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Controlled Synthesis of Metal-Nanoparticles Decorated Block Copolymer Hybrid Particles via Emulsion Confined Self-assembly and Their Catalytic Applications

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Chinese Journal of chemistry 2024年第8期42卷 835-840页

作者： Xiaohua Chang Qunli Yu Dan Ji Yutian Zhu College of material Chemistry and Chemical EngineeringKey Laboratory of Organosilicon Chemistry and Material TechnologyMinistry of EducationHangzhou Normal UniversityHangzhouZhejiang311121 China

Comprehensive Summary Metal nanoparticles(NPs)decorated block copolymer(BCP)hybrid nanoparticles have attracted enormous attention for their actual value in catalysis,medical therapy,and bioengineering.The confined assembly of BCPs within evaporative emulsion droplet is verified as an effective method to provide polymeric scaffolds to load metal NPs.However,to date,it remains challenging to generate different types of metal NPs decorated BCP hybrid nanoparticles.Herein,we employed the emulsion confined self-assembly of poly(styrene-b-2-vinylpyridine)(PS-b-P2VP)and the followed seed-mediated growth of Au and palladium(Pd)NPs onto well-defined BCP particles to design a series of Au/Pd decorated BCP hybrid nanoparticles,which exhibited excellent catalytic activity for the reduction of 4-nitrophenol to 4-aminophenol with the reductant of NaBH4.This work may inspire more researchers to investigate the selective decoration of different metal NPs onto the polymeric scaffolds,broadening the potential applications of the inorganic/organic hybrid nanoparticles.

关键词： Block copolymers Emulsion confined self-assembly Hybrid nanoparticles Catalytic activity Recyclability

Progress of additives for morphology control in organic photovoltaics

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Chinese Chemical Letters 2024年第6期35卷 38-46页

作者： Zhongjie Li Xiangyue Kong Yuhao Liu Huayu Qiu Lingling Zhan Shouchun Yin key laboratory of organosilicon chemistry and materials technology of ministry of education College of MaterialChemistry and Chemical EngineeringHangzhou Normal UniversityHangzhou 311121China

The microstructure of the active layer in organic photovoltaics(OPVs),such as the size of phase separation,purity of the phases,and molecular packing within each phase,plays a crucial role in influencing the behavior of excitons and charge carriers within the active layer.It is also a key determinant of the photovoltaic performance of the device.During the optimization of OPV devices,the use of additives has been demonstrated to be an effective strategy in microstructure control,leading to enhanced performance.Therefore,the quest for stable and efficient novel additives,along with an exploration and summarization of the mechanisms underlying additive-induced microstructure control,is essential for a better understanding of the developmental trends of high-performance additives.In this review,we categorize additives based on their chemical structures and discuss their effects on the microstructure of the active layer from both thermodynamic and kinetic perspectives.Furthermore,we elaborate on the working mechanisms and their impact on the photovoltaic performance of the devices.This review provides an overview of recent advances in additives for OPVs,offering potential guidance for the future development of additives and further optimization of the active layer in photovoltaic devices.

关键词： Organic photovoltaics Additives Active layer morphology Mechanisms Photovoltaic performances

Catalytic enantioselective N-silylation of sulfoximine

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Chinese Chemical Letters 2024年第4期35卷 352-356页

作者： Xingfen Huang Jiefeng Zhu Chuan He Shenzhen Grubbs Institute and Department of chemistry Guangdong Provincial Key Laboratory of CatalysisSouthern University of Science and TechnologyShenzhen 518055China key laboratory of organosilicon chemistry and material technology of ministry of education Hangzhou Normal UniversityHangzhou 311121China

A rhodium/diphosphine-catalyzed asymmetric cross-dehydrogenative coupling between sulfoximines and dihydrosilanes has been achieved. This is the first report on the enantioselective N-silylation of sulfoximines. The protocol gives access to a variety of Si-stereogenic N-silylated sulfoximines in decent yield(up to 99%) with excellent stereoselectivity(up to 99%), featuring high atom economy, and a cleaner manner with H2as the sole byproduct. The obtained bis-Si-stereogenic monohydrosilane product can be further converted into the corresponding chiral polymer with pendant sulfoximine groups.

关键词： N-Silylation of sulfoximine Chiral silylamine Si-stereogenic silanes Si-CADC Asymmetric catalysis

Atom Transfer Radical Polymerization of Methyl Methacrylate in [Hmim][HCOO]/THF Mixtures

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Journal of Wuhan University of technology(materials Science) 2010年第5期25卷 785-788页

作者：胡自强来国桥 key laboratory of organosilicon chemistry and material technology of ministry of education Hangzhou Normal University

The atom transfer radical polymerization （ATRP） of methyl methacrylate （MMA） employing ethyl 2-bromoisobutyrate （EBiB）/CuBr as the initiating system was analyzed at 30, 40, 50 and 60 ℃ in N-methylimidazolium formate （[Hmim][HCOO]）/THF mixtures. The polymerization was performed in a well-controlled manner as evidenced by kinetic study and the chain extension result. The apparent activation energy and the enthalpy of equilibrium for the preequilibrium were also investigated. Results show that Ea（app）=47.86 kJ/mol, △Heq^0=25.67 kJ/mol.

关键词： ATRP methyl methacrylate ionic liquids activation energy

Manipulating fast Li_(2)S redox via carbon confinement and oxygen defect engineering of In_(2)O_(3)for lithium-sulfur batteries

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Nano Research 2024年第6期17卷 5179-5187页

作者： Jinlei Qin Rui Wang Zilong Yuan Pei Xiao Deli Wang key laboratory of material chemistry for Energy Conversion and Storage Ministry of EducationHubei Key Laboratory of Material Chemistry and Service FailureSchool of Chemistry and Chemical EngineeringHuazhong University of Science and TechnologyWuhan 430074China

Lithium-sulfur(Li-S)batteries have been considered as promising energy storage systems due to the merits of high energy density and low cost.However,the lithium polysulfides(LiPSs)diffusion and sluggish redox kinetics hamper the battery performance.In this work,low-bandgap indium oxide(In_(2)O_(3))with dense oxygen vacancies(In_(2)O_(3−x),0

关键词： Li-S batteries nitrogen-doped carbon confinement oxygen vacancies bidirectional Li_(2)S redox

Kinetic-boosted CO_(2) electroreduction to formate via synergistic electric-thermal field on hierarchical bismuth with amorphous layer

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Journal of Energy chemistry 2024年第3期90卷 233-243,I0007页

作者： Bing Yang Junyi Zeng Zhenlin Zhang Lin Meng Donglin Shi Liang Chen Youju Huang College of material Chemistry and Chemical EngineeringKey Laboratory of Organosilicon Chemistry and Material TechnologyMinistry of EducationHangzhou Normal UniversityHangzhou 311121ZhejiangChina State key laboratory of Metastable materials Science and technology College of Materials Science and EngineeringYanshan UniversityQinhuangdao 066004HebeiChina

Electrocatalytic converting CO_(2) into chemical products has emerged as a promising approach to achieving carbon neutrality.Herein,we report a bismuth-based catalyst with high curvature terminal and amorphous layer which fabricated via two-step electrodeposition achieves stable formate output in a wide voltage window of 600 mV.The Faraday efficiency(FE) of formate reached up to 99.4% at-0.8 V vs.RHE and it remained constant for more than 92 h at-15 mA cm^(-2).More intriguingly,FE formate of95.4% can be realized at a current density of industrial grade(-667.7 mA cm^(-2)) in flow cell.The special structure promoted CO_(2) adsorption and reduced its activation energy and enhanced the electric-thermal field and K^(+) enrichment which accelerated the reaction kinetics.In situ spectroscopy and theoretical calculation further confirmed that the introduction of amorphous structure is beneficial to adsorpting CO_(2)and stabling*OCHO intermediate.This work provides special insights to fabricate efficient electrocatalysts by means of structural and crystal engineering and makes efforts to realize the industrialization of bismuth-based catalysts.

关键词： CO_(2) electroreduction Hierarchical bismuth Amorphous layer Electric-thermal field Kinetic-boosting

A meso–molecular muscle based on copillar[5]arenes

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Chinese Chemical Letters 2024年第3期35卷 308-311页

作者： Yu Yao Peiling Zhang Dan Zhou Zhinan Lai Shijun Li Feihe Huang Zibin Zhang College of material Chemistry and Chemical EngineeringKey Laboratory of Organosilicon Chemistry and Material TechnologyMinistry of EducationKey Laboratory of Organosilicon Material TechnologyHangzhou Normal UniversityHangzhou 311121China Department of chemistry Stoddart Institute of Molecular ScienceZhejiang UniversityHangzhou 310027China Green Catalysis Center and College of chemistry Zhengzhou UniversityZhengzhou 450001China

A meso–molecular muscle was prepared by capping the[c2]daisy chain based on a mono-functionalized copillar[5]arene with an imidazolium group in its axle.From its crystal structure,we observed that it was a cyclic dimer composed of two mirror image subcomponents,a pR-and a pS-copillar[5]arene.Their conformations were fixed by the doubly interlocked mechanical bond.By comparison of the^1H NMR and COSY spectra,we found that the length of this meso–molecular muscle could be controlled not only by the solvents,but also by the counter anions.

关键词： Pillararenes Molecular muscles [c2]daisy chains Planar chirality

Flame-retardant ammonium polyphosphate/MXene decorated carbon foam materials as polysulfide traps for fire-safe and stable lithium-sulfur batteries

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Journal of Energy chemistry 2024年第2期89卷 313-323,I0008页

作者： Yang Li Yong-Cheng Zhu Sowjanya Vallem Man Li Seunghyun Song Tao Chen Long-Cheng Tang Joonho Bae Department of Physics Gachon UniversitySeongnam-siGyeonggi-do 13120South Korea key laboratory of organosilicon chemistry and material technology of ministry of education College of MaterialChemistry and Chemical EngineeringHangzhou Normal UniversityHangzhou 311121ZhejiangChina key laboratory of Advanced Energy materials chemistry(ministry of education) College of ChemistryNankai UniversityTianjin 300071China School of materials Engineering Changzhou Vocational Institute of Industry TechnologyChangzhou 213164JiangsuChina

Lithium-sulfur(Li-S)batteries are one of the most promising modern-day energy supply systems because of their high theoretical energy density and low cost.However,the development of high-energy density Li-S batteries with high loading of flammable sulfur faces the challenges of electrochemical performance degradation owing to the shuttle effect and safety issues related to fire or explosion accidents.In this work,we report a three-dimensional(3D)conductive nitrogen-doped carbon foam supported electrostatic self-assembled MXene-ammonium polyphosphate(NCF-MXene-APP)layer as a heat-resistant,thermally-insulated,flame-retardant,and freestanding host for Li-S batteries with a facile and costeffective synthesis method.Consequently,through the use of NCF-MXene-APP hosts that strongly anchor polysulfides,the Li-S batteries demonstrate outstanding electrochemical properties,including a high initial discharge capacity of 1191.6 mA h g^(-1),excellent rate capacity of 755.0 mA h g^(-1)at 1 C,and long-term cycling stability with an extremely low-capacity decay rate of 0.12%per cycle at 2 C.More importantly,these batteries can continue to operate reliably under high temperature or flame attack conditions.Thus,this study provides valuable insights into the design of safe high-performance Li-S batteries.

关键词： Flame-retardant MXene Ammonium polyphosphate Safety Lithium-sulfur battery

Accelerating solar driven CO_(2) reduction via sulfur-doping boosted water dissociation and proton transfer

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Nano Research 2024年第3期17卷 1056-1065页

作者： Ke Yan Liang Chen Yangguang Hu Ting Wang Cong Chen Chao Gao Youju Huang Benxia Li School of chemistry and Chemical Engineering Key Laboratory of Surface&Interface Science of Polymer Materials of Zhejiang ProvinceZhejiang Sci-Tech UniversityHangzhou 310018China College of material Chemistry and Chemical EngineeringKey Laboratory of Organosilicon Chemistry and Material TechnologyMinistry of EducationHangzhou Normal UniversityHangzhou 311121China School of chemistry and materials Science University of Science and Technology of ChinaHefei 230026China

Exploring efficient photocatalysts for solar driven CO_(2) reduction with water(H_(2)O)as a proton donor is highly imperative but remains a great challenge because the synchronous enhancement of CO_(2) activation,H_(2)O dissociation and proton transfer is hardly achieved on a photocatalyst.Particularly,the sluggish H_(2)O dissociation impedes the photocatalytic CO_(2) reduction reaction involving multiple proton–electron coupling transfer processes.Herein,a sulfur-doped BiOCl(S-BiOCl)photocatalyst with abundant oxygen vacancies(OV)is developed,which exhibits broadband-light harvesting across solar spectrum and distinct photothermal effect due to photochromism.For photocatalytic CO_(2) reduction with H_(2)O in a gas–solid system,the high CO yield of 49.76μmol·g_(cat)^(-1)·h^(-1) with 100%selectivity is achieved over the S-BiOCl catalyst under a simulated sunlight.The H_(2)O-assisted CO_(2) reduction reaction on S-BiOCl catalyst is triggered by photocatalysis and the photothermal heating further enhances the reaction rate.The kinetic isotope experiments indicate that the sluggish H_(2)O dissociation affects the whole photocatalytic CO_(2) reduction process.The presence of oxygen vacancies promotes the adsorption and activation of H_(2)O and CO_(2),and the doped S sites play a crucial role in boosting H_(2)O dissociation and accelerating the dynamic migration of hydrogen species.As a result,the ingenious integration of OV defects,S sites and photothermal effect in S-BiOCl catalyst conjointly contributes to the significant improvement in photocatalytic CO_(2) reduction performance.

关键词： BiOCl sulfur doping photocatalytic CO_(2)reduction H_(2)O activation proton feeding