To achieve the target of carbon neutrality,it is crucial to develop an efficient and green synthesis methodology with good atomic economy to achieve sufficient utilization of energy and sustainable development.Photoin...To achieve the target of carbon neutrality,it is crucial to develop an efficient and green synthesis methodology with good atomic economy to achieve sufficient utilization of energy and sustainable development.Photoinduced electron transfer reversible addition-fragmentation chain-transfer(PET-RAFT)polymerization is a precise methodology for constructing polymers with well-defined structures.However,conventional semiconductor-mediated PET-RAFT polymerization still has considerable limitations in terms of efficiency as well as the polymerization environment.Herein,sulfur-doped carbonized polymer dots(CPDs)were hydrothermally synthesized for catalysis of aqueous PET-RAFT polymerization at unprecedented efficiency with a highest propagation rate of 5.05 h-1.The resulting polymers have well-controlled molecular weight and narrow molecular weight dispersion(Ð<1.10).Based on the optoelectronic characterizations,we obtained insights into the photoinduced electron transfer process and proposed the mechanism for CPD-mediated PET-RAFT polymerization.In addition,as-synthesized CPDs for PET-RAFT polymerization were also demonstrated to be suitable for a wide range of light sources(blue/green/solar irradiation),numerous monomers,low catalyst loading(low as 0.01 mg mL^(-1)),and multiple polar solvent environments,all of which allowed to achieve efficiencies much higher than those of existing semiconductor-mediated methods.Finally,the CPDs were confirmed to be non-cytotoxic and catalyzed PET-RAFT polymerization successfully in cell culture media,indicating broad prospects in biomedical fields.展开更多
Designing efficient and stable electrocatalysts for the oxygen evolution reaction(OER)is of paramount importance for many energy-related technologies and devices.Herein,we propose a controlled oxidation pyrolysis stra...Designing efficient and stable electrocatalysts for the oxygen evolution reaction(OER)is of paramount importance for many energy-related technologies and devices.Herein,we propose a controlled oxidation pyrolysis strategy to develop carbonized polymer dots(CPDs)-modified Rh-doped RuO_(2)electrocatalyst(Rh-RuO_(2)/CPDs).CPDs act as structure-directing agents,facilitating the formation of small-sized RhRuO_(2)/CPDs nanoparticles and engineering them with abundant defective structures and stable Ru-O sites.The experimental results and theoretical simulation unravel that the modulation effect of CPDs and Rh doping can effectively regulate the electronic structure,valence state and morphology of active Ru-O sites,thereby enhancing the electron transfer at the active site interface and optimizing the chemisorption behavior of oxygen intermediates.The resultant Rh-RuO_(2)/CPDs demonstrates overpotentials of 168 and 197 mV at 10 mA/cm^(2)for OER in 0.5 mol/L H_(2)SO_(4)and 1.0 mol/L KOH solution,respectively,and longterm catalytic stability.展开更多
Since the discovery of carbonized polymer dots(CPDs)two decades ago,this emerging family of carbonbased nanomaterials has rapidly risen to prominence.CPDs have found widespread applications in sensing,catalysis,energy...Since the discovery of carbonized polymer dots(CPDs)two decades ago,this emerging family of carbonbased nanomaterials has rapidly risen to prominence.CPDs have found widespread applications in sensing,catalysis,energy,and biomedicine due to their flexible precursors and synthesis methods,tunable photoluminescence(PL)properties,and excellent biocompatibility.This report presents the advancements made in the realm of CPD precursors,elucidates their luminescence properties and underlying mechanisms,and explores the diverse applications of CPD-based materials.It comprehensively addresses key issues by delving into several interconnected chapters:Initially exploring the intriguing fluorescence and afterglow properties exhibited by CPDs,subsequently unraveling the complex luminescence mechanisms that underlie these phenomena,emphasizing the crucial aspect of controllable synthesis of CPDs,and ultimately culminating in the precise construction of composite materials tailored for applications in laser and electroluminescent devices.Furthermore,this report aims to provide communication and assistance for the controlled synthesis and expanded applications of CPDs.展开更多
Aqueous zinc ion batteries(AZIBs)are considered to be one of the most promising energy storage devices due to the advantages of high cost-effectiveness,safety,and environmental friendliness.However,they suffer from pr...Aqueous zinc ion batteries(AZIBs)are considered to be one of the most promising energy storage devices due to the advantages of high cost-effectiveness,safety,and environmental friendliness.However,they suffer from problems such as Zn dendrites growth and by-product generation.Carbonized polymer dots(CPDs)with polar groups as additive have been introduced to modulate the solvated structure of Zn^(2+)and reduce the water activity,promoting the uniform deposition of Zn and inhibiting the occurrence of side reactions.However,CPDs with different functional group contents from different precursor molar ratios variably affect the electrochemical performance of aqueous electrolytes.Therefore,in this work,we designed and synthesized CPDs with different molar ratios of the precursors(citric acid and urea)as electrolyte additives for AZIBs and explore the optimal molar ratios of the precursors.The Zn//Zn symmetrical cells using electrolytes with the optimal ratios CPDs achieve an extended cycle life over 615 h at 2 mA∙cm^(−2) and 1 mAh∙cm^(−2).This work offers great potential for future practical applications of CPDs.展开更多
Stabilizing triplet excited states is important for room temperature phosphorescence(RTP)materials to achieve multifunctional applications in humid environment.However,due to the lack of preparation strategies,the rea...Stabilizing triplet excited states is important for room temperature phosphorescence(RTP)materials to achieve multifunctional applications in humid environment.However,due to the lack of preparation strategies,the realization of RTP materials in water still faces challenges.Herein,a new design strategy was presented to achieve RTP in water by confining carbonized polymer dots(CPDs)in amino functional mesoporous silica(MSNs-NH_(2)).The as-prepared MSNs-CPDs aqueous dispersion exhibited blue afterglow,lasting more than 3 s to naked eyes.The triplet excited states were protected from non-radiative deactivation by the double-confinement effect including covalent bonding fixation and mesoporous structure confinement.The MSNs-CPDs inherited the structure of MSNs-NH_(2),so the stability of morphology and properties were superior to CPDs and even most of silica-based CPDs RTP materials.A water-related encryption technique demonstrated the promising application of MSNs-CPDs as smart materials in the field of information security.Besides,the possibility of potential application in ion detection was also explored.展开更多
Identification of lymph nodes(LNs)is critical for studies of the structure,the role in disease development,and the efficacy of disease treatment.Carbonized polymer dots(CPDs)are expected to be potential LNs-targeted i...Identification of lymph nodes(LNs)is critical for studies of the structure,the role in disease development,and the efficacy of disease treatment.Carbonized polymer dots(CPDs)are expected to be potential LNs-targeted imaging agents due to their excellent properties with special structure,better photoluminescence(PL)and great biocompatibility.Herein,a red/near infrared(NIR)emission CPDs(RCPDs)with one and two-photon bioimaging based on citric acid(CA)and benzoylurea(BU)are prepared.Notably,the RCPDs are capable of targeting LNs for imaging.Lymphocyte homing has been demonstrated to be the cellular mechanism of RCPDs target LNs imaging.This work has developed a new nanomaterial for targeted imaging of LNs,while the biological applications of CPDs have been expanded and deepened.展开更多
It is highly desired to accurately and selectively detect and image intracellular L-lysine and pH in biological systems because they could act as the biomarkers in certain abnormal conditions and may give us a warning...It is highly desired to accurately and selectively detect and image intracellular L-lysine and pH in biological systems because they could act as the biomarkers in certain abnormal conditions and may give us a warning of the occurrence of diseases.It has been attracted more focuses to design new ratiometric fluorescent probe for monitoring L-lysine and pH to improve detection accuracy.Carbonized polymer dots(CPDs),which possess carbon/polymer hybrid structure rather than pure carbon structure and constitute of a carbon core and large amounts of functional groups/polymer chains on the surface,rise up as a new type of fluorescent nanomaterials and especially display many advantages for bioanalysis.In this study,o-phenylenediamine(o-PD)and poly(styrene-co-maleic anhydride)(PSMA)are used as the precursors to synthesize the desired CPDs through one-step hydrothermal amide method.The prepared CPDs display two well-resolved fluorescence emission bands,i.e.,a very weak emission centered at 470 nm in blue region and a strong emission centered at 558 nm in yellow region.It is found that the two emissions are both responsive to L-lysine based on the surface passivation mechanism,whereas,only the yellow emission is responsive to pH due to the protonation/deprotonation process of the amino groups.Based on the different responsive behaviors,ratiometric detection and imaging of L-lysine and pH are achieved.The prepared ratiometric CPDs probe is successfully applied for L-lysine and pH sensing and imaging at two emission channels in live cell and zebrafish with satisfactory results.展开更多
Development of high-performance solid state luminescent carbon-based nanomaterials remains challenging.Here,strong blue-green fluorescent carbonized polymer dots(CPDs)from o-aminobenzenethiol and thiosalicylic acid(o ...Development of high-performance solid state luminescent carbon-based nanomaterials remains challenging.Here,strong blue-green fluorescent carbonized polymer dots(CPDs)from o-aminobenzenethiol and thiosalicylic acid(o ABT-TSA-CPDs)with an absolute photoluminescence quantum yield(PLQY)of 76%in solid state without matrix were synthesized.Through adjusting the reaction temperature and time,the PL centers were proved to be carbon core state and surface state associated to carbonyl group which was the source of strong fluorescence emission in solid state.The mechanism of the unique phenomenon of enhanced emission from ethanol solution(PLQY=7%)to powder(PLQY=76%)was investigated by analyzing the chemical properties and structures of o ABT-TSA-CPDs at different temperatures and o ABT-TSACPDs/PVC composites,and was confirmed as fixation of PL centers.展开更多
Three kinds of carbonized polymer dots(CPDs) synthesized via a one-pot process from ophenylenediamine(OPD), m-phenylenediamine(MPD) and p-phenylenediamine(PPD) exhibit excitationwavelength independent yellow, green an...Three kinds of carbonized polymer dots(CPDs) synthesized via a one-pot process from ophenylenediamine(OPD), m-phenylenediamine(MPD) and p-phenylenediamine(PPD) exhibit excitationwavelength independent yellow, green and red emissions, respectively. In sharp contrast, two kinds of CPDs prepared via a hydrothermal process from citric acid(CA) and diethylenetriamine(DETA) exhibit obvious excitation-wavelength dependent emissions. Through the characterization and comparison of the two types of CPDs, it is concretely revealed that the polymer structure types during the formation of CPDs can effectively control the fluorescence excitation-wavelength independence/dependence. The homogeneous polymer structures contained in CPDs contribute to excitation-wavelength independence, whereas random copolymer structures contribute to excitation-wavelength dependence. These studies are of great significance for further understanding the polymer structures and designing unique optical properties of CPDs.展开更多
Carbonized polymer dots(CPDs)modified layer-structured CdBiO_(2)Br(CPDs/CdBiO_(2)Br)Z-scheme heterojunction hybrid material has been synthesized via simple solvothermal method.The hybrid material with Z-scheme heteroj...Carbonized polymer dots(CPDs)modified layer-structured CdBiO_(2)Br(CPDs/CdBiO_(2)Br)Z-scheme heterojunction hybrid material has been synthesized via simple solvothermal method.The hybrid material with Z-scheme heterojunction can effectively maintain the original highly oxidizing holes of CdBiO_(2)Br and the highly reducing electrons of CPDs.In addition,the construction of heterostructure is beneficial to the migration and separation of photogenerated carriers.Under visible light irradiation,6 wt%CPDs/CdBiO_(2)Br showed the best catalytic activity for degradation of organic pollutants.Free radical capture experiments and ESR analysis confirmed that the main active species are·O_(2)^(-)and h^(+).The decomposition process of organic pollutants was analyzed by LC-MS.Finally,the probable visible light mechanism performance of CPDs/CdBiO_(2)Br as direct Z-scheme heterojunction photocatalytic materials was proposed.展开更多
As emerging carbon-based nanoparticles,carbon dots(CDs)have attracted widespread attention in recent decades.Among the large family of CDs,carbonized polymer dots(CPDs)exhibit amazing charm due to their unique highly ...As emerging carbon-based nanoparticles,carbon dots(CDs)have attracted widespread attention in recent decades.Among the large family of CDs,carbonized polymer dots(CPDs)exhibit amazing charm due to their unique highly functionalized structure and typical polymeric characteristics.The polymerization and crosslinking of precursors during the synthesis process lead to the formation of a distinctive core-shell structure in CPDs,which consists of a hydrophobic carbon core and a polymer shell layer with entangled chain segments.In previous research,CPDs have been highlighted from the perspective of their outstanding photoluminescence properties.However,few discussions or summaries are available concerning the polymeric characteristics of CPDs.Herein,we try to provide a detailed discussion of the typical polymeric characteristics of CPDs and related applications.We first make an introduction to CPD synthesis in terms of the formation process,synthetic methods,and precursor varieties.Subsequently,we give a summary of several typical polymeric characteristics of CPDs and relevant characterization techniques.Furthermore,we list various applications of CPDs related to polymer characteristics,including sensing,optoelectronic devices,anti-counterfeiting,and so on.Finally,we put forward some reflections and perspectives for the development of CPDs.展开更多
Carbonized polymer dots(CPDs)have been widely applied in biomedical fields,such as imaging,diagnosis and drug delivery.Since the complex,non-equilibrated and dynamic nature of biological systems inevitably affect the ...Carbonized polymer dots(CPDs)have been widely applied in biomedical fields,such as imaging,diagnosis and drug delivery.Since the complex,non-equilibrated and dynamic nature of biological systems inevitably affect the predesigned properties of CPDs,then efficiency and ultimate outcome of CPDs in biological identity will be transformed by the ubiquitous nano-bio interactions.Herein,our recent progress about elucidating the behavior of CPDs at nano-bio interface from the perspective of physical chemistry has been summarized in the review,mainly at the bio-macromolecular,cellular membrane and cellular levels,which is crucial for characterize their relative cytotoxicity and clinical transformation.Moreover,we mainly focused on the quantitative relationship of nano-bio interactions between CPDs with biological identity and related thermodynamics parameters during this process is also obtained from advanced isothermal titration calorimetry technique.Finally,our recent study about the photoluminescence origin is also included in this review,which favors modulating the photoluminescence of CPDs.展开更多
The aggregate luminescence behavior of organic luminescent materials has been studied extensively.As a new kind of luminescent nanomaterials,carbonized polymer dots(CPDs)not only inherit the stability and biocompatibi...The aggregate luminescence behavior of organic luminescent materials has been studied extensively.As a new kind of luminescent nanomaterials,carbonized polymer dots(CPDs)not only inherit the stability and biocompatibility of carbon materials,but also possess the luminescence tunability,water solubility,and high photoluminescence quantum yield of organic luminescent materials,rendering them a strong candidate for the next generation of light-emitting materials.Previously,people mainly understood its luminescence from the perspective of carbon materials,but some luminescence mechanisms are still unclear.In this review,we discuss the luminescence mechanism by referring to organic luminescent materials with emphasis on their aggregation behavior.Firstly,three representative aggregate luminescence phenomena of organic luminescent materials are briefly introduced.Chromophores present in CPDs are elaborated to further discuss the potential interactions between them,with emphasis on the role of crosslinked polymer networks.On this basis,some special luminescence phenomena of CPDs in the aggregate state are summarized,and relevant mechanisms are discussed in detail to consolidate relevant statements.展开更多
Comprehensive Summary Currently,solid-state fluorescent carbonized polymer dots(CPDs)have attracted attention increasingly due to their applications for optoelectronic display.However,designing CPDs possessing solid-s...Comprehensive Summary Currently,solid-state fluorescent carbonized polymer dots(CPDs)have attracted attention increasingly due to their applications for optoelectronic display.However,designing CPDs possessing solid-state fluorescence and clarifying the fluorescence mechanism remain challenging.Herein,we initially synthesized a novel type of polythiophene derivatives CPDs,poly-4,4’-(thiophene-3,4-diyl)dibenzoic acid carbonized polymer dots(PDBA-CPDs)with solid-state fluorescence.Subsequently,the structural and optical characterization revealed that the solid-state fluorescence originated from the aggregation induced emission of the CPDs.In brief,in aggregation state,the remaining polymer structure groups on the surface of the CPDs overlapped and weakened the non-radiative transition,enhancing solid-state fluorescence emission.Thirdly,three polythiophene-derived CPDs were designed to further demonstrate the aggregation induced solid-state fluorescence mechanism.Finally,owing to their unique properties of solid-state fluorescence,the white LEDs(light emitting diodes)were fabricated with high color rendering index(CRI)of 82.7 and CIE coordinates of(0.37,0.39)using commercial 460 nm chip.展开更多
Stimulating and harnessing circularly polarized luminescence(CPL)is not only a sine qua non for fundamentally unveiling chirogenesis in physical chemistry,but also a pivotal prerequisite for implementation of such phe...Stimulating and harnessing circularly polarized luminescence(CPL)is not only a sine qua non for fundamentally unveiling chirogenesis in physical chemistry,but also a pivotal prerequisite for implementation of such phenomenon in research fields including chiral optoelectronics and theranostics.Herein,red-emissive carbonized polymer dots(CPDs)-based helical structures were synthesized in this work via biomolecule-tailored organic–inorganic co-assembly strategy.The surface statesrelated chirality exhibits enhanced circular dichroism(CD)and CPL activities with anisotropic factors as high as gCD,max=5.4×10^(−3) and glum,max=1.5×10^(−2),respectively.The obtained CPL signals can be further manipulated in an excitationdependent manner,indicating that a synergistic-competition phenomenon exists between configurational chirality and intermolecular energy-transfer dynamics,which is further supported by simulations based on density function theory(DFT).Such tunable CPL behavior triggers revolutionary designs and applications of these chiral CPDs into the realm of chirality-related biological issues and next-generation chiral optoelectronics.展开更多
Thermochromic smart windows have gained increasing popularity in light modulation and energy management in buildings.However,the fabrication of flexible thermochromic smart windows with high luminous transmittance(Tlu...Thermochromic smart windows have gained increasing popularity in light modulation and energy management in buildings.However,the fabrication of flexible thermochromic smart windows with high luminous transmittance(Tlum),tailorable critical temperature(τc),strong solar modulation ability(ΔTsol),and long-term durability remains a huge challenge.In this study,hydrogel-based thermochromic smart windows are fabricated by sandwiching thermochromic hydrogels of polyallylamine hydrochloride,polyacrylic acid,and carbonized polymer dots(CPDs)complexes between two pieces of transparent substrates.Benefiting from the incorporation of nanosized CPDs,the thermochromic hydrogel has an ultrahigh Tlum of~98.7%,a desirableτc of~24.2℃,aΔTsol of~89.3%and a rapid transition time of~3 s from opaque state to transparent state.Moreover,the thermochromic hydrogel exhibits excellent anti-freezing ability,tight adhesion toward various substrates,and excellent self-healing capability.The self-healing capability enables the fabrication of large-area smart windows by welding multiple hydrogel pieces.The smart windows retain their original thermochromic properties after being stored under ambient conditions for at least 147 days or undergoing 10,000 uninterrupted heating/cooling cycles.The model houses with smart windows can achieve a temperature reduction of 9.2℃,demonstrating the excellent indoor temperature modulation performance of the smart windows.展开更多
In order to uniformly disperse the ceramic reinforcements synthesized in-situ in the copper matrix composites,this study used Carbon Polymer Dot(CPD)as the carbon source and Cu–1.0%Ti alloy powder as the matrix for s...In order to uniformly disperse the ceramic reinforcements synthesized in-situ in the copper matrix composites,this study used Carbon Polymer Dot(CPD)as the carbon source and Cu–1.0%Ti alloy powder as the matrix for supplying Ti source to prepare in-situ synthesized TiC/Cu composites.The results show that TiC nano-precipitates,having the similar particle sizes with the CPD,form at the grains interior and grain boundaries,and maintain a uniform distribution state.Compared with the matrix,0.3 wt%CPD/Cu composite displays the best strengthplastic compatibility,the ultimate tensile strength achieves 385 MPa accompanied with a corresponding elongation of 21%,owing to the dislocation hindrance caused by nano-carbide and excellent interface bonding between nano TiC and the Cu matrix.The density function theory calculation supports our experimental results by showing a tighter and stronger interface contact.This work presents a new approach for studying in-situ carbide precipitates.展开更多
This study reports a new nitrogen-doped carbonized polymer dot(CPD)-based solvatochromic probe.Its color-changing for different solvents was explored in detail by the measurements of photophysical parameters(involving...This study reports a new nitrogen-doped carbonized polymer dot(CPD)-based solvatochromic probe.Its color-changing for different solvents was explored in detail by the measurements of photophysical parameters(involving Stokes shifts,fluorescence quantum yield,fluorescence lifetime,radiative decay rate constant,and non-radiative decay rate constant)and the following analyses according to Lippert–Mataga equation and Kamlet–Taft model.The hydrogen bonding effect of the CPD in protonic solvents was semi-quantitatively assessed.It takes charge of the solvatochromic phenomenon,especially in proton solvents.Interestingly,this CPD exhibits two-photon solvatochromism.Moreover,the relations between the photophysical parameters and the surface states of CPD in aprotic and proton solvents were depicted.The results reveal the nitrogen doping in the CPD impacts the up-and down-conversion solvatochromic features from the comparison between N-free and N-doped CPDs in many characterizations.In addition,this N-doped CPD was dispersed into polymer matrices to fabricate tunable solid-state luminescent films,which is another model for evidencing the interactions of the CPD with surroundings.This study is of significance in understanding the surface-state controlled luminescence in the CPDs,and will be beneficial for developing new smart,responsive carbon-based nanoprobes.展开更多
Carbonized polymer dots(CPDs)as one type of carbon dots have attracted widespread attention in recent years.The proposal of the“shell–core”structure of CPDs leads to further thinking about the association between t...Carbonized polymer dots(CPDs)as one type of carbon dots have attracted widespread attention in recent years.The proposal of the“shell–core”structure of CPDs leads to further thinking about the association between their special structures and luminescent properties.In recent years,great progress has been made in the field of CPD-based room-temperature phosphorescent materials.This review pays particular attention to how the special“core–shell”structure of CPDs influences the activation of roomtemperature phosphorescence(RTP).The strategies and vital factors to activate RTP for CPD-based materials in both solid state and water were reviewed in detail to elaborate on the effect of the special structure on RTP generation.Furthermore,some perspectives on the current challenges were also provided to guide the further development of CPD-based room-temperature phosphorescent materials.展开更多
Noncovalentlycross-linkedpolymermaterials through healing,recycling,and reprocessing can reduce materials consumption and alleviate environmental pollution.However,it remains a huge challenge to fabricate super-strong...Noncovalentlycross-linkedpolymermaterials through healing,recycling,and reprocessing can reduce materials consumption and alleviate environmental pollution.However,it remains a huge challenge to fabricate super-strong noncovalently cross-linked polymer materials with mechanical strength comparable to high-performance engineering polymers.Herein,healable and reprocessable noncovalently cross-linked polymer compositeswith an unprecedented mechanical strength are fabricated by complexation of polyacrylic acid(PAA),polyvinylpyrrolidone(PVPON),and carbonized polymer dots(CPDs)(denoted as PAA-PVPON-CPDs).The incorporation of 15 wt%CPDs generates PAA-PVPON-CPDs compositeswith a tensile strength of∼158 MPa and Young’s modulus of∼8.2GPa.Servingas nanofillers,theCPDs can establish strong interactions with polymers in PAA-PVPON composites.The CPDs and the in situ-formed PAAPVPON nanoparticles work in concert to significantly strengthen the PAA-PVPON-CPDs composites to an unprecedented strength.The PAA-PVPON-CPDs composites exhibit excellent impact resistance and damage tolerance because of the high mechanical strength of the composites and the energy dissipation mechanism of the CPDs and PAA-PVPON nanoparticles.Moreover,the fractured PAA-PVPON-CPDs composites can be healed to restore their original mechanical strength.展开更多
基金supported by the National Natural Science Foundation of China(NSFC)under Grant No.22035001 and No.52233005.
文摘To achieve the target of carbon neutrality,it is crucial to develop an efficient and green synthesis methodology with good atomic economy to achieve sufficient utilization of energy and sustainable development.Photoinduced electron transfer reversible addition-fragmentation chain-transfer(PET-RAFT)polymerization is a precise methodology for constructing polymers with well-defined structures.However,conventional semiconductor-mediated PET-RAFT polymerization still has considerable limitations in terms of efficiency as well as the polymerization environment.Herein,sulfur-doped carbonized polymer dots(CPDs)were hydrothermally synthesized for catalysis of aqueous PET-RAFT polymerization at unprecedented efficiency with a highest propagation rate of 5.05 h-1.The resulting polymers have well-controlled molecular weight and narrow molecular weight dispersion(Ð<1.10).Based on the optoelectronic characterizations,we obtained insights into the photoinduced electron transfer process and proposed the mechanism for CPD-mediated PET-RAFT polymerization.In addition,as-synthesized CPDs for PET-RAFT polymerization were also demonstrated to be suitable for a wide range of light sources(blue/green/solar irradiation),numerous monomers,low catalyst loading(low as 0.01 mg mL^(-1)),and multiple polar solvent environments,all of which allowed to achieve efficiencies much higher than those of existing semiconductor-mediated methods.Finally,the CPDs were confirmed to be non-cytotoxic and catalyzed PET-RAFT polymerization successfully in cell culture media,indicating broad prospects in biomedical fields.
基金financially supported by the National Natural Science Foundation of China(No.22035001)the Natural Science Foundation of Jilin Province(No.***202402011)。
文摘Designing efficient and stable electrocatalysts for the oxygen evolution reaction(OER)is of paramount importance for many energy-related technologies and devices.Herein,we propose a controlled oxidation pyrolysis strategy to develop carbonized polymer dots(CPDs)-modified Rh-doped RuO_(2)electrocatalyst(Rh-RuO_(2)/CPDs).CPDs act as structure-directing agents,facilitating the formation of small-sized RhRuO_(2)/CPDs nanoparticles and engineering them with abundant defective structures and stable Ru-O sites.The experimental results and theoretical simulation unravel that the modulation effect of CPDs and Rh doping can effectively regulate the electronic structure,valence state and morphology of active Ru-O sites,thereby enhancing the electron transfer at the active site interface and optimizing the chemisorption behavior of oxygen intermediates.The resultant Rh-RuO_(2)/CPDs demonstrates overpotentials of 168 and 197 mV at 10 mA/cm^(2)for OER in 0.5 mol/L H_(2)SO_(4)and 1.0 mol/L KOH solution,respectively,and longterm catalytic stability.
基金financial support from the National Natural Science Foundation of China(Nos.52203244,22101267)the Key Scientific and Technological Project of Henan Province(No.222102310683)+1 种基金the China Postdoctoral Science Foundation(Nos.2021M692905,2024T170832)Natural Science Foundation of Henan Province(Nos.242300421068,242300421123)。
文摘Since the discovery of carbonized polymer dots(CPDs)two decades ago,this emerging family of carbonbased nanomaterials has rapidly risen to prominence.CPDs have found widespread applications in sensing,catalysis,energy,and biomedicine due to their flexible precursors and synthesis methods,tunable photoluminescence(PL)properties,and excellent biocompatibility.This report presents the advancements made in the realm of CPD precursors,elucidates their luminescence properties and underlying mechanisms,and explores the diverse applications of CPD-based materials.It comprehensively addresses key issues by delving into several interconnected chapters:Initially exploring the intriguing fluorescence and afterglow properties exhibited by CPDs,subsequently unraveling the complex luminescence mechanisms that underlie these phenomena,emphasizing the crucial aspect of controllable synthesis of CPDs,and ultimately culminating in the precise construction of composite materials tailored for applications in laser and electroluminescent devices.Furthermore,this report aims to provide communication and assistance for the controlled synthesis and expanded applications of CPDs.
基金supported by the National Natural Science Foundation of China(22035001 and 22275030)Jilin Provincial Education Department(JJKH20231304KJ)the Fundamental Research Funds(Science and Technology Achievements Transformation)for the Central Universities of China(CGZH202203)
文摘Aqueous zinc ion batteries(AZIBs)are considered to be one of the most promising energy storage devices due to the advantages of high cost-effectiveness,safety,and environmental friendliness.However,they suffer from problems such as Zn dendrites growth and by-product generation.Carbonized polymer dots(CPDs)with polar groups as additive have been introduced to modulate the solvated structure of Zn^(2+)and reduce the water activity,promoting the uniform deposition of Zn and inhibiting the occurrence of side reactions.However,CPDs with different functional group contents from different precursor molar ratios variably affect the electrochemical performance of aqueous electrolytes.Therefore,in this work,we designed and synthesized CPDs with different molar ratios of the precursors(citric acid and urea)as electrolyte additives for AZIBs and explore the optimal molar ratios of the precursors.The Zn//Zn symmetrical cells using electrolytes with the optimal ratios CPDs achieve an extended cycle life over 615 h at 2 mA∙cm^(−2) and 1 mAh∙cm^(−2).This work offers great potential for future practical applications of CPDs.
基金financially supported by the National Natural Science Foundation of China (NSFC, No. 22035001)
文摘Stabilizing triplet excited states is important for room temperature phosphorescence(RTP)materials to achieve multifunctional applications in humid environment.However,due to the lack of preparation strategies,the realization of RTP materials in water still faces challenges.Herein,a new design strategy was presented to achieve RTP in water by confining carbonized polymer dots(CPDs)in amino functional mesoporous silica(MSNs-NH_(2)).The as-prepared MSNs-CPDs aqueous dispersion exhibited blue afterglow,lasting more than 3 s to naked eyes.The triplet excited states were protected from non-radiative deactivation by the double-confinement effect including covalent bonding fixation and mesoporous structure confinement.The MSNs-CPDs inherited the structure of MSNs-NH_(2),so the stability of morphology and properties were superior to CPDs and even most of silica-based CPDs RTP materials.A water-related encryption technique demonstrated the promising application of MSNs-CPDs as smart materials in the field of information security.Besides,the possibility of potential application in ion detection was also explored.
基金supported by National Natural Science Foundation of China(No.U21A20308)Sichuan Science and Technology Program(Nos.21ZDYF3218,2022ZYD0048)Talent Project of Sichuan Province,Sichuan Provincial College Student Innovation Training Program(Nos.S202010650073,S202210623049).
文摘Identification of lymph nodes(LNs)is critical for studies of the structure,the role in disease development,and the efficacy of disease treatment.Carbonized polymer dots(CPDs)are expected to be potential LNs-targeted imaging agents due to their excellent properties with special structure,better photoluminescence(PL)and great biocompatibility.Herein,a red/near infrared(NIR)emission CPDs(RCPDs)with one and two-photon bioimaging based on citric acid(CA)and benzoylurea(BU)are prepared.Notably,the RCPDs are capable of targeting LNs for imaging.Lymphocyte homing has been demonstrated to be the cellular mechanism of RCPDs target LNs imaging.This work has developed a new nanomaterial for targeted imaging of LNs,while the biological applications of CPDs have been expanded and deepened.
基金financially supported by the National Natural Science Foundation of China(Nos.21874001,21575004)the Foundation for Innovation Team of Bioanalytical Chemistry of Anhui Province。
文摘It is highly desired to accurately and selectively detect and image intracellular L-lysine and pH in biological systems because they could act as the biomarkers in certain abnormal conditions and may give us a warning of the occurrence of diseases.It has been attracted more focuses to design new ratiometric fluorescent probe for monitoring L-lysine and pH to improve detection accuracy.Carbonized polymer dots(CPDs),which possess carbon/polymer hybrid structure rather than pure carbon structure and constitute of a carbon core and large amounts of functional groups/polymer chains on the surface,rise up as a new type of fluorescent nanomaterials and especially display many advantages for bioanalysis.In this study,o-phenylenediamine(o-PD)and poly(styrene-co-maleic anhydride)(PSMA)are used as the precursors to synthesize the desired CPDs through one-step hydrothermal amide method.The prepared CPDs display two well-resolved fluorescence emission bands,i.e.,a very weak emission centered at 470 nm in blue region and a strong emission centered at 558 nm in yellow region.It is found that the two emissions are both responsive to L-lysine based on the surface passivation mechanism,whereas,only the yellow emission is responsive to pH due to the protonation/deprotonation process of the amino groups.Based on the different responsive behaviors,ratiometric detection and imaging of L-lysine and pH are achieved.The prepared ratiometric CPDs probe is successfully applied for L-lysine and pH sensing and imaging at two emission channels in live cell and zebrafish with satisfactory results.
基金supported financially by the National Science Foundation of China(Nos.22035001,21774041)Jilin University Science and Technology Innovative Research Team(No.2017TD-06)。
文摘Development of high-performance solid state luminescent carbon-based nanomaterials remains challenging.Here,strong blue-green fluorescent carbonized polymer dots(CPDs)from o-aminobenzenethiol and thiosalicylic acid(o ABT-TSA-CPDs)with an absolute photoluminescence quantum yield(PLQY)of 76%in solid state without matrix were synthesized.Through adjusting the reaction temperature and time,the PL centers were proved to be carbon core state and surface state associated to carbonyl group which was the source of strong fluorescence emission in solid state.The mechanism of the unique phenomenon of enhanced emission from ethanol solution(PLQY=7%)to powder(PLQY=76%)was investigated by analyzing the chemical properties and structures of o ABT-TSA-CPDs at different temperatures and o ABT-TSACPDs/PVC composites,and was confirmed as fixation of PL centers.
基金the Priority Academic Program Development of Jiangsu Higher Education Institutions (No. 1107047002)the Key Research and Development Plan (Modern Agriculture) of Jiangsu Province (No. BE2018385)Innovation Platform Project supported by Jiangsu Province (No. 6907041203)。
文摘Three kinds of carbonized polymer dots(CPDs) synthesized via a one-pot process from ophenylenediamine(OPD), m-phenylenediamine(MPD) and p-phenylenediamine(PPD) exhibit excitationwavelength independent yellow, green and red emissions, respectively. In sharp contrast, two kinds of CPDs prepared via a hydrothermal process from citric acid(CA) and diethylenetriamine(DETA) exhibit obvious excitation-wavelength dependent emissions. Through the characterization and comparison of the two types of CPDs, it is concretely revealed that the polymer structure types during the formation of CPDs can effectively control the fluorescence excitation-wavelength independence/dependence. The homogeneous polymer structures contained in CPDs contribute to excitation-wavelength independence, whereas random copolymer structures contribute to excitation-wavelength dependence. These studies are of great significance for further understanding the polymer structures and designing unique optical properties of CPDs.
基金supported by the National Natural Science Foundation of China(No.22108106,21676128)China Postdoctoral Science Foundation(No.2020M680065)+1 种基金Hong Kong Scholar Program(No.XJ2021021)Key Laboratory of Electrochemical Energy Storage and Energy Conversion of Hainan Province(No.KFKT2021005).
文摘Carbonized polymer dots(CPDs)modified layer-structured CdBiO_(2)Br(CPDs/CdBiO_(2)Br)Z-scheme heterojunction hybrid material has been synthesized via simple solvothermal method.The hybrid material with Z-scheme heterojunction can effectively maintain the original highly oxidizing holes of CdBiO_(2)Br and the highly reducing electrons of CPDs.In addition,the construction of heterostructure is beneficial to the migration and separation of photogenerated carriers.Under visible light irradiation,6 wt%CPDs/CdBiO_(2)Br showed the best catalytic activity for degradation of organic pollutants.Free radical capture experiments and ESR analysis confirmed that the main active species are·O_(2)^(-)and h^(+).The decomposition process of organic pollutants was analyzed by LC-MS.Finally,the probable visible light mechanism performance of CPDs/CdBiO_(2)Br as direct Z-scheme heterojunction photocatalytic materials was proposed.
基金supported by the Natural Science Foundation of Jilin Province(no.202402011)the National Natural Science Foundation of China(NSFC)under Grant No.22035001.
文摘As emerging carbon-based nanoparticles,carbon dots(CDs)have attracted widespread attention in recent decades.Among the large family of CDs,carbonized polymer dots(CPDs)exhibit amazing charm due to their unique highly functionalized structure and typical polymeric characteristics.The polymerization and crosslinking of precursors during the synthesis process lead to the formation of a distinctive core-shell structure in CPDs,which consists of a hydrophobic carbon core and a polymer shell layer with entangled chain segments.In previous research,CPDs have been highlighted from the perspective of their outstanding photoluminescence properties.However,few discussions or summaries are available concerning the polymeric characteristics of CPDs.Herein,we try to provide a detailed discussion of the typical polymeric characteristics of CPDs and related applications.We first make an introduction to CPD synthesis in terms of the formation process,synthetic methods,and precursor varieties.Subsequently,we give a summary of several typical polymeric characteristics of CPDs and relevant characterization techniques.Furthermore,we list various applications of CPDs related to polymer characteristics,including sensing,optoelectronic devices,anti-counterfeiting,and so on.Finally,we put forward some reflections and perspectives for the development of CPDs.
基金the Nation-al Key R&D Program of China(2018FYA0703700)the National Natural Science Foundation of China(21873075,21603067)+2 种基金Guangxi Science and Technology Project(GuiKeAD17195081)Bagui Scholar Program of Guangxi Province(2016)Hubei Na-ture Science Foundation of China(2019CFB748).
文摘Carbonized polymer dots(CPDs)have been widely applied in biomedical fields,such as imaging,diagnosis and drug delivery.Since the complex,non-equilibrated and dynamic nature of biological systems inevitably affect the predesigned properties of CPDs,then efficiency and ultimate outcome of CPDs in biological identity will be transformed by the ubiquitous nano-bio interactions.Herein,our recent progress about elucidating the behavior of CPDs at nano-bio interface from the perspective of physical chemistry has been summarized in the review,mainly at the bio-macromolecular,cellular membrane and cellular levels,which is crucial for characterize their relative cytotoxicity and clinical transformation.Moreover,we mainly focused on the quantitative relationship of nano-bio interactions between CPDs with biological identity and related thermodynamics parameters during this process is also obtained from advanced isothermal titration calorimetry technique.Finally,our recent study about the photoluminescence origin is also included in this review,which favors modulating the photoluminescence of CPDs.
基金National Natural Science Foundation of China,Grant/Award Number:21774041。
文摘The aggregate luminescence behavior of organic luminescent materials has been studied extensively.As a new kind of luminescent nanomaterials,carbonized polymer dots(CPDs)not only inherit the stability and biocompatibility of carbon materials,but also possess the luminescence tunability,water solubility,and high photoluminescence quantum yield of organic luminescent materials,rendering them a strong candidate for the next generation of light-emitting materials.Previously,people mainly understood its luminescence from the perspective of carbon materials,but some luminescence mechanisms are still unclear.In this review,we discuss the luminescence mechanism by referring to organic luminescent materials with emphasis on their aggregation behavior.Firstly,three representative aggregate luminescence phenomena of organic luminescent materials are briefly introduced.Chromophores present in CPDs are elaborated to further discuss the potential interactions between them,with emphasis on the role of crosslinked polymer networks.On this basis,some special luminescence phenomena of CPDs in the aggregate state are summarized,and relevant mechanisms are discussed in detail to consolidate relevant statements.
基金the National Natural Science Foundation of China(Grant Nos.52272052,51972315,21873110,and 61720106014).
文摘Comprehensive Summary Currently,solid-state fluorescent carbonized polymer dots(CPDs)have attracted attention increasingly due to their applications for optoelectronic display.However,designing CPDs possessing solid-state fluorescence and clarifying the fluorescence mechanism remain challenging.Herein,we initially synthesized a novel type of polythiophene derivatives CPDs,poly-4,4’-(thiophene-3,4-diyl)dibenzoic acid carbonized polymer dots(PDBA-CPDs)with solid-state fluorescence.Subsequently,the structural and optical characterization revealed that the solid-state fluorescence originated from the aggregation induced emission of the CPDs.In brief,in aggregation state,the remaining polymer structure groups on the surface of the CPDs overlapped and weakened the non-radiative transition,enhancing solid-state fluorescence emission.Thirdly,three polythiophene-derived CPDs were designed to further demonstrate the aggregation induced solid-state fluorescence mechanism.Finally,owing to their unique properties of solid-state fluorescence,the white LEDs(light emitting diodes)were fabricated with high color rendering index(CRI)of 82.7 and CIE coordinates of(0.37,0.39)using commercial 460 nm chip.
基金National Natural Science Foundation of China,Grant/Award Number:22075240Shenzhen Fundamental Research Foundation,Grant/Award Number:JCYJ20180508162801893+3 种基金National Natural Science Foundation of Hubei Province,Grant/Award Numbers:2020CFB200,2021CFB018Guangdong Basic and Applied Basic Research Foundation,Grant/Award Number:2019A1515012094Project of Department of Education of Guangdong Province,Grant/Award Number:2018KTSCX198Shenzhen Basic Research Project of Science and Technology,Grant/Award Number:JCYJ20210324094414039。
文摘Stimulating and harnessing circularly polarized luminescence(CPL)is not only a sine qua non for fundamentally unveiling chirogenesis in physical chemistry,but also a pivotal prerequisite for implementation of such phenomenon in research fields including chiral optoelectronics and theranostics.Herein,red-emissive carbonized polymer dots(CPDs)-based helical structures were synthesized in this work via biomolecule-tailored organic–inorganic co-assembly strategy.The surface statesrelated chirality exhibits enhanced circular dichroism(CD)and CPL activities with anisotropic factors as high as gCD,max=5.4×10^(−3) and glum,max=1.5×10^(−2),respectively.The obtained CPL signals can be further manipulated in an excitationdependent manner,indicating that a synergistic-competition phenomenon exists between configurational chirality and intermolecular energy-transfer dynamics,which is further supported by simulations based on density function theory(DFT).Such tunable CPL behavior triggers revolutionary designs and applications of these chiral CPDs into the realm of chirality-related biological issues and next-generation chiral optoelectronics.
基金supported by the National Natural Science Foundation of China (No.21935004).
文摘Thermochromic smart windows have gained increasing popularity in light modulation and energy management in buildings.However,the fabrication of flexible thermochromic smart windows with high luminous transmittance(Tlum),tailorable critical temperature(τc),strong solar modulation ability(ΔTsol),and long-term durability remains a huge challenge.In this study,hydrogel-based thermochromic smart windows are fabricated by sandwiching thermochromic hydrogels of polyallylamine hydrochloride,polyacrylic acid,and carbonized polymer dots(CPDs)complexes between two pieces of transparent substrates.Benefiting from the incorporation of nanosized CPDs,the thermochromic hydrogel has an ultrahigh Tlum of~98.7%,a desirableτc of~24.2℃,aΔTsol of~89.3%and a rapid transition time of~3 s from opaque state to transparent state.Moreover,the thermochromic hydrogel exhibits excellent anti-freezing ability,tight adhesion toward various substrates,and excellent self-healing capability.The self-healing capability enables the fabrication of large-area smart windows by welding multiple hydrogel pieces.The smart windows retain their original thermochromic properties after being stored under ambient conditions for at least 147 days or undergoing 10,000 uninterrupted heating/cooling cycles.The model houses with smart windows can achieve a temperature reduction of 9.2℃,demonstrating the excellent indoor temperature modulation performance of the smart windows.
基金supported by the Chinese National Science Foundation(Grant No.52174345,52064032)the Yunnan Science and Technology Projects(Grant No.202002AB080001)Science and Technology Major Project of Yunnan Province(Grant No.202202AG050004).
文摘In order to uniformly disperse the ceramic reinforcements synthesized in-situ in the copper matrix composites,this study used Carbon Polymer Dot(CPD)as the carbon source and Cu–1.0%Ti alloy powder as the matrix for supplying Ti source to prepare in-situ synthesized TiC/Cu composites.The results show that TiC nano-precipitates,having the similar particle sizes with the CPD,form at the grains interior and grain boundaries,and maintain a uniform distribution state.Compared with the matrix,0.3 wt%CPD/Cu composite displays the best strengthplastic compatibility,the ultimate tensile strength achieves 385 MPa accompanied with a corresponding elongation of 21%,owing to the dislocation hindrance caused by nano-carbide and excellent interface bonding between nano TiC and the Cu matrix.The density function theory calculation supports our experimental results by showing a tighter and stronger interface contact.This work presents a new approach for studying in-situ carbide precipitates.
基金the National Natural Science Foundation of China(No.21873039)Interdisciplinary Integration Innovation Project of Jilin University(No.JLUXKJC2020106).
文摘This study reports a new nitrogen-doped carbonized polymer dot(CPD)-based solvatochromic probe.Its color-changing for different solvents was explored in detail by the measurements of photophysical parameters(involving Stokes shifts,fluorescence quantum yield,fluorescence lifetime,radiative decay rate constant,and non-radiative decay rate constant)and the following analyses according to Lippert–Mataga equation and Kamlet–Taft model.The hydrogen bonding effect of the CPD in protonic solvents was semi-quantitatively assessed.It takes charge of the solvatochromic phenomenon,especially in proton solvents.Interestingly,this CPD exhibits two-photon solvatochromism.Moreover,the relations between the photophysical parameters and the surface states of CPD in aprotic and proton solvents were depicted.The results reveal the nitrogen doping in the CPD impacts the up-and down-conversion solvatochromic features from the comparison between N-free and N-doped CPDs in many characterizations.In addition,this N-doped CPD was dispersed into polymer matrices to fabricate tunable solid-state luminescent films,which is another model for evidencing the interactions of the CPD with surroundings.This study is of significance in understanding the surface-state controlled luminescence in the CPDs,and will be beneficial for developing new smart,responsive carbon-based nanoprobes.
基金supported by the National Science Foundation of China(NSFC)under grant no.22035001.
文摘Carbonized polymer dots(CPDs)as one type of carbon dots have attracted widespread attention in recent years.The proposal of the“shell–core”structure of CPDs leads to further thinking about the association between their special structures and luminescent properties.In recent years,great progress has been made in the field of CPD-based room-temperature phosphorescent materials.This review pays particular attention to how the special“core–shell”structure of CPDs influences the activation of roomtemperature phosphorescence(RTP).The strategies and vital factors to activate RTP for CPD-based materials in both solid state and water were reviewed in detail to elaborate on the effect of the special structure on RTP generation.Furthermore,some perspectives on the current challenges were also provided to guide the further development of CPD-based room-temperature phosphorescent materials.
基金supported by the National Natural Science Foundation of China(NSFC grant no.21935004).
文摘Noncovalentlycross-linkedpolymermaterials through healing,recycling,and reprocessing can reduce materials consumption and alleviate environmental pollution.However,it remains a huge challenge to fabricate super-strong noncovalently cross-linked polymer materials with mechanical strength comparable to high-performance engineering polymers.Herein,healable and reprocessable noncovalently cross-linked polymer compositeswith an unprecedented mechanical strength are fabricated by complexation of polyacrylic acid(PAA),polyvinylpyrrolidone(PVPON),and carbonized polymer dots(CPDs)(denoted as PAA-PVPON-CPDs).The incorporation of 15 wt%CPDs generates PAA-PVPON-CPDs compositeswith a tensile strength of∼158 MPa and Young’s modulus of∼8.2GPa.Servingas nanofillers,theCPDs can establish strong interactions with polymers in PAA-PVPON composites.The CPDs and the in situ-formed PAAPVPON nanoparticles work in concert to significantly strengthen the PAA-PVPON-CPDs composites to an unprecedented strength.The PAA-PVPON-CPDs composites exhibit excellent impact resistance and damage tolerance because of the high mechanical strength of the composites and the energy dissipation mechanism of the CPDs and PAA-PVPON nanoparticles.Moreover,the fractured PAA-PVPON-CPDs composites can be healed to restore their original mechanical strength.
