Pseudocapacitive Heteroatom-Doped Carbon Cathode for Aluminum-Ion Batteries with Ultrahigh Reversible Stability

Aluminum(Al)-ion batteries have emerged as a potential alternative to conventional ion batteries that rely on less abundant and costly materials like lithium.Nonetheless,given the nascent stage of advancement in Al-ion batteries(AIBs),attaining electrode materials that can leverage both intercalation capacity and structural stability remains challenging.Herein,we demonstrate a C3N4-derived layered N,S heteroatom-doped carbon,obtained at different pyrolysis temperatures,as a cathode material for AIBs,encompassing the diffusion-controlled intercalation and surface-induced capacity with ultrahigh reversibility.The developed layered N,S-doped corbon(N,S-C)cathode,synthesized at 900℃,delivers a specific capacity of 330 mAhg^(-1)with a relatively high coulombic efficiency of~85%after 500 cycles under a current density of 0.5 A g^(-1).Owing to its reinforced adsorption capability and enlarged interlayer spacing by doping N and S heteroatoms,the N,S-C900 cathode demonstrates outstanding energy storage capacity with excellent rate performance(61 mAhg^(-1)at 20 A g^(-1))and ultrahigh reversibility(90 mAhg^(-1)at 5Ag^(-1)after 10000cycles).

Co-Ru alloy nanoparticles decorated onto two-dimensional nitrogen doped carbon nanosheets towards hydrogen/oxygen evolution reaction and oxygen reduction reaction

Constructing highly-efficient electrocatalysts toward hydrogen evolution reaction(HER)/oxygen evolution reaction(OER)/oxygen reduction reaction(ORR)with excellent stability is quite important for the development of renewable energy-related applications.Herein,Co-Ru based compounds supported on nitrogen doped two-dimensional(2D)carbon nanosheets(NCN)are developed via one step pyrolysis procedure(Co-Ru/NCN)for HER/ORR and following low-temperature oxidation process(Co-Ru@RuO_(x)/NCN)for OER.The specific 2D morphology guarantees abundant active sites exposure.Furthermore,the synergistic effects arising from the interaction between Co and Ru are crucial in enhancing the catalytic performance.Thus,the resulting Co-Ru/NCN shows remarkable electrocatalytic performance for HER(70 mV at 10 mA cm^(-2))in 1 M KOH and ORR(half-wave potential E_(1/2)=0.81 V)in 0.1 M KOH.Especially,the Co-Ru@RuO_(x)/NCN obtained by oxidation exhibits splendid OER performance in both acid(230 mV at 10 mA cm^(-2))and alkaline media(270 mV at 10 mA cm^(-2))coupled with excellent stability.Consequently,the fabricated two-electrode water-splitting device exhibits excellent performance in both acidic and alkaline environments.This research provides a promising avenue for the advancement of multifunctional nanomaterials.

不同碳黑填料含量2D-SiC_f/SiC复合材料介电及雷达吸波性能研究

对先驱体浸渍裂解工艺（PIP）制备的含碳黑填料2D—SiCf／SiC复合材料介电以及雷达吸波性能进行研究。研究表明，由于KD-I型SiC纤维表面具有连续碳涂层，不能直接用于吸波材料，需通过空气热处理手段将其除去。对纤维表面去碳后制成的不同碳黑填料含量2D．SiCf／SiC复合材料微波介电常数进行测试，结果表明，随碳黑含量增加，复合材料介电常数明显增大，但由于碳黑的高比表面和先驱体溶液粘度的限制，复合材料中碳黑体积分数最大仅能达到7％～8％，介电常数难以继续增大，介电损耗低于0．3，并且介电常数频散效应不理想。对不同碳黑填料含量复合材料反射率进行计算，结果表明，单层复合材料在某一频段内具有较好的吸波性能，但由于复合材料介电常数频散效应较差，宽频吸波性能不理想，采用不同吸收剂含量复合材料层铺工艺可能可以解决吸波性能带宽问题。

粉煤灰混凝土2D和3D碳化试验

首先建立了2D和3D碳化测试方法,在此基础上系统研究了粉煤灰混凝土在加速碳化试验中2D和3D碳化深度的依时变化规律,探讨了粉煤灰掺量(0%,10%,20%,40%,60%)、粉煤灰种类(Ⅰ级、Ⅱ级)、水胶质量比(0.3,0.35,0.4)、胶凝材料用量(458,380kg/m3)、养护龄期(28,90d)5个重要因素对粉煤灰混凝土2D和3D碳化深度的影响规律.另外,还将2D和3D碳化试验结果与同条件下1D碳化进行了定量比较,发现2D和3D碳化明显存在交互作用,为量化该交互作用提出了2D和3D碳化交互系数概念,并给出了2D和3D碳化交互系数随时间变化的数学表达式.以期为准确预测实际混凝土结构在真实状态下碳化寿命提供科学依据.

基体对PIP法制备2D C_f/SiC材料抗氧化性能的影响

以3k JC1^#纤维布为增强体，以聚碳硅烷为先驱体，采用先驱体转化工艺制备了2D Cf／SiC复合材料，考察了基体结构对材料抗氧化性能的影响。结果表明，先驱体转化2D Cf／SiC复合材料的抗氧化性能主要与材料基体中的游离碳含量及孔隙率有关，基体中游离碳含量和孔隙率越高，材料的抗氧化性能越差。通过减少基体中的孔隙率和游离碳含量，可以制备抗氧化性能较好的2D Cf／SiC复合材料，在1300℃，马弗炉中氧化20min后，材料的失重率仅为2．2％，弯曲强度和断裂韧性保留率达到83．6％和80．9％。

Ultrathin 2D Metal–Organic Framework Nanosheets In situ Interpenetrated by Functional CNTs for Hybrid Energy Storage Device

The controllable construction of two-dimensional(2D)metal–organic framework(MOF)nanosheets with favorable electrochemical performances is greatly challenging for energy storage.Here,we design an in situ induced growth strategy to construct the ultrathin carboxylated carbon nanotubes(C-CNTs)interpenetrated nickel MOF(Ni-MOF/C-CNTs)nanosheets.The deliberate thickness and specific surface area of novel 2D hybrid nanosheets can be effectively tuned via finely controlling C-CNTs involvement.Due to the unique microstructure,the integrated 2D hybrid nanosheets are endowed with plentiful electroactive sites to promote the electrochemical performances greatly.The prepared Ni-MOF/C-CNTs nanosheets exhibit superior specific capacity of 680 C g^−1 at 1 A g^−1 and good capacity retention.The assembled hybrid device demonstrated the maximum energy density of 44.4 Wh kg^−1 at a power density of 440 W kg^−1.Our novel strategy to construct ultrathin 2D MOF with unique properties can be extended to synthesize various MOF-based functional materials for diverse applications.

Hydrothermal Synthesis and Crystal Structure of a New 2D Layered Cadmium(II) Coordination Polymer:[Cd(bimc)_2]_n(bimc=1H-Benzimidazole-5-carboxylate)

A new coordination polymer [Cd（bimc）2]n was obtained by the reaction of Hbimc with Cd（NO3） 2·4H2O in NaOH solution, and characterized by elemental analysis, IR and singlecrystal X-ray diffraction. The crystal belongs to orthorhombic, space group Pbcn with a = 12.533（4）, b = 15.705（5）, c = 15.200（5） A, V= 2991.8（15） A^3, Mr = 434.68, Z = 8, Dc = 1.930 g/cm^3, F（000） = 1712,μ（MoKa） = 1.492 mm^-1, the final R = 0.0410 and wR = 0.0804 for 1661 observed reflections （I 〉 2σ（I））. The Cd atom exhibits a distorted six-coordinate CdNzOa octahedral coordination geometry. The complex molecules are linked by both μ2-（η2-O, O^-）, NI and μ2-（η2-O, O^-）, N3 coordination modes of ligands to form cross-like wave （4, 4） layer structures which are further stacked through interlayer hydrogen bonds and π-π stacking interactions in an offset fashion to form a 3D supramolecular structure.

具有负泊松比效应的2D碳纳米结构设计及其性能的理论计算研究

本文利用第一性原理PBE密度泛函理论计算的方法设计了一种由炔基链、吡啶环及少量氢原子组成的具有内凹六边形结构单元的新型理想二维碳纳米结构,并对其平面内负泊松比效应等力学性能和光学性能与电子结构进行了预测.计算表明,该2D材料具有较好的结构稳定性和特殊的力学性能.当将该2D结构在面内(bc面)沿c方向压缩时,其在b方向收缩;当沿c方向拉伸时,其在b方向伸长,即该2D结构同样具有期望的负泊松比效应.材料的泊松比为-3.26;将该2D结构沿b方向拉伸时,c方向将随之伸长;沿b方向压缩时,c方向将随之收缩.沿b方向拉伸或压缩时,泊松比约为-1.951.即该2D材料在面内具有非常显著的负泊松比效应.此外,该2D材料表现出半导体材料的电子结构特征和良好的光反射和折射性能.希望本工作能为具有本征负泊松比效应和优良电子与光学功能的理想二维碳纳米材料的开发提供一种理想的结构设计策略.

金属离子诱导富含缺陷的二维碳基材料的构筑及其电催化制双氧水性能研究

二维碳基材料具有特殊的电荷传输通道和高效传质界面,是气-液-固三相电催化系统中优异的反应界面。提出了一种新颖的、可方便有效地实现二维碳材料构建的钠离子封端策略,在此基础上通过缺陷羰基化方法将丰富的不饱和含氧基团接枝到二维碳表面。结果表明,最终的产物在H型电解池中表现出高达90%的过氧化氢电催化选择性和270 mmol/(g_(catalyst)·h)的实际过氧化氢生产速率。该研究不仅为二维碳基结构的设计提供了一个新的方法,而且为富含不饱和含氧基团的二维碳在要求快速反应扩散和高密度活性位的气液固三相电催化系统中的应用提供了策略。

超临界二氧化碳辅助制备二维非晶材料

二维非晶材料不仅具有二维材料的高比表面积和高表面原子活性,还具有非晶材料的多缺陷和活性位点等优势,是理想的催化材料。近年来,超临界二氧化碳辅助制备工艺在制备二维非晶材料方面取得了一系列成功。介绍了利用超临界二氧化碳辅助制备各种二维非晶材料,讨论了其可能的非晶化机理及其对二维材料结构和性能的影响,并进一步展示了它们在不同领域的应用。对超临界二氧化碳辅助制备二维非晶材料的研究不仅能从理论层面理解二维非晶材料的形成机制,更为制备具有特定结构和性能的二维非晶材料提供指导。相关研究展示了超临界二氧化碳辅助制备工艺在材料设计和工程应用中具有广阔的前景。

二维碳基Janus薄膜的研究进展

以碳纳米管(CNTs)及石墨烯为代表的碳纳米材料具有卓越的物理、化学、电学和光学性质。其可控组装的二维碳基薄膜具有高比表面积、高透过率和良好柔性,广泛应用于柔性薄膜、微电子器件及储能领域。在此基础上引入高分子组分结合形成二维碳基Janus薄膜,不仅维持了其导电导热性,还结合了高分子的刺激响应和调控特性,通过非对称特征,实现了物理和化学性质的协同,大幅拓宽了其应用领域。文中综述了二维碳基Janus薄膜的研究近况。首先从物理法和化学法两方面介绍了二维碳基Janus薄膜的制备方法及其优缺点,物理法包括界面成膜法、真空抽滤法和层层组装法等;化学法包含界面聚合及化学接枝等方法。然后总结了二维碳基Janus薄膜在传感、驱动、海水淡化、油水分离等多个领域的应用现状。最后讨论了二维碳基Janus膜的发展前景及面临的挑战。

2D–3D dual carbon layer confined ultrasmall VN nanoparticles for improving lithium-ion storage in hybrid capacitors

Lithium-ion capacitors(LICs) of achieving high power and energy density have garnered significant attention. However, the kinetics unbalance between anode and cathode can impede the application of LICs. Vanadium nitride(VN) with a high theoretical specific capacity(~ 1200 m Ah·g^(-1)) is a better pseudocapacitive anode to match the response of cathode in LICs. However, the insertion/extraction of Li-ions in VN's operation results in significant volume expansion. Herein, the VN/N-r GO-5composite that three-dimentional(3D) dicyandiamidederived-carbon(DDC) tightly wrapped VN quantum dots(VN QDTs) on two-dimentional(2D) reduced graphene oxid(r GO) was prepared by a facile strategy. The VN QDTs can reduce ion diffusion length and improve charge transfer kinetics. The 2D r GO as a template provides support for nanoparticle dispersion and improves electrical conductivity. The 3D DDC tightly encapsulated with VN QDTs mitigates agglomeration of VN particles as well as volume expansion. Correspondingly, the LICs with VN/Nr GO-5 composite as anode and activated carbon(AC) as cathode were fabricated, which exhibits a high energy density and power density. Such strategy provides a perspective for improving the electrochemical properties of LIC anode materials by suppressing volume expansion and enhancing conductivity.

交通低碳出行对城市大气污染的改善作用研究

分析交通低碳出行对城市大气污染的改善作用。通过相关资料采集,计算居民出行结构导致的碳排放基准量;在交通低碳出行政策全面推广条件下,对交通排放气体中,影响大气环境的主要成分展开分析,计算交通碳减排量;结合交通工具能源消耗与污染物排放量之间关系,建立二维协同坐标系,引入弹性系数,测算交通低碳出行造成的城市大气污染物成分降低程度。仿真实验证明,调整交通工具使用比例,在基准、中度减排出行与强化交通低碳出行3种情景下,大气主要污染成分的含量大幅降低。

粉煤灰混凝土二维、三维碳化深度的预测

通过快速碳化试验,研究了不同粉煤灰掺量(0%,20%,40%,60%)下高性能混凝土一维、二维和三维碳化深度;定义了二维和三维碳化的交互系数;分析了二氧化碳扩散时间依赖性系数n和二维、三维交互系数K;推导了包含n和K的二维和三维碳化数学模型.实验表明,混凝土的二维、三维碳化具有一个明显的交互作用;交互系数服从经时衰减函数;通过傅立叶级数展开多维扩散交互系数,可求解基于Fick第一扩散定律的二维和三维碳化寿命预测的数学模型.通过对苏通大桥箱梁部位结构混凝土寿命进行预测,其一维、二维和三维预测寿命分别为1 595年、882年和758年,二维和三维碳化寿命明显降低.

高碳糖希夫碱的~1H NMR和^(13)C NMR全归属

对7个高碳糖希夫碱进行了~1H和^(13)C NMR检测,通过 DEPT和~1H-~1H COSY,HMQC,HMBC等 2D NMR技术对其~1H和^(13)C NMR数据进行了全归属和较详细的解析,并指出其NMR特征。

CoS_(2)nanowires supported graphdiyne for highly efficient hydrogen evolution reaction

Transition metal sulfides are an important category for hydrogen evolution reaction(HER).However,only few edge unsaturated sulfurs functionalize as catalytic sites,which has dramatically limited the catalytic activity and stability.In this work,planar unsaturated sulfurs in(211)plane of the CoS_(2)nanowires have been successfully activated through constructing Graphdiyne-CoS_(2)heterojunction nanocomposites.The corresponding electrons transfer energy barriers for these planar unsaturated sulfurs have been significantly diminished,which are induced by the synergetic effects of the sp~1 hybridized carbons and unsaturated planar sulfurs.In addition,DFT simulations reveal the synergetic effects of the sp~1 hybridized carbons and unsaturated planar sulfurs can promote electron transfer kinetics of the key step,VolmerHeyrovsky step,of the reaction.As expected,the Graphdiyne-CoS_(2)heterojunction nanocomposites exhibit superior HER catalytic performance with low overpotential of 97 mV at 10 mA cm^(-2),and the Tafel slope of 56 mV dec^(-1).Furthermore,the heterojunction shows outstanding stability as well due to the pr tection of the Graphdiyne(GDY).The approach thus paves the way for the further efficient transition metal disulfides catalyst manufactures.

考虑应力状态的二维混凝土碳化过程数值模拟

混凝土碳化过程的数值模拟为研究碳化机理、碳化影响因素、碳化过程与力的耦合作用等提供了新的定量分析工具.为定量分析应力状态对混凝土截面角部碳化发展的影响,建立了混凝土碳化过程的2维数值计算模型,使得混凝土组分、应力状态等影响可以得到定量考虑,并模拟应力状态下混凝土构件角部的碳化过程.详细介绍了这一模型的数值计算实现过程,研究了网格尺寸及时间步长对数值计算结果的影响.该模型数值计算结果与快速碳化试验和长期暴露碳化试验结果的对比验证了模型计算结果的准确性.最后,对某混凝土构件的角部混凝土碳化过程进行了数值分析.结果表明,混凝土截面角部双向碳化作用以及拉应力状态均会加速混凝土碳化,角部是整个构件截面碳化发展最为迅速的部位,其耐久性应当予以考虑.

二维气相色谱法分析天然气水合物区沉积物间隙水中示踪气体的浓度

利用微流路控制技术中心切割装置（Deans Switch）、两根色谱柱（PoraPLOT Q和Molsieve5A）和3个检测器（脉冲氦离子化检测器、火焰光度检测器、热导检测器）,建立了一种二维气相色谱分析系统,实现了海洋中多种示踪气体组分（氢气、甲烷、二氧化碳、硫化氢）的同时分析和精确测定。氢气、甲烷、二氧化碳、硫化氢的含量分别在2-1 030、0.6-501、120-10 500和0.2-49.1μmol/mol范围内的校正曲线线性关系良好,检出限分别为0.51、0.17、82和0.08μmol/mol,10次重复测定含量的相对标准偏差均小于10%。通过对南海天然气水合物区沉积物间隙水顶空气的测定,表明该方法方便、灵敏、可靠,易于实现海上现场测定;与以往采用多种分析方法分别测定示踪气体相比,大大节省了样品量。该方法适用于海洋天然气水合物、海底热液等资源的调查和海洋溶解态气体的研究等。

Tunable 2D tremella-derived carbon nanosheets with enhanced pseudocapacitance behavior for ultrafast potassium-ion storage

The sluggish intercalation kinetics of potassium ions in various anode materials severely hinders the practical application of potassium ion batteries(PIBs) in the field of new energy storage. To overcome this difficulty, we developed a green and recyclable molten-salt(MS) strategy using natural tremella as raw material to construct self-N-doped two-dimensional(2D)tremella-derived carbon nanosheets(TCNs), which possesses large specific surface area(SSA), expanded interlayer spacing and rich defects/active sites. Thanks to the unique 2D nanosheet structure and self-N doping, TCNs800 electrode exhibits superior K+storage capacity(386.3 mA h g^(-1) at 0.1 A g^(-1)), ultrafast rate performance(119.7 mA h g^(-1) at 2.0 A g^(-1)) and long-term cycling stability(122.9 mA h g^(-1) with the Coulombic efficiency of near 100% after 1000 cycles). Moreover, detailed electrochemical kinetic analysis shows that the potassium-ion storage mechanism of TCNs800 electrode has enhanced by the pseudocapacitancecontrolled behavior. This work proves an effective green and environmentally friendly MS strategy to prepare 2D biomass nanosheet materials, and provides a reference for exploring excellent electrode materials with pseudocapacitance-controlled behavior.

二维凝胶体系中碳酸钙分形结构的形成与机理研究

本文研究了二维琼脂凝胶圆盘体系中碳酸钙分形结构的形成过程,发现随着反应时间的增加,碳酸钙的形态经过了细小颗粒-枝晶结构-分形结构的转变过程,该分形结构实际上是由纳微米级碳酸钙晶粒聚集而成的。增加琼脂和反应物的浓度,碳酸钙微晶的形貌和尺寸发生了变化,呈现立方体与球形,由其构成的分形结构的尺寸也随着改变,但碳酸钙的晶型均为方解石型,无明显变化。二维凝胶体系中碳酸钙分形结构的形成主要与琼脂极性基团提供成核位点、多糖的网络结构、沉淀剂离子扩散受限有关。