共轭聚合物荧光纳米粒子研究进展

近年来,共轭聚合物荧光纳米粒子因其优异的光学性能,在化学、医学和环境科学等研究领域显示了极其广阔的应用前景.相比于传统无机半导体荧光纳米材料,共轭聚合物荧光纳米粒子具有结构多样性、功能可设计性、生物相容性好等显著优势.本文从共轭聚合物荧光粒子的制备方法、光学性能、表面功能化修饰出发,重点讨论了近年来共轭聚合物纳米粒子作为荧光探针在细胞成像及生物化学检测方面的研究进展,阐述了当前研究的主要发展方向和仍需解决的问题.     

Overview on conducting polymer in energy storage and energy conversion system

Polymer-based electrochemical devices such as supercapacitor, battery, and fuel cell have been developed and advanced for energy related application. In this regard, conducting polymers own several tunable characteristics for energy conversion and energy storage relevance. Consequently, efficient, reliable, low cost, conducting, stable, and environment friendly energy systems have been developed using conducting polymers. To enhance the efficiency and commercialization of energy systems, design, structure, composition, and fabrication technique used for conducting polymers and related composite have been focused. Challenges and future trend associated with current state of the art conducting polymer materials in supercapacitor, battery, and fuel cell are highlighted.     

Redox flow batteries for energy storage: Recent advances in using organic active materials

The development of redox electrolytes using organic active materials as alternatives to metal-based species for redox flow batteries is booming recently. However, challenges and gaps remain toward commercialization. This review briefly discusses the most recent advances of using electroactive organic materials. Strategies such as chemical modification through molecular engineering and new efforts toward energy-rich electrolytes and high-power electrolytes are addressed. Furthermore, the limiting factors governing the cycling life are summarized.     

Recent advances of transition metal oxalate-based micro- and nanomaterials for electrochemical energy storage: a review

A key challenge in the development of electrochemical energy storage (EES) is the design and engineering of electrode materials for electrochemical reactions. Transition metal oxalates (TMOxs) have been widely used in various EES applications due to their low cost, simple synthesis, and excellent electrochemical performance. In this review, the recent advances in the design and engineering of transition metal oxalate-based micro- and nanomaterials for EES are summarized. Specifically, the survey will focus on three types of micro- and nano-scale TMOxs (monometallic, bimetallic, and trimetallic TMOxs), their composites (TMOx-metal oxide, TMOx-hydroxide, TMOx-GO, and TMOx-MOFs composites), and derivatives, including transition metal oxides (TiO₂, V₂O₅, Mn_xO_y, Co₃O₄, NiO, CuO, and Nb₂O₅), multi-transition metal oxides (MCo₂O₄ (M = Ni, Cu, and Zn), NiMn₂O₄, and N_xO_y-M_xO_y), transition metal sulfide (NiS₂), and carbon materials (ordinary carbon, GO and their composites), within the context of their intrinsic structure and corresponding electrochemical performance. A range of experimental variables will be carefully analyzed, such as sample synthesis, crystal structure, and electrochemical reaction mechanism. The applications of these materials as EES electrodes are then featured for supercapacitors (SCs) and lithium-ion batteries (LIBs). We conclude the review with a perspective of future research prospects and challenges.     

Silafluorene‐based polymers for electrochromic and polymer solar cell applications

In this study, four novel silafluorene (SiF) and benzotriazole (Btz) bearing conjugated polymers are synthesized. In the context of electrochemical and optical studies, these polymers are promising materials both for electrochromic device (ECD) and polymer solar cell (PSC) applications. All of the polymers are ambipolar (both p‐ and n‐dopable) and multichromic. Electrochemistry experiments indicate that incorporation of selenophene instead of thiophene unit increases the HOMO energy level of the polymers. Power conversion efficiency of the PSCs reached 1.75% for PTBTSiF, 1.55% for PSBSSiF, 2.57% for PBTBTSiF, and 1.82% for PBSBSSiF. The hole mobilities of the polymers are estimated through space charge limited current (SCLC) model. PBTBTSiF has the highest hole mobility as 2.44 × 10^?3 cm² V s^?1. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1541–1547     

Nanoparticulate Conjugated Microporous Polymer with Post-Modified Benzils for Enhanced Pseudocapacitor Performance

Conjugated microporous polymer (CMP)-based energy-storage materials were developed for pseudocapacitors. Nanoparticulate CMP (N-CMP) with an average diameter of 41±4 nm was prepared through kinetic growth control in the Sonogashira coupling of 1,3,5-triethynylbenzene with 1,4-diiodobenzene. The N-CMP is rich in a diphenylacetylene moiety in its chemical structure. Through the FeCl₃-catalyzed oxidation of diphenylacetylene moieties, N-CMP with benzil moieties (N-CMP-BZ) was prepared and showed enhanced electrochemical performance as an electrode material of pseudocapacitors, compared with CMP, CMP-BZ, and N-CMP. In model studies, the benzil was redox active and showed two-electron reduction behavior. The excellent electrochemical performance of N-CMP-BZ is attributable to the enhanced utilization of functional sites by a nanosize effect and the additional redox contribution of benzil moieties.     

Conjugated Molecules and Polymers in Secondary Batteries: A Perspective

Intrinsically conducting polymers constituting a subclass of macromolecules, as well as a still growing family of large, conjugated molecules, oligomers, and polymers, have attracted research interest for the recent decades. Closely corresponding to the fascination of these materials, combining typical properties of organic polymers and metallic materials, numerous applications have been suggested, explored, and sometimes transferred into products. In electrochemistry, they have been used in various functions beyond the initially proposed and obvious application as active masses in devices for electrochemical energy conversion and storage. This perspective contribution wraps up basic facts that are necessary to understand the behavior and properties of the oligo and polymers and their behavior in electrochemical cells for energy conversion by electrode reactions and associated energy storage. Representative examples are presented and discussed, and an overview of the state of research and development is provided. Particular attention is paid to stability and related aspects of practical importance. Future trends and perspectives are indicated.     

A Novel Blue to Transparent Polymer for Electrochromic Supercapacitor Electrodes

Electrochromic supercapacitors may alert the user on the remaining capacity of the devices. The color change indicating the remaining capacity can be simply and rapidly recognized by the human eye or by optical instruments. A rapid indication of charged state may extend device service life and prevent overcharging, which would otherwise result in electrode aging and decomposition. In this study, a blue to the transmissive electrochromic polymer, poly(4,7‐bis(2,3‐dihydrothieno[3, 4‐B][1, 4]dioxin‐5‐YI)‐2‐(2‐octyldodecyl)‐2H‐benzo[D][1, 2,3]triazole) (P1C), was used in nanocomposite form with transparent silver nanowire (Ag NW) network current collectors for the fabrication of electrochromic supercapacitor electrodes. Highly conductive and transparent Ag NW networks have an important role in the realization of electrochromic supercapacitors using P1C. Fabricated Ag NW/P1C nanocomposite electrodes had a specific capacitance of 65.0 F g⁻¹ at a current density of 0.1 A g⁻¹. Nanocomposite electrode showed excellent stability (capacity retention of>98 %) after 11000 cycles associated with a resistance decrease associated with charge transfer.     

Recent advances in solid-state polymer electrolytes and innovative ionic liquids based polymer electrolyte systems

Solid polymer electrolytes are a promising alternative to widely used liquid carbonate electrolytes to deliver next-generation lithium-ion batteries with improved safety. However, the limited ionic conductivity and high interfacial resistance with electrodes limit their widespread use. This review aims to give an overview of the recent research on performance aspects and strategies of solid polymer electrolytes, including ionic conductivity, lithium transference number, design flexibility, scale-up, and integration of ionic liquids with a focus on safety.     

Soft template synthesis of donor–acceptor conjugated polymer nanoparticles: Structural effects,stability, and photothermal studies

Donor–acceptor conjugated polymer nanoparticles and nanofibers, based on Poly[4,4‐bis(2‐ethylhexyl)‐cyclopenta[2,1‐b;3,4‐b']dithiophene‐2,6‐diyl‐alt?2,1,3‐benzoselenadiazole‐4,7‐diyl] (PCPDTBSe), were synthesized using Pluronic F127 as a template. The nanomaterials were compared to previously reported PCPDTBSe nanoparticles, which were synthesized without the use of a template. Our goal was to improve on the aqueous stability and photothermal heating efficiency of the previously synthesized PCPDTBSe nanoparticles by decreasing their size and coating them with a biocompatible surfactant. The pluronic wrapped PCPDTBSe (PW‐PCPDTBSe) nanoparticles (40–60 nm) showed excellent aqueous stability compared to the PW‐PCPDTBSe nanofibers (d = 20–60 nm, l = 200–1000 nm) and previously synthesized PCPDTBSe nanoparticles (150 nm). Under stimulation from 800 nm near infrared light (3 W, 1 min), the PW‐PCPDTBSe nanoparticles showed greater heat generation (ΔT = 47 °C) compared to bare PCPDTBSe nanoparticles and PW‐PCPDTBSe nanofibers (ΔT = 35 °C for both). Cytotoxicity studies determined that both the PW‐PCPDTBSe nanoparticles and PW‐PCPDTBSe nanofibers displayed no significant toxicity toward either noncancerous small intestinal cells (FHs 74 Int) or colorectal cancer cells (CT26). Photothermal ablation studies confirmed that both the PW‐PCPDTBSe nanoparticles and the PW‐PCPDTBSe nanofibers can be used as localized photothermal agents to eradicate colorectal cancer cells due to their excellent ablation efficiency (>95% cell death at 15 µg/mL concentration). © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1622–1632     

Tuning the energy gap of conjugated polymer zwitterions for efficient interlayers and solar cells

Narrow band gap conjugated polymer zwitterions (CPZs) were synthesized by Suzuki polymerization and characterized to understand their electronic properties and utility as cathode modification layers in solar cells. The polymers were prepared from diketopyrrolopyrrole (DPP) and iso-indigo monomers containing sulfobetaine (SB) pendant groups, benefiting from an ion-rich aqueous phase in the polymerizations. UV–vis absorption spectroscopy revealed the optical energy gap value for the CPZs, ranging from 1.7 to 1.2 eV. Ultraviolet photoelectron spectroscopy of the CPZs as thin layers on Ag metal showed that the pendent zwitterions impart an interfacial dipole (Δ) to the metal and a work function reduction of ∼0.9 eV. OPVs fabricated using a conventional bulk heterojunction (BHJ) device architecture of ITO/PEDOT:PSS/(PTB7:PC₇₁BM)/CPZ/Ag led to dramatic improvements in power conversion efficiency (PCE) values relative to devices having bare Ag cathodes (PCE < 2% for bare Ag vs. 6.7–7.7% for CPZ/Ag). The benzothiadiazole (BT)/DPP polymer denoted as PT₂BTDPPSB gave an optimal PCE of 7.7% in a conventional BHJ OPV device architecture fabricated on a Ag cathode. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 327–336     

Synthesis and characterization of thiazolothiazole‐based polymers and their applications in polymer solar cells

A novel series of thiazolothiazole (Tz)‐based copolymers, poly[9,9‐didecylfluorene‐2,7‐diyl‐alt‐2,5‐bis‐(3‐hexylthiophene‐2‐yl)thiazolo[5,4‐d]thiazole] (P1), poly[9,9‐dioctyldibenzosilole‐2,7‐diyl‐alt‐2,5‐bis‐(3‐hexylthiophene‐2‐yl)thiazolo[5,4‐d]thiazole] (P2), and poly[4,4′‐bis(2‐ethylhexyl)‐dithieno[3,2‐b:2′,3′‐d]silole‐alt‐2,5‐bis‐(3‐hexylthiophene‐2‐yl)thiazolo[5,4‐d]thiazole] (P3), were synthesized for the use as donor materials in polymer solar cells (PSCs). The field‐effect carrier mobilities and the optical, electrochemical, and photovoltaic properties of the copolymers were investigated. The results suggest that the donor units in the copolymers significantly influenced the band gap, electronic energy levels, carrier mobilities, and photovoltaic properties of the copolymers. The band gaps of the copolymers were in the range of 1.80–2.14 eV. Under optimized conditions, the Tz‐based polymers showed power conversion efficiencies (PCEs) for the PSCs in the range of 2.23–2.75% under AM 1.5 illumination (100 mW/cm²). Among the three copolymers, P1, which contained a fluorene donor unit, showed a PCE of 2.75% with a short‐circuit current of 8.12 mA/cm², open circuit voltage of 0.86 V, and a fill factor (FF) of 0.39, under AM 1.5 illumination (100 mW/cm²). © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Graphene/polymer composites for energy applications

Graphene has wide potential applications in energy-related systems, mainly because of its unique atom-thick two-dimensional structure, high electrical or thermal conductivity, optical transparency, great mechanical strength, inherent flexibility, and huge specific surface area. For this purpose, graphene materials are frequently blended with polymers to form composites, especially when fabricating flexible devices. Graphene/polymer composites have been explored as electrodes of supercapacitors or lithium ion batteries, counter electrodes of dye-sensitized solar cells, transparent conducting electrodes and active layers of organic solar cells, catalytic electrodes, and polymer electrolyte membranes of fuel cells. In this review, we summarize the recent advances on the synthesis and applications of graphene/polymer composites for energy applications. The challenges and prospects in this field have also been discussed. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

氧化石墨烯诱导的Ni-Co氢氧化物整体电极的制备及电储能特性

超级电容器作为一种新型储能装置,由于其能量密度、功率密度高和良好的循环稳定性,而在实际工业应用中(新能源汽车、航天航空业、电子通信系统、可穿戴设备等)显示出巨大的潜力.但目前面临的最大挑战是构造柔性、轻薄可变形的储能设备.在本项研究工作中,利用溶剂热法和真空抽滤法开发了一种碳基/层状金属氢氧化物的复合材料.设计将氧化石...     

Acceptor–acceptor conjugated copolymers based on perylenediimide and benzothiadiazole for all‐polymer solar cells

Donor–acceptor (D–A) conjugated copolymers are one of known classes of organic optoelectronic materials and have been well developed. However, less attention has been paid on acceptor–acceptor (A–A) conjugated analogs. In this work, two types of A–A conjugated copolymers, namely P1‐Cn and P2‐Cn (n is the carbon number of their alkyl side chains), were designed and synthesized based on perylenediimide ( PDI ) and 2,1,3‐benzothiadiazole ( BT ). Different from P1‐Cn , P2‐Cn polymers have additional acetylene π‐spacers between PDI and BT and thus hold a more planar backbone configuration. Property studies revealed that P2‐Cn polymers possess a much red‐extended UV–vis absorption spectrum, stronger π–π interchain interactions, and one‐order larger electron mobility in their neat film state than P1‐Cn . However, all‐polymer solar cells using P1‐Cn as acceptor component and poly(3‐hexyl thiophene) or poly(2,7‐(9,9‐didodecyl‐fluoene)‐alt?5,5′‐(4,7‐dithienyl‐2‐yl‐2,1,3‐benzothiadiazole) as donor component exhibited much better performance than those based on P2‐Cn . Apart from their backbone chemical structure, the side chains were found to have little influence on the photophysical, electrochemical, and photovoltaic properties for both P1‐Cn and P2‐Cn polymers. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1200–1215     

Precipitation polymerization of aniline in the presence of water‐soluble organic acids

The precipitation polymerization of aniline in the presence of organic acids, including toluene‐4‐sulfonic acid, phenylphosphonic acid, 4‐aminophenylphosphonic acid, and acetophosphonic acid, led in one step to conductive polyaniline. The polyaniline showed very good affinity for water and was easily modified to be water‐soluble. In comparison with the widely studied postpolymerization of doped polyaniline, this reaction allowed reasonably good conductivity to be achieved at a lower acid/polyaniline ratio. Moreover, the easy in situ incorporation of the dopant into the polymer structure caused high stability of the created salt; that is, no dedoping was observed after it was washed with water, methanol, or other solvents. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3562–3569, 2002     

Self-amplifying sensory materials: energy migration in polymer semiconductors

Signal amplification for ultra-sensitive detection has been achieved by energy migration in conjugated semiconducting polymeric assemblies. Critical to optimizing this effect is the synthesis of non-aggregate polymers, the multidimensional directional transport of excited states (excitons), and extending the intrinsic excited state lifetime of conjugated polymers. We developed new water-soluble non-ionic conjugated polymers for use in biosensory applications, which can be used to provide highly sensitive/specific ultra-trace detection that is immune to specificity problems that plauge ionic conjugated polymers.     

Free‐Standing Conducting Polymer Films for High‐Performance Energy Devices

Thick, uniform, easily processed, highly conductive polymer films are desirable as electrodes for solar cells as well as polymer capacitors. Here, a novel scalable strategy is developed to prepare highly conductive thick poly(3,4‐ethylenedioxythiophene):polystyrene sulfonate (HCT‐PEDOT:PSS) films with layered structure that display a conductivity of 1400 S cm^?1 and a low sheet resistance of 0.59 ohm sq^?1. Organic solar cells with laminated HCT‐PEDOT:PSS exhibit a performance comparable to the reference devices with vacuum‐deposited Ag top electrodes. More importantly, the HCT‐PEDOT:PSS film delivers a specific capacitance of 120 F g^?1 at a current density of 0.4 A g^?1. All‐solid‐state flexible symmetric supercapacitors with the HCT‐PEDOT:PSS films display a high volumetric energy density of 6.80 mWh cm^?3 at a power density of 100 mW cm^?3 and 3.15 mWh cm^?3 at a very high power density of 16160 mW cm^?3 that outperforms previous reported solid‐state supercapacitors based on PEDOT materials.     

Novel siloxane polymers as polymer electrolytes for high energy density lithium batteries

A variety of disubstituted (double-comb) polysiloxane polymers have been prepared containing linear, branched, and cyclic oligoethyleneoxide units, –(OCH₂CH₂)_n–, in the side chains and as part of the siloxane backbone. Copolymers, using mixtures of linear ethylene oxide side chains, were also synthesized. These polymers were doped with LiN(SO₂CF₃)₂ (LiTFSI, 1) and conductivities of the polymer-salt complexes were determined as a function of temperature and doping level. The maximum conductivity of these polymers at 25 ° C was 2.99 ×10^–4, for a copolymer containing equimolar amounts of side chains with n = 5 and 6.     

Engineering Active Sites of Polyaniline for AlCl2+ Storage in an Aluminum-Ion Battery

The reversible capacity of AlCl₄⁻ intercalation/de-intercalation in conventional cathodes of aluminum-ion batteries (AIBs) is difficult to improve due to the large size of AlCl₄⁻ anions. Therefore, it is highly desirable to realize the intercalation/de-intercalation of smaller Al-based ions. Here, we fabricated polyaniline/single-walled carbon nanotubes (PANI/SWCNTs) composite films and protonated the PANI nanorods. The protonation endows PANI with more active sites and enhanced conductivity. Hyper self-protonated PANI (PANI(H⁺)) exhibits reversible AlCl₂⁺ intercalation/de-intercalation during the discharge/charge process. As a result, the discharge capacity of the Al/PANI(H⁺) battery is twice as high as that of the initial composite films. PANI(H⁺)@SWCNT electrodes also have a stable cycling life with only 0.003 % capacity decay per cycle over 8000 cycles. Owing to the excellent mechanical properties, PANI(H⁺)@SWCNT composite films can act as the electrodes of flexible AIBs.