered Ru-modified Pd mesoporous nanosheets(Pd-Ru MNSs)with the exposure of both Pd and Ru active sites as well as the high atomic utilization of two-dimensional structure.The obtained Pd-Ru MNSs can act as a highly efficient multifunctional catalyst for hydrogen evolution reaction(HER)and alcohol oxidation reactions including ethylene glycol oxidation(EGOR)and ethanol oxidation(EOR),offering new opportunities towards the alcohol oxidation assisted hydrogen production.Specifically,Pd-Ru MNSs demonstrate excellent HER performance in alkaline electrolyte,requiring an overpotential of only 16mV to reach 10mAcm^(−2),significantly outperforming Pd mesoporous nanosheets and commercial catalysts.Density functional theory calculations reveal that the Ru sites in Pd-Ru MNSs could facilitate the water adsorption,accelerate the water dissociation,and optimize the hydrogen desorption,leading to the superior HER activity.Pd-Ru MNSs also exhibit high mass activities of 11.19 A mg^(−1)Pd for EGOR and 8.84 A mg^(−1)Pd for EOR,which is 7.8 and 9.6 times than that of commercial Pd/C,respectively.The EGOR reaction pathway over Pd-Ru MNSs was further investigated by using in situ Fourier-transform infrared spectroscopy.展开更多
Particle formulation engineering stands as a focal point of research and a critical trajectory within the chemical industry.In response to the challenges associated with antigen/drug delivery,our research group has pr...Particle formulation engineering stands as a focal point of research and a critical trajectory within the chemical industry.In response to the challenges associated with antigen/drug delivery,our research group has proposed a suite of strategies centered on micro/nanoparticle platforms.This review integrates our investigations into the applications of particles across various dimensions in biomedical delivery systems.Specifically,it delineates the mechanisms by which particles augment vaccine-induced immune responses,notably through antigen cross-presentation,and the pivotal roles they play in facilitating drug-mediated targeting of cancer cells via confined mass transfer.This review also encompasses recent advancements in particle formulations,offering prospective insights into the utilization of chemical engineering principles in the design of nextgeneration biomedical delivery systems.展开更多
1.EMT in cancer metastasis and chemoresistance Cancer metastasis is contingent on the epithelial-mesenchymal transition(EMT)of cancer cells.During EMT,epithelial cancer cells transform into a mesenchymal phenotype,whi...1.EMT in cancer metastasis and chemoresistance Cancer metastasis is contingent on the epithelial-mesenchymal transition(EMT)of cancer cells.During EMT,epithelial cancer cells transform into a mesenchymal phenotype,which endows cancer cells with enhanced migratory and invasive abilities,promoting their dissemination throughout the body.EMT also contributes significantly to chemoresistance,allowing cancer cells to survive and metastasize even after chemotherapy[1].展开更多
Sonodynamic therapy(SDT)as an emerging modality for malignant tumors mainly involves in sonosensitizers and low-intensity ultrasound(US),which can safely penetrate the tissue without significant attenuation.SDT not on...Sonodynamic therapy(SDT)as an emerging modality for malignant tumors mainly involves in sonosensitizers and low-intensity ultrasound(US),which can safely penetrate the tissue without significant attenuation.SDT not only has the advantages including high precision,non-invasiveness,and minimal side effects,but also overcomes the limitation of low penetration of light to deep tumors.The cytotoxic reactive oxygen species can be produced by the utilization of sonosensitizers combined with US and kill tumor cells.However,the underlying mechanism of SDT has not been elucidated,and its unsatisfactory efficiency retards its further clinical application.Herein,we shed light on the main mechanisms of SDT and the types of sonosensitizers,including organic sonosensitizers and inorganic sonosensitizers.Due to the development of nanotechnology,many novel nanoplatforms are utilized in this arisen field to solve the barriers of sonosensitizers and enable continuous innovation.This review also highlights the potential advantages of nanosonosensitizers and focus on the enhanced efficiency of SDT based on nanosonosensitizers with monotherapy or synergistic therapy for deep tumors that are difficult to reach by traditional treatment,especially orthotopic cancers.展开更多
Hollow multi-shelled structure(HoMS)is the novel multifunctional structural system,which are con-structed with nanoparticles as structural units,featuring two or more shells,multiple interfaces,and numerous chan-nels ...Hollow multi-shelled structure(HoMS)is the novel multifunctional structural system,which are con-structed with nanoparticles as structural units,featuring two or more shells,multiple interfaces,and numerous chan-nels and demonstrating outstanding properties in energy conversion and mass transfer.In recent years,owing to the breakthroughs in synthetic methods,the diversity of composition and structure of HoMS has been greatly enriched,showing broad application prospects in energy,catalysis,environment and other fields.This review focuses on the research status of HoMS for catalytic applications.Firstly,the new synthesis method for HoMS,namely the sequen-tial templating approach,is introduced from both practical and theoretical perspectives.Then,it summarizes and discusses the structure-performance relationship between the shell structure and catalytic performance.The unique temporal-spatial ordering property of mass transport in HoMS and the major breakthroughs it brings in catalytic applications are discussed.Finally,it looks forward to the opportunities and challenges in the development of HoMS.展开更多
In recent years,peptide-based therapies have gained remarkable attention as promising tools for cancer treatment,offering notable advantages in specifcity,modifability,and reduced systemic toxicity.Various peptide cla...In recent years,peptide-based therapies have gained remarkable attention as promising tools for cancer treatment,offering notable advantages in specifcity,modifability,and reduced systemic toxicity.Various peptide classes-including cell-penetrating,tumor-homing,pro-apoptotic,and immunemodulating peptides-have shown appreciable efcacy in selectively targeting cancer cells and modulating immune responses against tumors.Despite this potential,peptide therapies face signifcant challenges,such as susceptibility to rapid degradation,limited bioavailability,and inadequate accumulation within tumors.To address these issues,bacterial systems have emerged as innovative peptide delivery platforms,improving peptide stability,enhancing localized concentrations,and enabling controlled release directly at tumor sites.This review explores the synergistic potential of therapeutic peptides combined with bacterial delivery systems,with a focus on methods such as bacterial lysis for peptide release,secretion pathways,and peptide surface display.By harnessing the tumor-targeting properties and secretion capabilities of bacteria,these integrated approaches offer promising solutions to overcome the inherent limitations of peptide therapies,positioning them as advanced tools in precision oncology.展开更多
Inspired by the visual neurons of biological systems,optoelectronic synaptic devices integrate photoresponsive semiconductor materials to convert light into electrical signals,enabling biomimetic visual perception sys...Inspired by the visual neurons of biological systems,optoelectronic synaptic devices integrate photoresponsive semiconductor materials to convert light into electrical signals,enabling biomimetic visual perception systems.Achieving memory retention and intelligent perceptual functions continues to pose a major hurdle in the advancement of neuromorphic artificial synapse devices.This review begins with an exploration of biological neural synapses,analyzing the fundamental characteristics and structures of biomimetic optoelectronic synapses.It then delves into the design of device and material structures to achieve postsynaptic current and memory behavior,elucidating their underlying mechanisms.Furthermore,the latest application scenarios of these devices are summarized,highlighting the opportunities and challenges in their future development.This review aims to provide a comprehensive understanding of the advancements in optoelectronic synapses,from material innovations to neuromorphic applications,paving the way for next-generation artificial visual systems and neuromorphic computing.展开更多
The mRNA vaccines have become a transformative platform in medicine,with their success during the COVID-19 pandemic accelerating research in viral prevention and cancer therapy.Lipid nanoparticles(LNPs)enhance the sta...The mRNA vaccines have become a transformative platform in medicine,with their success during the COVID-19 pandemic accelerating research in viral prevention and cancer therapy.Lipid nanoparticles(LNPs)enhance the stability and efficacy of mRNA vaccines,but achieving an optimal balance between innate immune activation and mRNA expression is crucial for their effectiveness.Classical cationic lipids,although largely replaced by ionizable lipids due to concerns over excessive immunogenicity,have demonstrated potential in cancer immunotherapy by inducing strong immune responses.In this study,we investigated whether incorporating cationic lipids into mRNA-LNP formulations could enhance immunogenicity without requiring new lipid designs.We introduced varying proportions of cationic lipids into D-Lin-MC3-DMA and SM-102-based LNPs and evaluated their impact on innate immune activation,along with long-term humoral and cellular immune responses.Our results showed that in MC3-based LNPs,cationic lipids significantly improved anti-tumor efficacy,though slightly diminished long-term humoral and cellular immunity.In contrast,in SM-102-based LNPs,cationic lipids enhanced anti-tumor effects without negatively impacting long-term immunity.These findings suggest that adding cationic lipid as an additional component allows for the fine-tuning of mRNA-LNP immunogenicity,expanding the potential applications of mRNA vaccines and simplifying LNP design.展开更多
Metabolism is a general term for a series of ordered chemical reactions in an organism used to maintain life,mainly divided into anabolic and catabolic metabolism.Nucleic acid therapy can not only precisely up-regulat...Metabolism is a general term for a series of ordered chemical reactions in an organism used to maintain life,mainly divided into anabolic and catabolic metabolism.Nucleic acid therapy can not only precisely up-regulate and down-regulate the expression of target genes but also correct mutated disease-causing genes,which demonstrates irreplaceable and outstanding advantages in the treatment of metabolismrelated diseases and has been applied to the clinical treatment of metabolism-related diseases.In this review,we introduce the structures of several major nucleic acid drugs and the mechanism of nucleic acid therapy.Subsequently,we describe the mechanisms of various biomolecular and tissue metabolisms and the etiology of metabolic disorders,classified according to metabolic substrates.We analyze the signal pathways and potential targets affecting the metabolism of each substrate and describe the nucleic acid drugs applied to these targets and their delivery technologies.This review aims to provide new ideas and targets for treating these diseases by investigating the role played by metabolism in developing diseases and providing guidance for the selection and design of nucleic acid drugs.展开更多
Melanin is an advanced polymer with exceptional properties,widely used across cosmetics,pharmaceuticals,environmental applications,and more.However,its broader use is constrained by high production costs and limited a...Melanin is an advanced polymer with exceptional properties,widely used across cosmetics,pharmaceuticals,environmental applications,and more.However,its broader use is constrained by high production costs and limited availability.Lignin,the most abundant and renewable aromatic compound in nature,presents a promising alternative for synthesizing melanin.This study focuses on converting plentiful and cost-effective lignin into melanin through the metabolic engineering of Cupriavidus necator H16.By constructing and optimizing metabolic pathways,engineered C.necator strains were developed to synthesize melanin from lignin monomers and lignin hydrolysates.Using substrates like p-coumaric acid,caffeic acid,ferulic acid,and lignin hydrolysates,the resting cell method with C.necator produced 0.86,1.00,0.52,and 0.32 g L^(-1)of melanin,respectively.The purified melanin was analyzed and identified spectrally,revealing characteristics of isomelanin.Furthermore,sun protection factor studies demonstrated that the produced melanin offered significant UV protection.The use of engineered C.necator to convert abundant lignin hydrolysates into melanin holds great promise for reducing production costs and expanding its applications.展开更多
Ferritin has emerged as a promising nanocarrier for delivering therapeutic agents to tumours.However,the limited drug loading and the off-target impacts after systemic administration remain challenges for cancer treat...Ferritin has emerged as a promising nanocarrier for delivering therapeutic agents to tumours.However,the limited drug loading and the off-target impacts after systemic administration remain challenges for cancer treatment with ferritin-based agents.Herein,we develop a microneedle patch loaded with ferritin-nanocaged doxorubicin(DoxFe@Fn/MN)for skin cancer treatment.Briefly,doxorubicin(Dox)is encapsulated in ferritin(Fn)using an iron core-assisted strategy,which results in a 3.4-fold increase in Dox loading compared to the direct loading method.Then,a polyvinyl alcohol-based microneedle(MN)patch is used for the transdermal delivery of DoxFe@Fn,enabling targeted tumour accumulation of DoxFe@Fn and preventing off-target impacts.The released DoxFe@Fn can bind to CD71 highly expressed on skin cancer cells,facilitating its uptake.As a result,the DoxFe@Fn/MN therapy presents a robust antitumour effect in a melanoma tumour model,showing its potential as a promising therapeutic modality for skin cancer treatment.展开更多
Immune checkpoint blockade(ICB)has emerged as a promising immunotherapeutic modality against cancer in the clinic.However,only 10-30%of patients respond to ICB,primarily due to poor immunogenicity and insufficient T c...Immune checkpoint blockade(ICB)has emerged as a promising immunotherapeutic modality against cancer in the clinic.However,only 10-30%of patients respond to ICB,primarily due to poor immunogenicity and insufficient T cell infiltration in solid tumors.Herein,we presented an approach for high-performance cancer treatment using the programmed cell death protein-1 and programmed cell death ligand-1(PD-1/PD-L1)inhibitor(BMS-202)-loaded PEGylated graphene oxide(GPi).On the one hand,GPi dissociated tight junctions of vascular endothelial cells(VECs)in tumor,thus promoting the extravasation and intratumoral accumulation of liposomal doxorubicin(LipDox),which then effectively induced immunogenic cell death of tumor cells.On the other hand,GPi also stimulated VECs to upregulate the expression of cell-cell interaction molecules,such as intercellular cell adhesion molecule-1 and vascular cell adhesion molecule-1,which facilitated the infiltration of T cells in tumor.Beyond acting as a stimulator of VECs,GPi could exert responsive release of BMS-202 under the acidic tumor microenvironment and blockade PD-1/PD-L1 axis in tumors.Finally,the alternating administration of GPi and LipDox effectively inhibited tumor growth in a 4T1 tumor model,providing a novel treatment mode for chemo-immunotherapy.展开更多
Tumor immunotherapy,particularly cancer vaccines,holds promise for combating cancer by harnessing tailored immune responses against malignant cells.However,conventional approaches face challenges in efficiently delive...Tumor immunotherapy,particularly cancer vaccines,holds promise for combating cancer by harnessing tailored immune responses against malignant cells.However,conventional approaches face challenges in efficiently delivering antigens for optimal immune activation.Emulsion adjuvants,like MF59,enhance cellular uptake but struggle to induce robust CD8^(+)T cell responses.Here,we introduce a novel strategy employing a water-in-oil-in-water(W/O/W)multiple Pickering emulsion(mPE)for antigen delivery.The mPE,utilizing biocompatible,pH-sensitive particles,encapsulates antigens within the inner water phase,ensuring enhanced intracellular processing and dictating the intracellular fate of antigens for improved cross-presentation.In vitro and in vivo studies demonstrated that mPEs induced robust dendritic cells activation and antigen cross-presentation,leading to a significantly enhanced immune response.Notably,calcium phosphate-stabilized mPE(CaP-mPE)illustrated the more robust IFN-γ^(+)T cell responses.In comparison with traditional surfactant-stabilized multiple emulsions,CaP-mPE significantly inhibit tumor growth and effectively prolong the survival of tumor-bearing mice.This innovative approach offers a promising avenue for the development of effective cancer vaccines with potent cellular immune responses.展开更多
The ultimate goal of photocatalytic CO_(2)reduction is to efficiently convert atmospheric CO_(2)into value-added products by designing hierarchical photocatalysts that combine effective harvesting and accelerate activ...The ultimate goal of photocatalytic CO_(2)reduction is to efficiently convert atmospheric CO_(2)into value-added products by designing hierarchical photocatalysts that combine effective harvesting and accelerate activation capabilities of CO_(2)molecules.In this work,we demonstrated direct air-level CO_(2)reduction by hollow multishell structure(HoMS)nanoreactors with zeolitic imidazolate framework-8(ZIF-8)-modified ZnO heteroshells,which offers a promising solution to optimize the mass transfer process via selective sieving and effective enrichment of CO_(2)molecules from the atmospheric environments.Specifically,heteroshells with ZIF-8 matrix act as pumps that effectively capture CO_(2)molecules,while the cavities serve as tanks to hold these molecules,thus significantly enhancing the transfer kinetics for CO_(2)photoreduction.The periodic shell-cavity configuration allows the nanoreactor to effectively gather CO_(2)molecules near the catalytic sites,thus increasing conversion opportunities for activated molecules.Simultaneously,the surface atomic steps on the ZnO/ZIF-8 heterointerfaces with staggered geometry expedite charge transfer and adsorption efficiency,which synergistically boosts the CO_(2)-CO yield up to 3.7μmol/h under CO_(2)flow and 0.7μmol/h under atmospheric conditions with almost complete CO selectivity.Hopefully,the HoMS nanoreactors offer a potential strategy for solving the“last mile”challenge in practical CO_(2)valorization.展开更多
Fusobacterium nucleatum(Fn),an oral anaerobic commensal,has recently been identified as a crucial oncogenic contributor to colorectal cancer pathogenesis through its ectopic colonization in the gastrointestinal tract....Fusobacterium nucleatum(Fn),an oral anaerobic commensal,has recently been identified as a crucial oncogenic contributor to colorectal cancer pathogenesis through its ectopic colonization in the gastrointestinal tract.Accumulating evidence reveals its multifaceted involvement in colorectal cancer initiation,progression,metastasis,and therapeutic resistance to conventional treatments,including chemotherapy,radiotherapy,and immunotherapy.This perspective highlights recent advances in anti-Fn strategies,including small-molecule inhibitors,nanomedicines,and biopharmaceuticals,while critically analyzing the translational barriers in developing targeted antimicrobial interventions.We further propose potential strategies to overcome current challenges in Fn modulation,aiming to pave the way for more effective therapeutic interventions and better clinical outcomes.展开更多
The unique physiological characteristics and complexity of tumor,in addition to drug resistance result in traditional therapies,such as chemotherapy and radiotherapy,being unable to achieve complete elimination of can...The unique physiological characteristics and complexity of tumor,in addition to drug resistance result in traditional therapies,such as chemotherapy and radiotherapy,being unable to achieve complete elimination of cancer cells.Meanwhile,the emerging immunotherapy suffers from a low patient response rate.Bacterial therapies are highly targeted.Bacteria can penetrate deep into the tumor and show good tumor inhibition.However,natural bacteria have the limitation of high toxicity and inability to meet the demand for efficient therapeutics.Recent advances in synthetic biology and materials science relate to the safety and efficacy of bacterial therapeutics,promising to develop engineered bacteria with low toxicity and complex therapeutic functions.Engineered bacteria that express anticancer drug molecules can target the tumor region,synthesizing and releasing payloads in response to internal and external stimuli.This process leads to the regression of the tumor and the effective inhibition of recurrence.This review outlines the recent advancements in the field of engineered bacteria research,particularly focusing on their applications in anti-tumor therapy.It also includes the advantageous features and mechanisms of engineered bacteria therapy,synthetic biology modification methods,and future challenges and directions of engineered bacteria therapy.展开更多
Developing noble-metal-free oxygen evolution reaction(OER)electrocatalysts with stable performance at large working current is an imperative and yet formidable challenge for practical large scale water splitting.In th...Developing noble-metal-free oxygen evolution reaction(OER)electrocatalysts with stable performance at large working current is an imperative and yet formidable challenge for practical large scale water splitting.In this study,by inheriting hierarchical nanostructure and elemental homogeneity of Prussian blue analogues,a series of medium entropy transition metal phosphides(METMP)OER catalysts with high cost-effectivity,efficiency and stability were precisely prepared.Specifically,the METMP-based((FeCoNi)P/Ni_(2)P-NF)catalyst demonstrates exceptional performance with an overpotential of only 232 mV at 50 mA·cm^(-2)and a Tafel slope of 52.7 mV·dec^(-1),significantly superior to its less entropy counterparts and commercial RuO_(2-).Moreover,it even maintains stability at the industrial standard current density of 500 mA·cm^(-2)for over 200 h.Density functional theory(DFT)calculations indicates that the synergistic effect of Fe,Co,Ni modulates electronic structure of METMPs,which effectively reduces the energy barrier for the rate-determining HOO*formation step,thereby considerably enhancing catalytic activity.This work not only contributes to the fundamental understanding of the role of medium/high entropy in catalysis but also paves the way for the development of next-generation electrocatalysts for energy-related applications.展开更多
基金supported by the National Science Fund for National Natural Science Foundation of China(Grant Nos.22232006,22377127,and 52361145848)Chinese Academy of Sciences(CAS)Project for Young Scientists in Basic Research(Grant No.YSBR-083)+2 种基金the Beijing Nova Program(Grant Nos.20230484352 and 20240484650)Institute of Process Engineering Project for Frontier Basic Research(Grant No.QYJC-2023-05)Progress of Strategy Priority Research Program(Category B)of CAS(Grant No.XDB0520300).
文摘Microneedles(MNs)offer a precise and minimally invasive platform for delivering vaccines and therapeutic agents directly into the skin,leveraging the abundance of tissue-resident immune cells to elicit robust and durable immune responses.Compared to traditional intramuscular or subcutaneous vaccination methods,MNbased vaccines demonstrate superior patient compliance,enhanced antigen stability,and heightened immunogenicity,positioning them as a promising tool in biomedical applications.This review provides a comprehensive overview of the materials and fabrication techniques used in MN preparation,explores their structural classifications,and examines the role of antigens and adjuvants in optimizing vaccine efficacy.Furthermore,the diverse applications of MN delivery systems in preventing infectious diseases,advancing tumor immunotherapy,and addressing other immune-related conditions are discussed.
基金financially supported by the National Natural Science Foundation of China(51701127,92163209,12264053)Shenzhen Fundamental Research Program(JCYJ20220811170904003,JCYJ20210324094000001)+6 种基金Shenzhen Peacock Plan(20180703896C)Shenzhen Key Laboratory of 2D Metamaterials for Information Technology(ZDSYS201707271014468)the research projects of Guangdong Provincial Education Office(2024KCXTD064)ZJUHIC start-up fund(02090200-K02013002)Beijing Natural Science Foundation(JQ22004)the Natural Science Foundation of Hangzhou(2024SZRYBB020001)the Scientific Research and Innovation Project of Postgraduate Students in the Academic Degree of Yunnan University(KC-23234366).
文摘The semi-hydrogenation of alkynes to alkenes is of great significance in the industrial production of pharmaceutical and fine chemicals.Electrochemical semi-hydrogenation(ECSH)has emerged as a promising alternative to conventional thermochemical hydrogenation.However,its practical application is hindered by low reaction rate and competing hydrogen evolution reaction(HER).In this work,the controllable incorporation of sulfur into the lattice of Pd nanostructures is proposed to develop disordered and electron-deficient Pd-based nanosheets on Ni foam and enhance their ECSH performance of alkynes.Mechanistic investigations demonstrate that the electronic and geometric structures of Pd sites are optimized by lattice sulfur,which tunes the competitive adsorption of H*and alkynes,inherently inhibits the H*coupling and weakens alkene adsorption,thereby promotes the semi-hydrogenation of alkynes and prevents the over-hydrogenation of alkenes.The optimized Pd-based nanosheets exhibit efficient electrocatalytic semi-hydrogenation performance in an H-cell,achieving 97%alkene selectivity,94%Faradaic efficiency,and a reaction rate of 303.7μmol mgcatal.^(-1) h^(-1) using 4-methoxyphenylacetylene as the model substrate.Even in a membrane electrode assembly(MEA)configuration,the optimized Pd-based nanosheets achieves a single-cycle alkyne conversion of 96%and an alkene selectivity of 97%,with continuous production of alkene at a rate of 1901.1μmol mgcatal.^(-1) h^(-1).The potential-and time-independent selectivity,good substrate universality with excellent tolerance to active groups(C–Br/Cl/C]O,etc.)further highlight the potential of this strategy for advanced catalysts design and green chemistry.
基金Project supported by the Thousand Talents Program of Jiangxi Province,China(JXSQ2023201003)National Natural Science Foundation of China(42107254)+4 种基金Science and Technology Major Program of Ordos City(2022EEDSKJZDZX014-2)Technological Innovation Guidance Program of Jiangxi Province(20212BDH81029)Rare Earth Industry Fund(IAGM2020DB06)Selfdeployed Projects of Ganjiang Innovation Academy,Chinese Academy of Sciences(E055A01)the Key Research Program of the Chinese Academy of Sciences(ZDRW-CN-2021-3-3)。
文摘The rare earth elements(REEs)extraction by chemical leaching from ion-adsorption type rare earth ores(IAREO)has led to serious ecological and environmental risks.Conversely,demand for bioleaching is on the rise with the advantage of being environmental-friendly.As one of the organic acids produced by biological metabolism,citric acid was used to leach REEs and explore the performance and process.The results demonstrate that citric acid exhibits higher leaching efficiency(96.00%)for REEs at a relatively low concentration of 0.01 mol/L compared with(NH_(4))_(2)SO_(4)(84.29%,0.1 mol/L)and MgSO_(4)(83.99%,0.1 mol/L).Citric acid shows a preference for leaching heavy rare earth elements,with 99%leaching efficiency in IAREO,which shows higher capacity than(NH_(4))_(2)SO_(4)and MgSO_(4)(as inorganic leaching agents).Kinetic analysis indicates that the leaching process of REEs with citric acid is controlled by both the internal diffusion kinetics and chemical reaction kinetics,which is different from inorganic leaching agents.Visual Minteq calculations confirm that RE-Citrate is the main constituent of the extract solution in the leaching process of the IAREO,thereby enhancing the leaching efficiency of REEs from the IAREO.It suggests that citric acid may be used as a promising organic leaching agent for the environmentalfriendly extraction of REEs from IAREO.
基金financial support from the National Natural Science Foundation of China(No.52471219)the Fundamental Research Funds for the Central Universities(No.00007838)+5 种基金financial support from the National Natural Science Foundation of China(No.52471220 and U2441264)the Guangdong Basic and Applied Basic Research Foundation(No.2022A1515140051)financial support from the National Natural Science Foundation of China(No.92163209)Beijing Natural Science Foundation(No.JQ22004)financial support from the National Natural Science Foundation of China(No.52476146)Guangdong Basic and Applied Basic Research Foundation(2023A1515140059,2025A1515011255).
文摘The structural modulation of metal-based heterostructure plays a vital role in achieving enhanced performances for highly efficient electrocatalysis.Here we design submonolayered Ru-modified Pd mesoporous nanosheets(Pd-Ru MNSs)with the exposure of both Pd and Ru active sites as well as the high atomic utilization of two-dimensional structure.The obtained Pd-Ru MNSs can act as a highly efficient multifunctional catalyst for hydrogen evolution reaction(HER)and alcohol oxidation reactions including ethylene glycol oxidation(EGOR)and ethanol oxidation(EOR),offering new opportunities towards the alcohol oxidation assisted hydrogen production.Specifically,Pd-Ru MNSs demonstrate excellent HER performance in alkaline electrolyte,requiring an overpotential of only 16mV to reach 10mAcm^(−2),significantly outperforming Pd mesoporous nanosheets and commercial catalysts.Density functional theory calculations reveal that the Ru sites in Pd-Ru MNSs could facilitate the water adsorption,accelerate the water dissociation,and optimize the hydrogen desorption,leading to the superior HER activity.Pd-Ru MNSs also exhibit high mass activities of 11.19 A mg^(−1)Pd for EGOR and 8.84 A mg^(−1)Pd for EOR,which is 7.8 and 9.6 times than that of commercial Pd/C,respectively.The EGOR reaction pathway over Pd-Ru MNSs was further investigated by using in situ Fourier-transform infrared spectroscopy.
基金supported by the National Natural Science Foundation of China(Grant Nos.82341405,32030062,and U20A20361)the National Key Research and Development Program of China(Grant Nos.2021YFC2302603 and 2023YFC2307700)+1 种基金the CAS Project for Young Scientists in Basic Research(Grant No.YSBR-083)the IPE Project for Frontier Basic Research(Grant No.QYJC-2022-012).
文摘Particle formulation engineering stands as a focal point of research and a critical trajectory within the chemical industry.In response to the challenges associated with antigen/drug delivery,our research group has proposed a suite of strategies centered on micro/nanoparticle platforms.This review integrates our investigations into the applications of particles across various dimensions in biomedical delivery systems.Specifically,it delineates the mechanisms by which particles augment vaccine-induced immune responses,notably through antigen cross-presentation,and the pivotal roles they play in facilitating drug-mediated targeting of cancer cells via confined mass transfer.This review also encompasses recent advancements in particle formulations,offering prospective insights into the utilization of chemical engineering principles in the design of nextgeneration biomedical delivery systems.
基金support from the National Science Foundation CAREER Award,USA(Grant No.:2143972)the National Institutes of Health through the Award,USA(Grant No.:R15CA274349).
文摘1.EMT in cancer metastasis and chemoresistance Cancer metastasis is contingent on the epithelial-mesenchymal transition(EMT)of cancer cells.During EMT,epithelial cancer cells transform into a mesenchymal phenotype,which endows cancer cells with enhanced migratory and invasive abilities,promoting their dissemination throughout the body.EMT also contributes significantly to chemoresistance,allowing cancer cells to survive and metastasize even after chemotherapy[1].
基金supported by the National Natural Science Foundation of China(Nos.U23A20573,U23A20140,22072154,and 22377127)Hebei Natural Science Foundation(B2024208046 and H2022423314)+2 种基金Huang jin tai plan project of Hebei provincial department of education(HJZD202512)S&T Program of Hebei,the Youth innovation Promotion Association of Chinese Academy of Sciences(No.2021048)the Beijing Nova Program(No.20230484352).
文摘Sonodynamic therapy(SDT)as an emerging modality for malignant tumors mainly involves in sonosensitizers and low-intensity ultrasound(US),which can safely penetrate the tissue without significant attenuation.SDT not only has the advantages including high precision,non-invasiveness,and minimal side effects,but also overcomes the limitation of low penetration of light to deep tumors.The cytotoxic reactive oxygen species can be produced by the utilization of sonosensitizers combined with US and kill tumor cells.However,the underlying mechanism of SDT has not been elucidated,and its unsatisfactory efficiency retards its further clinical application.Herein,we shed light on the main mechanisms of SDT and the types of sonosensitizers,including organic sonosensitizers and inorganic sonosensitizers.Due to the development of nanotechnology,many novel nanoplatforms are utilized in this arisen field to solve the barriers of sonosensitizers and enable continuous innovation.This review also highlights the potential advantages of nanosonosensitizers and focus on the enhanced efficiency of SDT based on nanosonosensitizers with monotherapy or synergistic therapy for deep tumors that are difficult to reach by traditional treatment,especially orthotopic cancers.
文摘Hollow multi-shelled structure(HoMS)is the novel multifunctional structural system,which are con-structed with nanoparticles as structural units,featuring two or more shells,multiple interfaces,and numerous chan-nels and demonstrating outstanding properties in energy conversion and mass transfer.In recent years,owing to the breakthroughs in synthetic methods,the diversity of composition and structure of HoMS has been greatly enriched,showing broad application prospects in energy,catalysis,environment and other fields.This review focuses on the research status of HoMS for catalytic applications.Firstly,the new synthesis method for HoMS,namely the sequen-tial templating approach,is introduced from both practical and theoretical perspectives.Then,it summarizes and discusses the structure-performance relationship between the shell structure and catalytic performance.The unique temporal-spatial ordering property of mass transport in HoMS and the major breakthroughs it brings in catalytic applications are discussed.Finally,it looks forward to the opportunities and challenges in the development of HoMS.
基金supported by the National Key R&D Program of China(2023YFA0915300)National Natural Science Foundation of China(Nos.22232006 and 22025207).
文摘In recent years,peptide-based therapies have gained remarkable attention as promising tools for cancer treatment,offering notable advantages in specifcity,modifability,and reduced systemic toxicity.Various peptide classes-including cell-penetrating,tumor-homing,pro-apoptotic,and immunemodulating peptides-have shown appreciable efcacy in selectively targeting cancer cells and modulating immune responses against tumors.Despite this potential,peptide therapies face signifcant challenges,such as susceptibility to rapid degradation,limited bioavailability,and inadequate accumulation within tumors.To address these issues,bacterial systems have emerged as innovative peptide delivery platforms,improving peptide stability,enhancing localized concentrations,and enabling controlled release directly at tumor sites.This review explores the synergistic potential of therapeutic peptides combined with bacterial delivery systems,with a focus on methods such as bacterial lysis for peptide release,secretion pathways,and peptide surface display.By harnessing the tumor-targeting properties and secretion capabilities of bacteria,these integrated approaches offer promising solutions to overcome the inherent limitations of peptide therapies,positioning them as advanced tools in precision oncology.
基金financially supported by the National Key Research and Development Program of China(Nos.2022YFA1204500 and 2022YFA1204502)the National Natural Science Foundation of China(Nos.22293043 and 92163209)the IPE Project for Frontier Basic Research,China(No.QYJC-2023-08)
文摘Inspired by the visual neurons of biological systems,optoelectronic synaptic devices integrate photoresponsive semiconductor materials to convert light into electrical signals,enabling biomimetic visual perception systems.Achieving memory retention and intelligent perceptual functions continues to pose a major hurdle in the advancement of neuromorphic artificial synapse devices.This review begins with an exploration of biological neural synapses,analyzing the fundamental characteristics and structures of biomimetic optoelectronic synapses.It then delves into the design of device and material structures to achieve postsynaptic current and memory behavior,elucidating their underlying mechanisms.Furthermore,the latest application scenarios of these devices are summarized,highlighting the opportunities and challenges in their future development.This review aims to provide a comprehensive understanding of the advancements in optoelectronic synapses,from material innovations to neuromorphic applications,paving the way for next-generation artificial visual systems and neuromorphic computing.
基金This work was supported by National Key Research and Development Program of China(grant No.2021YFC2302400)Major Program of the National Natural Science Foundation of China(grant Nos.T2394503 and T2394501)+2 种基金CAS Project for Young Scientists in Basic Research(grant No.YSBR-010)Key Project of the National Natural Science Foundation of China(grant No.32030062)IPE Project for Frontier Basic Research(grant No.QYJC2023-04)。
文摘The mRNA vaccines have become a transformative platform in medicine,with their success during the COVID-19 pandemic accelerating research in viral prevention and cancer therapy.Lipid nanoparticles(LNPs)enhance the stability and efficacy of mRNA vaccines,but achieving an optimal balance between innate immune activation and mRNA expression is crucial for their effectiveness.Classical cationic lipids,although largely replaced by ionizable lipids due to concerns over excessive immunogenicity,have demonstrated potential in cancer immunotherapy by inducing strong immune responses.In this study,we investigated whether incorporating cationic lipids into mRNA-LNP formulations could enhance immunogenicity without requiring new lipid designs.We introduced varying proportions of cationic lipids into D-Lin-MC3-DMA and SM-102-based LNPs and evaluated their impact on innate immune activation,along with long-term humoral and cellular immune responses.Our results showed that in MC3-based LNPs,cationic lipids significantly improved anti-tumor efficacy,though slightly diminished long-term humoral and cellular immunity.In contrast,in SM-102-based LNPs,cationic lipids enhanced anti-tumor effects without negatively impacting long-term immunity.These findings suggest that adding cationic lipid as an additional component allows for the fine-tuning of mRNA-LNP immunogenicity,expanding the potential applications of mRNA vaccines and simplifying LNP design.
基金financially supported by the National Natural Science Foundation of China(Nos.32225029,22205240,52073287,22075289,82071552 and 22376006)National Key R&D Program of China(No.2023YFC2605003)。
文摘Metabolism is a general term for a series of ordered chemical reactions in an organism used to maintain life,mainly divided into anabolic and catabolic metabolism.Nucleic acid therapy can not only precisely up-regulate and down-regulate the expression of target genes but also correct mutated disease-causing genes,which demonstrates irreplaceable and outstanding advantages in the treatment of metabolismrelated diseases and has been applied to the clinical treatment of metabolism-related diseases.In this review,we introduce the structures of several major nucleic acid drugs and the mechanism of nucleic acid therapy.Subsequently,we describe the mechanisms of various biomolecular and tissue metabolisms and the etiology of metabolic disorders,classified according to metabolic substrates.We analyze the signal pathways and potential targets affecting the metabolism of each substrate and describe the nucleic acid drugs applied to these targets and their delivery technologies.This review aims to provide new ideas and targets for treating these diseases by investigating the role played by metabolism in developing diseases and providing guidance for the selection and design of nucleic acid drugs.
基金supported by the National Key Research and Development Program of China(2023YFC3403600)。
文摘Melanin is an advanced polymer with exceptional properties,widely used across cosmetics,pharmaceuticals,environmental applications,and more.However,its broader use is constrained by high production costs and limited availability.Lignin,the most abundant and renewable aromatic compound in nature,presents a promising alternative for synthesizing melanin.This study focuses on converting plentiful and cost-effective lignin into melanin through the metabolic engineering of Cupriavidus necator H16.By constructing and optimizing metabolic pathways,engineered C.necator strains were developed to synthesize melanin from lignin monomers and lignin hydrolysates.Using substrates like p-coumaric acid,caffeic acid,ferulic acid,and lignin hydrolysates,the resting cell method with C.necator produced 0.86,1.00,0.52,and 0.32 g L^(-1)of melanin,respectively.The purified melanin was analyzed and identified spectrally,revealing characteristics of isomelanin.Furthermore,sun protection factor studies demonstrated that the produced melanin offered significant UV protection.The use of engineered C.necator to convert abundant lignin hydrolysates into melanin holds great promise for reducing production costs and expanding its applications.
基金supported by the National Natural Science Foundation of China(grant No.22108284,and No.22208354)China Postdoctoral Science Foundation(grant No.2023M733522).
文摘Ferritin has emerged as a promising nanocarrier for delivering therapeutic agents to tumours.However,the limited drug loading and the off-target impacts after systemic administration remain challenges for cancer treatment with ferritin-based agents.Herein,we develop a microneedle patch loaded with ferritin-nanocaged doxorubicin(DoxFe@Fn/MN)for skin cancer treatment.Briefly,doxorubicin(Dox)is encapsulated in ferritin(Fn)using an iron core-assisted strategy,which results in a 3.4-fold increase in Dox loading compared to the direct loading method.Then,a polyvinyl alcohol-based microneedle(MN)patch is used for the transdermal delivery of DoxFe@Fn,enabling targeted tumour accumulation of DoxFe@Fn and preventing off-target impacts.The released DoxFe@Fn can bind to CD71 highly expressed on skin cancer cells,facilitating its uptake.As a result,the DoxFe@Fn/MN therapy presents a robust antitumour effect in a melanoma tumour model,showing its potential as a promising therapeutic modality for skin cancer treatment.
文摘Immune checkpoint blockade(ICB)has emerged as a promising immunotherapeutic modality against cancer in the clinic.However,only 10-30%of patients respond to ICB,primarily due to poor immunogenicity and insufficient T cell infiltration in solid tumors.Herein,we presented an approach for high-performance cancer treatment using the programmed cell death protein-1 and programmed cell death ligand-1(PD-1/PD-L1)inhibitor(BMS-202)-loaded PEGylated graphene oxide(GPi).On the one hand,GPi dissociated tight junctions of vascular endothelial cells(VECs)in tumor,thus promoting the extravasation and intratumoral accumulation of liposomal doxorubicin(LipDox),which then effectively induced immunogenic cell death of tumor cells.On the other hand,GPi also stimulated VECs to upregulate the expression of cell-cell interaction molecules,such as intercellular cell adhesion molecule-1 and vascular cell adhesion molecule-1,which facilitated the infiltration of T cells in tumor.Beyond acting as a stimulator of VECs,GPi could exert responsive release of BMS-202 under the acidic tumor microenvironment and blockade PD-1/PD-L1 axis in tumors.Finally,the alternating administration of GPi and LipDox effectively inhibited tumor growth in a 4T1 tumor model,providing a novel treatment mode for chemo-immunotherapy.
基金the National Key R&D Program of China(grant No.2022YFE0202500)Distinguished Young Scholars of the National Natural Science Foundation of China(grant No.T2222022)+2 种基金National Key Research and Development Program of China(grant No.2021YFC2302400,2021YFC2302600)Major Program of the National Natural Science Foundation of China(grant No.T2394503,T2394501)Key Project of the National Natural Science Foundation of China(grant No.32030062),CAS Project for。
文摘Tumor immunotherapy,particularly cancer vaccines,holds promise for combating cancer by harnessing tailored immune responses against malignant cells.However,conventional approaches face challenges in efficiently delivering antigens for optimal immune activation.Emulsion adjuvants,like MF59,enhance cellular uptake but struggle to induce robust CD8^(+)T cell responses.Here,we introduce a novel strategy employing a water-in-oil-in-water(W/O/W)multiple Pickering emulsion(mPE)for antigen delivery.The mPE,utilizing biocompatible,pH-sensitive particles,encapsulates antigens within the inner water phase,ensuring enhanced intracellular processing and dictating the intracellular fate of antigens for improved cross-presentation.In vitro and in vivo studies demonstrated that mPEs induced robust dendritic cells activation and antigen cross-presentation,leading to a significantly enhanced immune response.Notably,calcium phosphate-stabilized mPE(CaP-mPE)illustrated the more robust IFN-γ^(+)T cell responses.In comparison with traditional surfactant-stabilized multiple emulsions,CaP-mPE significantly inhibit tumor growth and effectively prolong the survival of tumor-bearing mice.This innovative approach offers a promising avenue for the development of effective cancer vaccines with potent cellular immune responses.
基金supported by National Natural Science Foundation of China(grant nos.21821005,21931012,21820102002,22293043,52272097,and 52202354)the Beijing Natural Science Foundation(grant no.2242019)the DNL Cooperation Fund,Chinese Academy of Sciences(CAS)(grant no.DNL202020).
文摘The ultimate goal of photocatalytic CO_(2)reduction is to efficiently convert atmospheric CO_(2)into value-added products by designing hierarchical photocatalysts that combine effective harvesting and accelerate activation capabilities of CO_(2)molecules.In this work,we demonstrated direct air-level CO_(2)reduction by hollow multishell structure(HoMS)nanoreactors with zeolitic imidazolate framework-8(ZIF-8)-modified ZnO heteroshells,which offers a promising solution to optimize the mass transfer process via selective sieving and effective enrichment of CO_(2)molecules from the atmospheric environments.Specifically,heteroshells with ZIF-8 matrix act as pumps that effectively capture CO_(2)molecules,while the cavities serve as tanks to hold these molecules,thus significantly enhancing the transfer kinetics for CO_(2)photoreduction.The periodic shell-cavity configuration allows the nanoreactor to effectively gather CO_(2)molecules near the catalytic sites,thus increasing conversion opportunities for activated molecules.Simultaneously,the surface atomic steps on the ZnO/ZIF-8 heterointerfaces with staggered geometry expedite charge transfer and adsorption efficiency,which synergistically boosts the CO_(2)-CO yield up to 3.7μmol/h under CO_(2)flow and 0.7μmol/h under atmospheric conditions with almost complete CO selectivity.Hopefully,the HoMS nanoreactors offer a potential strategy for solving the“last mile”challenge in practical CO_(2)valorization.
基金supported by the National Natural Science Foundation of China(32422042 and 52203185 to D.Z.and T2225021 to W.W.)the National Key Research and Development Program of China(2023YFC2307700to W.W.)the China Postdoctoral Science Foundation(2024M763294to J.L.).
文摘Fusobacterium nucleatum(Fn),an oral anaerobic commensal,has recently been identified as a crucial oncogenic contributor to colorectal cancer pathogenesis through its ectopic colonization in the gastrointestinal tract.Accumulating evidence reveals its multifaceted involvement in colorectal cancer initiation,progression,metastasis,and therapeutic resistance to conventional treatments,including chemotherapy,radiotherapy,and immunotherapy.This perspective highlights recent advances in anti-Fn strategies,including small-molecule inhibitors,nanomedicines,and biopharmaceuticals,while critically analyzing the translational barriers in developing targeted antimicrobial interventions.We further propose potential strategies to overcome current challenges in Fn modulation,aiming to pave the way for more effective therapeutic interventions and better clinical outcomes.
基金the National Natural Science Foundation of China(62375093 and 32422042)Technology Innovation Program of Hubei Province(2024BCB058)。
文摘The unique physiological characteristics and complexity of tumor,in addition to drug resistance result in traditional therapies,such as chemotherapy and radiotherapy,being unable to achieve complete elimination of cancer cells.Meanwhile,the emerging immunotherapy suffers from a low patient response rate.Bacterial therapies are highly targeted.Bacteria can penetrate deep into the tumor and show good tumor inhibition.However,natural bacteria have the limitation of high toxicity and inability to meet the demand for efficient therapeutics.Recent advances in synthetic biology and materials science relate to the safety and efficacy of bacterial therapeutics,promising to develop engineered bacteria with low toxicity and complex therapeutic functions.Engineered bacteria that express anticancer drug molecules can target the tumor region,synthesizing and releasing payloads in response to internal and external stimuli.This process leads to the regression of the tumor and the effective inhibition of recurrence.This review outlines the recent advancements in the field of engineered bacteria research,particularly focusing on their applications in anti-tumor therapy.It also includes the advantageous features and mechanisms of engineered bacteria therapy,synthetic biology modification methods,and future challenges and directions of engineered bacteria therapy.
基金the National Natural Science Foundation of China(Nos.52372170 , 92163209)the Beijing Natural Science Foundation(No.2232068)the Beijing-Tianjin-Hebei Basic Research Cooperation Special Project(No.B2024204027).
文摘Developing noble-metal-free oxygen evolution reaction(OER)electrocatalysts with stable performance at large working current is an imperative and yet formidable challenge for practical large scale water splitting.In this study,by inheriting hierarchical nanostructure and elemental homogeneity of Prussian blue analogues,a series of medium entropy transition metal phosphides(METMP)OER catalysts with high cost-effectivity,efficiency and stability were precisely prepared.Specifically,the METMP-based((FeCoNi)P/Ni_(2)P-NF)catalyst demonstrates exceptional performance with an overpotential of only 232 mV at 50 mA·cm^(-2)and a Tafel slope of 52.7 mV·dec^(-1),significantly superior to its less entropy counterparts and commercial RuO_(2-).Moreover,it even maintains stability at the industrial standard current density of 500 mA·cm^(-2)for over 200 h.Density functional theory(DFT)calculations indicates that the synergistic effect of Fe,Co,Ni modulates electronic structure of METMPs,which effectively reduces the energy barrier for the rate-determining HOO*formation step,thereby considerably enhancing catalytic activity.This work not only contributes to the fundamental understanding of the role of medium/high entropy in catalysis but also paves the way for the development of next-generation electrocatalysts for energy-related applications.
