Oxygen self-doping pyrolyzed polyacrylic acid as sulfur host with physical/chemical adsorption dual function for lithium-sulfur batteries

Lithium-sulfur(Li-S)batteries with high theoretical capacity and energy density need to solve problems such as the high decomposition energy barrier of Li_(2)S and large volume change of sulfur in the charging process caused by the shuttle effect before practical application.Herein,a green synthesis method is used to prepare polyacrylic acid(PAA)superabsorbent material,and then the pyrolyzed PAA(P/PAA)material is obtained as the positive electrode of Li-S battery.Density functional calculation reveals that the oxygen self-doping pyrolyzed polyacrylic acid(P/PAA)delivered stronger binding energy toward Li2S species in carbonyl C=O than that of graphite powder(GP)which are-1.58 eV and-1.02 eV,respectively.Coupled with the distribution of relaxation time analysis and the in-situ electrochemical impedance approach,it is further demonstrated that the designed P/PAA as sulfur host plays a physical/chemical adsorption dual function in maintaining the stability and rate performance of batteries.With an initial discharge capacity of 1258 mAh/g at 0.1 C and a minimal capacity decline of 0.05%per cycle even after 800 cycles at 0.5 C,the produced cathode demonstrated outstanding electrochemical performance.The average Coulombic efficiency is nearly 100%.The P/PAA electrodes may typically retain 96%of their capacity while declining on average only 0.033%per cycle after 130 cycles at 3 C.This effort provides a new method for the future development of heteroatomic self-doping superabsorbent with promising adsorption properties for polysulfides as cathode materials of Li-S batteries.

Self-doping active sites in microbe-derived carbonaceous electrocatalysts for the oxygen reduction reaction performance

Microorganisms are rich in heteroatoms,which can be self-doped to form active sites during pyrolysis and loaded on microbederived carbonaceous materials.In recent years,microbe-derived carbonaceous materials,characterized with abundant selfdoping sites,have been continuously developed as cost-effective electrocatalysts for oxygen reduction reaction(ORR).To fully unlock the catalytic potential of microbe-derived carbonaceous materials,a comprehensive analysis of catalytic sites and mechanisms for ORR is essential.This paper provides a summary of the ORR catalytic performance of microbe-derived carbonaceous materials reported to date,with a specific focus on the self-doping sites introduced during their pyrolytic fabrication.It highlights the mono-or co-doping sites involving nonmetallic elements such as oxygen(O),nitrogen(N),phosphorus(P),and sulfur(S)atoms,as well as covers the doping of metallic iron(Fe)atoms with various coordination configurations in microbe-derived carbonaceous materials.Understanding the impact of these self-doping sites on ORR catalytic performance can guide the design of doping sites in microbe-derived carbonaceous materials.This approach has the potential to maximize electrocatalytic activity of microbe-derived carbonaceous materials and contributes to the development of more efficient and cost-effective carbonaceous electrocatalysts.

In situ synthesis of Ti^(3+) self-doped mesoporous TiO_2 as a durable photocatalyst for environmental remediation

This study developed a facile approach for in situ synthesis of a Ti3＋ self-doped mesoporous TiO 2photocatalyst by an evaporation-induced self-assembly method using TiC l3,water,and F127 as the titanium precursor,solvent,and soft template agent,respectively. The as-prepared samples were investigated by X-ray diffraction,N2 adsorption-desorption measurements,ultraviolet-visible diffuse reflectance spectroscopy,electron paramagnetic resonance,and transmission electron microscopy. The influence of different reaction parameters such as the dosage of F127 and calcination temperature on the photocatalytic performance of the resulting products was evaluated. The optimized product exhibited high photocatalytic activity and stability in the oxidation of nitric oxide in air and photocatalytic degradation of methylene blue. The excellent photocatalytic performance of the Ti3＋ self-doped mesoporous TiO 2 photocatalyst is attributed to the cooperation between the mesoporous structure and self-doped Ti3＋ enhancing light absorption and effectively suppressing the recombination of photogenerated electrons and holes.

Biomass seaweed-derived n itrogen self-doped porous carb on anodes for sodium-ion batteries:Insights into the structure and electrochemical activity

Sustainable transformation and efficient utilization of biomasses and their derived materials are environ-mentally as well as economically compliant strategies.Biomass seaweed-derived nitrogen self-doped porous carbon with tailored surface area and pore structures are prepared through carb on izatio n and activation.The in fluence of carb on ization temperature on morphology,surface area,and heteroatom dopants are investigated to optimize sodium-ion storage capability.Seaweed-derived nitrogen selfdoped activated carbon(SAC)as anode materials for sodium-ion batteries exhibits remarkable reversible capacity of 303/192 mAh g^(-1) after 100/500 cycles at current densities of 100/200 mA g^(-1) respectively,and a good rate capability.The interconnected and porous conducting nature along with the heteroatom dopant role in creating defective sites and charge stabilization are favorable for ion storage and diffusion and electron transport,indicating the electrodes can offer improved electrochemical performances.In addition,post-mortem analysis of the cycled carbon electrodes through ex-situ tools demonstrates the sodium-ion storage mechanism.

Ti^(3+) self-doped TiO_2 photoelectrodes for photoelectrochemical water splitting and photoelectrocatalytic pollutant degradation

To improve the harvesting of visible light and reduce the recombination of photogenerated electrons and holes, Ti3+ self-doped TiO2 nanoparticles were synthesized and assembled into photoanodes with high visible light photoelectrochemical properties. X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectra, electron resonance spectroscopy and energy dispersive X-ray spectra were used to characterize the structure, crystallinity, morphology and other properties of the obtained nanoparticles. UV-visible diffuse reflectance spectra showed that the Ti3+ self-doped TiO2 nanoparticles had a strong absorption between 400 and 800 nm. Moreover, when hydrothermal treatment time was prolonged to 22 h, the heterogeneous junction was formed between the anatase and rutile TiO2, where the anatase particles exposed highly active {001} facets. Under visible light irradiation, the Ti3+ self-doped TiO2 electrode exhibited an excellent photoelectrocatalytic degradation of rhodamine B (RhB) and water splitting performance. Intriguingly, by selecting an appropriate hydrothermal time, the high photoconversion efficiency of 1.16% was achieved. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.

Nitrogen-doped TiO_2 microsheets with enhanced visible light photocatalytic activity for CO_2 reduction

Nitrogen-doped anatase TiO 2 microsheets with 65%（001） and 35%（101） exposed faces were fabricated by the hydrothermal method using TiN as precursor in the presence of HF and HCl. The samples were characterized by scanning electron microscopy,X-ray diffraction,N2 adsorption,X-ray photoelectron spectroscopy,UV-visible spectroscopy,and electrochemical impedance spectroscopy. Their photocatalytic activity was evaluated using the photocatalytic reduction of CO2. The N-doped TiO 2 sample exhibited a much higher visible light photocatalytic activity for CO2 reduction than its precursor TiN and commercial TiO 2（P25）. This was due to the synergistic effect of the formation of surface heterojunctions on the TiO 2 microsheet surface,enhanced visible light absorption by nitrogen-doping,and surface fluorination.

Two-dimensional ultrathin MoS2-modified black Ti^3+-TiO2 nanotubes for enhanced photocatalytic water splitting hydrogen production

Two-dimensional (2D) ultrathin MoS2-modified black Ti^3+-TiO2 nanotubes were fabricated using an electrospinning-hydrothermal treatment-reduction method.Bare TiO2 nanotubes were fabricated via electrospinning.Then,2D MoS2 lamellae were grown on the surface of the nanotubes and Ti^3+/Ov ions were introduced by reduction.The photocatalytic performance of the 2D MoS2/Ti^3+-TiO2 nanotubes was^15 times better than that of TiO2.The HER enhancement of the MoS2/Ti^3+-TiO2 nanotubes can be attributed to the Pt-like behavior of 2D MoS2 and the presence of Ti^3+-ions,which facilitated the quick diffusion of the photogenerated electrons to water,reducing the H2 activation barrier.The presence of Ov ions in the nanotubes and their hollow structure increased their solar utilization.

Effects of Elemental Chemical State in NiFe2O4@TiO2 on the Photocatalytic Performance

The elemental chemical state of NiFe2O4@TiO2 was changed by the reduction in order to investigate its effects on the photocatalytic performance.The synthesized NiFe2O4@TiO2 samples were characterized by means of X-ray diffraction (XRD),high-resolution transmission electron microscopy (HRTEM),Fourier-transform infrared spectroscopy (FT-IR),X-ray photoelectron spectroscopy (XPS),magnetic and photocatalytic measurements.Unexpectedly,the reduction reaction does not produce oxygen vacancies Ov and TiOx in the TiO2 lattice.The optimal catalyst was obtained at the reducing temperature of 800℃,and its degradation efficiency De to the methylene blue and reaction rate constant Kapp are the highest,reaching 99.9% and 3×10^-2 min-1,respectively.The reason could not be explained by both the visible light absorption and the appropriate amount of Ov and TiOx.Instead,the lowest ratios of TiOH and Ti-O-Fe(Ni) may be responsible for the optimum photocatalytic performance.

Heteroatom self-doped graphitic carbon materials from Sargassum thunbergii with improved supercapacitance performance

It is well-known that high specific surface area and improved pore structure is significantly desired for the application of supercapacitor based on biomass-based activated carbon.Herein,Sargassum thunbergii was selected as carbon precursor.Then,a simple and environmentally friendly method was designed to synthesize heteroatom self-doped porous carbon materials via synchronous activation and graphitization by using K_(2)FeO_(4).Our results demonstrated that activation temperature plays an important role in porous structure,morphology,and degree of graphitization,thus affecting the performance of supercapacitance.Sargassum thunbergii-based graphitized porous carbons STGPC-2 sample(calcination temperature at 700℃)has a large specific surface area(1641.98 m^(2)g^(-1)),pore volume(0.91 cm^(3)g^(-1)),high microporosity(Vmicro=0.62 cm^(3)g1,more than 68%),and a certain degree of graphitization.In three-electrode system,The STGPC-2 electrode exhibited a high specific capacitance of 325.5 F g^(-1)at 0.5 A g^(-1)and displays high rate capability(248 F g^(-1)at 10 A g^(-1)in 6 M KOH electrolyte).The symmetric STGPC-2 supercapacitor exhibits energy density as high as 21.3 Wh kg^(-1)(at a power density of 450 W kg^(-1))and excellent long-term cycling stability(97%capacitance retention after 3000 cycles)in 1 M Na2SO4 electrolyte.

Molecular Conformational Isomerization:An Efficient Way to Design Novel Emitters with Dual-Thermally Activated Delayed Fluorescence Characteristics and Their Optoelectronic and Bioimaging Applications

Single-molecule luminophores with dual-thermally activated delayed fluorescence(TADF)properties are receiving increasing attention.However,how to achieve these goals requires more in-depth studies.Herein,we demonstrate a novel example emitter,10-(5-(2-(pyridin-3-yl)-[4,5′-bipyrimidin]-6-yl)pyridin-2-yl)-10Hphenoxazine(PmPy-PXZ),enabling dual-TADF properties due to its key feature of conformational isomerization.Introducing a pyridine bridge can greatly reduce the steric hindrance and facilitate dual-stable conformations in the ground state,where the quasi-axial(QA)forms predominate.Moreover,unlike previously reported TADF molecules with dual confirmations,both theoretical and experimental measurements show that not only the quasi-equatorial(QE)forms but also the QA forms exhibit distinct TADF characteristics,which can be attributed to an additional higher reverse intersystem crossing pathway.This is the first time that dual-TADF properties of single molecules have been achieved based on conformational isomerism.Its applications in“self-doping”organic light-emitting diode and biomedical imaging have further been investigated.All these results show the good potential of such dual-band TADF emitters based on molecular conformational isomerization.

Light-responsive color switching of self-doped TiO_(2-x)/WO_(3)·0.33H_(2)O hetero-nanoparticles for highly efficient rewritable paper

Smart materials that reversibly change color upon light illumination are widely explored for diverse appealing applications.However,light-responsive color switching materials are mainly limited to organic molecules.The synthesis of inorganic counterparts has remained a significant challenge because of their slow light response and poor reversibility.Here,we report a seeded growth strategy for the synthesis of TiO_(2-x)/WO_(3)·0.33H_(2)Ohetero-nanoparticles(HNPs)with networked wire-like structure of〜10 nm in diameters that enable the highly reversible light-responsive color switching properties.For the TiO_(2-x)/WO_(3)·0.33H_(2)OHNPs,T P species self-doped in TiO_(2-x)nanoparticles(NPs)act as efficient sacrificial electron donors(SEDs)and Ti-O-W linkages formed between TiO2-x and WO30.33H2O NPs ensure the nanoscale interfacial contact,endowing the HNPs enhanced photoreductive activity and efficient interfacial charge transfer upon ultraviolet(UV)illumination to achieve highly efficient color switching.The TiO_(2-x)/WO_(3)·0.33H_(2)OHNPs exhibits rapid light response(<15 s)and long reversible color switching cycles(>180 times).We further demonstrate the applications of TiO_(2-x)/WO_(3)·0.33H_(2)O HNPs in ink-free,light-printable rewritable paper that can be written on freehand or printed on through a photomask using UV light.This work opens an avenue for designing inorganic light-responsive color switching nanomaterials and their smart applications.

Ti^(3+) self-doped TiO_(2) as a photocatalyst for cyclohexane oxidation under visible light irradiation

Most of TiO_(2) particles can be used as a photocatalyst for the selective oxidation of cyclohexane under ultraviolet light illumination.In this paper,Ti^(3+) self-doped TiO_(2) submicron-sized particles(i.e.,Ti^(3+)/TiO_(2) SMP)were used as a catalyst for visible-light driven photocatalytic cyclohexane oxidation.The microstructure and properties of the Ti^(3+)/TiO_(2) SMP were characterized by X-ray diffraction(XRD),UVevisible diffuse reflection(UVeVis DRS),scanning electron microscopy(SEM),electron paramagnetic resonance(EPR),solid-state photoluminescence spectroscopy(PLS)and X-ray photoelectron spectroscopy(XPS).The Ti^(3+)/TiO_(2) SMP exhibits good visible-light driven photocatalytic performances for cyclohexane oxidation with cyclohexanone as a dominate product.Effects of solvent,reaction temperature,reaction time and oxygen pressure on the formation of cyclohexanone were investigated.The cyclohexane oxidation over the Ti^(3+)/TiO_(2) SMP photocatalyst using carbon tetrachloride as a solvent under the optimal conditions presents a greater selectivity to cyclohexane(i.e.,95.1%).Based on the controlled experimental results with different radical scavengers,the hole(h^(+))is critical for the activation of cyclohexane.

Self-doped n-type small molecular electron transport materials for high-performance organic solar cells

Two naphthalene diimide （NDI） and perylene diimide （PDI） based n-type water/alcohol soluble small molecules （NFN and PFP） are designed and utilized as electron transport layers （ETLs） for organic solar cells （OSCs）. NFN and PFP are synthesized by using Sonogashira coupling from alkynyl modified fluorene with mono-bromo substituted NDI and PDI. Density functional theory study results of NFN and PFP show that they possess excellent planarity due to the employment of triple bonds as connection units. Moreover, it was shown by electron paramagnetic resonance study that both NFN and PFP possess obvious self-doping behaviors, which may effectively enhance their charge transporting capability as ETLs in OSCs. Power conversion efficiencies of 8.59% and 9.80% can be achieved for OSCs with NFN and PFP as ETLs, respectively. The higher power conversion efficiency （PCE） of PFP based photovoltaic device is originated from the stronger doping property and higher mobility of PFR

Thermally activated delayed fluorescence materials for nondoped organic light-emitting diodes with nearly 100%exciton harvest

High-performance nondoped organic light-emitting diodes(OLEDs)are promising technologies for future commercial applications.Herein,we synthesized two new thermally activated delayed fluorescence(TADF)emitters that enable us,for the first time,to combine three effective approaches for enhancing the efficiency of nondoped OLEDs.First,the two emitters are designed to have high steric hindrances such that their emitting cores will be suitably isolated from those of their neighbors to minimize concentration quenching.On the other hand,each of the two emitters has two stable conformations in solid films.In their neat films,molecules with the minority conformation behave effectively as dopants in the matrix composing of the majority conformation.One hundred percent exciton harvesting is thus theoretically feasible in this unique architecture of“self-doped”neat films.Furthermore,both emitters have relatively high aspect ratios in terms of their molecular shapes.This leads to films with preferred molecular orientations enabling high populations of horizontal dipoles beneficial for optical outcoupling.With these three factors,OLEDs with nondoped emitting layers of the respective emitters both achieve nearly 100%exciton utilization and deliver over 30%external quantum efficiencies and ultralow efficiency roll-off at high brightness,which have not been observed in reported nondoped OLEDs.

Tuning the structures of polypyridinium salts as bifunctional cathode interfacial layers for all-solution-processed red quantum-dot light-emitting diodes

Self-doping cathode interfacial layers(CILs) with both favorable electron injection and transport characteristics meet the key requirement for realizing high-performance optoelectronic devices with simplified structures. Herein, four different polypyridinium salts with tunable backbones, side chains and counterions are elaborately designed to afford them desirable film-forming property, polarity, structural rigidity and self-doping feature. All-solution-processed red quantum dot light-emitting diodes(QLEDs) employing them as bifunctional CILs render remarkably improved device performances in contrast to the typical CIL material of poly[(9,9-bis(30-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)](PFN).The maximum external quantum efficiency of 2.74% achieved in this work represents one of the best values among the all-solution-processed QLEDs with individual organic CILs.

Black titanium dioxide nanomaterials for photocatalytic removal of pollutants:A review

Semiconductor photocatalysis is one of the most widely used environment-friendly technologies for removing various contaminants.As a well-developed photocatalyst,titanium dioxide(TiO_(2))still has limits in its wide bandgap and rapid recombination rate of photogenerated charge carriers.Recently,black TiO_(2)appears as a strong candidate in the improvement of sunlight harvesting,because of its excellent absorption capacity and utilization of solar radiation.Despite extensive applications in both environmental and energy fields,the use of black TiO_(2)as a photocatalyst in pollutant removal is ambiguous.The primary objective of the review is to comprehensively evaluate the applications of black TiO_(2)in photocatalytic removal of contaminants,including conventional organic contaminants,emerging contaminants,microbes,and heavy metals.The basic properties,photocatalytic mechanism,and synthesis of black TiO_(2)have been summarized and analyzed.Moreover,the stability and recoverability of black TiO_(2)have also been discussed.Finally,the perspectives of the application of black TiO_(2)in pollutant removal have been further discussed.

Investigation on morphology and broadband blue-white emission modification of La_(1–x)Bi_xOCl polycrystals

Tetragonal structure La1-xBixOCl polycrystals were prepared by solid state synthesis. With increase in bismuth content, the morphology of the prepared samples changed from non-oriented particles to layered crystals and the broadband blue-white emission from LaOCl polycrystals decreased dramatically. Comparative experiments and X-ray photoelectron spectroscopy（XPS） analysis indicated that the host emission more possibly originated from Cl self-doping in oxychloride crystals. According to a close composition relationship of the Cl self-doping behavior and crystal morphology, it was suggested that the La composition strengthened the interlayer interaction between Cl^– anion and crystal cell lamellar, hindering the orientation of LaOCl crystals. The results of our work would deepen the understanding of the orientation structure of tetragonal oxyhalides and offer an insight into the origin of its host luminescence.