Rational design of high-performance electrocatalysts for hydrogen evolution reaction(HER)is vital for future renewable energy systems.The incorporation of foreign metal ions into catalysts can be an effective approach...Rational design of high-performance electrocatalysts for hydrogen evolution reaction(HER)is vital for future renewable energy systems.The incorporation of foreign metal ions into catalysts can be an effective approach to optimize its performance.However,there is a lack of systematic theoretical studies to reveal the quantitative relationships at the electronic level.Here,we develop a multi-level screening methodology to search for highly stable and active dopants for CoP catalysts.The density functional theory(DFT)calculations and symbolic regression(SR)were performed to investigate the relationship between the adsorption free energy(ΔG_(H^(*)))and 10 electronic parameters.The mathematic formulas derived from SR indicate that the difference of work function(ΔΦ)between doped metal and the acceptor plays the most important role in regulatingΔG_(H^(*)),followed by the d-band center(d-BC)of doped system.The descriptor of HER can be expressed asΔG_(H^(*))=1.59×√|0.188ΔΦ+d BC+0.120|1/2-0.166 with a high determination coefficient(R^(2)=0.807).Consistent with the theoretical prediction,experimental results show that the Al-CoP delivers superior electrocatalytic HER activity with a low overpotential of75 m V to drive a current density of 10 mA cm^(-2),while the overpotentials for undoped CoP,Mo-CoP,and V-CoP are 206,134,and 83 m V,respectively.The current work proves that theΔΦis the most significant regulatory parameter ofΔG_(H^(*))for ion-doped electrocatalysts.This finding can drive the discovery of high-performance ion-doped electrocatalysts,which is crucial for electrocatalytic water splitting.展开更多
Discrete Pt(Ⅱ)metallacycles have attracted particular attention for the chemotherapeutic treatment of cancer.However,a single chemotherapy cannot simultaneously balance efficiency and safety because the continuous ad...Discrete Pt(Ⅱ)metallacycles have attracted particular attention for the chemotherapeutic treatment of cancer.However,a single chemotherapy cannot simultaneously balance efficiency and safety because the continuous administration throughout the entire therapy period will lead to inefficient therapy and potentially long-term systemic toxicity.Therefore,the development of a novel organoplatinum(Ⅱ)metallacycle with multimodal treatment capabilities is urgently needed to overcome these issues.Herein,a discrete Pt(II)metallacycle(SCY)bearing the near-infrared(NIR)photosensitizer heptamethine cyanine was fabricated and further encapsulated by amphiphilic 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-methoxy(polyethyleneglycol)(DSPEmPEG)to form P@SCY nanoparticles.Heptamethine cyanine,which has excellent photoconversion efficiency,can generate reactive oxygen species(ROS)and heat simultaneously,and the cyanine moiety can target mitochondria in cancer cells due to their quaternary ammonium salt cations,which improve the effect of phototherapy.Due to its excellent phototherapy and chemotherapy properties,P@SCY exhibited remarkable trimodal therapeutic effects[chemo-/photodynamic therapy(PDT)/photothermal therapy(PTT)]against cancer cells(HepG2 cells,MCF-7 cells,and 4T1 cells)in vitro.Furthermore,in vivo results also confirmed thatP@SCY had superior antitumor properties with minimal side effects in the 4T1 tumor model.Thiswork presents a practicable approach to develop a multifunctional organoplatinum(Ⅱ)metallacycle for multimodal tumor therapy.展开更多
基金Financial support from the National Natural Science Foundation of China(21676216)the Special project of Shaanxi Provincial Education Department(20JC034)+1 种基金GHfund B(202202022563)Hefei Advanced Computing Center。
文摘Rational design of high-performance electrocatalysts for hydrogen evolution reaction(HER)is vital for future renewable energy systems.The incorporation of foreign metal ions into catalysts can be an effective approach to optimize its performance.However,there is a lack of systematic theoretical studies to reveal the quantitative relationships at the electronic level.Here,we develop a multi-level screening methodology to search for highly stable and active dopants for CoP catalysts.The density functional theory(DFT)calculations and symbolic regression(SR)were performed to investigate the relationship between the adsorption free energy(ΔG_(H^(*)))and 10 electronic parameters.The mathematic formulas derived from SR indicate that the difference of work function(ΔΦ)between doped metal and the acceptor plays the most important role in regulatingΔG_(H^(*)),followed by the d-band center(d-BC)of doped system.The descriptor of HER can be expressed asΔG_(H^(*))=1.59×√|0.188ΔΦ+d BC+0.120|1/2-0.166 with a high determination coefficient(R^(2)=0.807).Consistent with the theoretical prediction,experimental results show that the Al-CoP delivers superior electrocatalytic HER activity with a low overpotential of75 m V to drive a current density of 10 mA cm^(-2),while the overpotentials for undoped CoP,Mo-CoP,and V-CoP are 206,134,and 83 m V,respectively.The current work proves that theΔΦis the most significant regulatory parameter ofΔG_(H^(*))for ion-doped electrocatalysts.This finding can drive the discovery of high-performance ion-doped electrocatalysts,which is crucial for electrocatalytic water splitting.
基金supported by the National Natural Science Foundation of China (21875063 and 21871006)the Science and Technology Commission of Shanghai Municipality for Shanghai International Cooperation Program (19440710600)the Open Funding Project of the State Key Laboratory of Bioreactor Engineering。
基金the National Natural Science Foundation of China(nos.21875063,21922506,and 21871092)the Science and Technology Commission of Shanghai Municipality for the Shanghai International Cooperation Program(no.19440710600).
文摘Discrete Pt(Ⅱ)metallacycles have attracted particular attention for the chemotherapeutic treatment of cancer.However,a single chemotherapy cannot simultaneously balance efficiency and safety because the continuous administration throughout the entire therapy period will lead to inefficient therapy and potentially long-term systemic toxicity.Therefore,the development of a novel organoplatinum(Ⅱ)metallacycle with multimodal treatment capabilities is urgently needed to overcome these issues.Herein,a discrete Pt(II)metallacycle(SCY)bearing the near-infrared(NIR)photosensitizer heptamethine cyanine was fabricated and further encapsulated by amphiphilic 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-methoxy(polyethyleneglycol)(DSPEmPEG)to form P@SCY nanoparticles.Heptamethine cyanine,which has excellent photoconversion efficiency,can generate reactive oxygen species(ROS)and heat simultaneously,and the cyanine moiety can target mitochondria in cancer cells due to their quaternary ammonium salt cations,which improve the effect of phototherapy.Due to its excellent phototherapy and chemotherapy properties,P@SCY exhibited remarkable trimodal therapeutic effects[chemo-/photodynamic therapy(PDT)/photothermal therapy(PTT)]against cancer cells(HepG2 cells,MCF-7 cells,and 4T1 cells)in vitro.Furthermore,in vivo results also confirmed thatP@SCY had superior antitumor properties with minimal side effects in the 4T1 tumor model.Thiswork presents a practicable approach to develop a multifunctional organoplatinum(Ⅱ)metallacycle for multimodal tumor therapy.
