Manipulating the Macroscopic and Microscopic Morphology of Large-Area Gravure-Printed ZnO Films for High-Performance Flexible Organic Solar Cells

Gravure printing is a promising large-scale fabrication method for flexible organic solar cells(FOSCs)because it is compatible with two-dimension patternable roll-to-roll fabrication.However,the unsuitable rheological property of ZnO nanoinks resulted in unevenness and looseness of the gravure-printed ZnO interfacial layer.Here we propose a strategy to manipulate the macroscopic and microscopic of the gravure-printed ZnO films through using mixed solvent and poly(vinylpyrrolidone)(PVP)additive.The regulation of drying speed effectively manipulates the droplets fusion and leveling process and eliminates the printing ribbing structure in the macroscopic morphology.The additive of PVP effectively regulates the rheological property and improves the microscopic compactness of the films.Following this method,large-area ZnO∶PVP films(28×9 cm^(2))with excellent uniformity,compactness,conductivity,and bending durability were fabricated.The power conversion efficiencies of FOSCs with gravure-printed AgNWs and ZnO∶PVP films reached 14.34%and 17.07%for the 1 cm^(2)PM6:Y6 and PM6∶L8-BO flexible devices.The efficiency of 17.07%is the highest value to date for the 1 cm^(2)FOSCs.The use of mixed solvent and PVP addition also significantly enlarged the printing window of ZnO ink,ensuring high-quality printed thin films with thicknesses varying from 30 to 100 nm.

Quantitative characterizations of anisotropic dynamic properties in organic-rich shale with different kerogen content

Understanding the quantitative responses of anisotropic dynamic properties in organic-rich shale with different kerogen content(KC)is of great significance in hydrocarbon exploration and development.Conducting controlled experiments with a single variable is challenging for natural shales due to their high variations in components,diagenesis conditions,or pore fluid.We employed the hot-pressing technique to construct 11 well-controlled artificial shale with varying KC.These artificial shale samples were successive machined into prismatic shape for ultrasonic measurements along different directions.Observations revealed bedding perpendicular P-wave velocities are more sensitive to the increasing KC than bedding paralleling velocities due to the preferential alignments of kerogen.All elastic stiffnesses except C_(13)are generally decreasing with the increasing KC,the variation of C_(1) and C_(33)on kerogen content are more sensitive than those of C_(44)and C_(66).Apparent dynamic mechanical parameters(v and E)were found to have linear correlation with the true ones from complete anisotropic equations independent of KC,which hold value towards the interpretation of well logs consistently across formations,Anisotropic mechanical parameters(ΔE and brittlenessΔB)tend to decrease with the reducing KC,withΔB showing great sensitivity to KC variations.In the range of low KC(<10%),the V_(P)/V_(S) ratio demonstrated a linearly negative correlation with KC,and the V_(P)/V_(S) ratio magnitude of less than 1.75may serve as a significant characterization for highly organic-rich(>10%)shale,compilation of data from natural organic rich-shales globally verified the similar systematic relationships that can be empirically used to predict the fraction of KC in shales.

Impacts of Water-Sediment Regulation Scheme on Chromophoric Dissolved Organic Matter in the Lower Yellow River

As a river with more than 3000 reservoirs in its watershed,the Yellow River has been affected by dams not only on the sediment load,but also on the water quality.Water-sediment regulation scheme(WSRS),which has been carried out annually in the Yellow River since 2002,is a typical human activity affecting river water quality.Chromophoric dissolved organic matter(CDOM)in river is susceptible to changes in ecological and environmental conditions as well as human activities.Here,we report variations in dissolved organic carbon concentrations,compositions and sources of CDOM in time series samples in the lower Yellow River during WSRS.In addition,a parallel factor fluorescence analysis(PARAFAC)method is applied to identify different fluorescent components in water samples during WRSR,showing four major components including tryptophan-like component(C1),microbial humic-like component(C2),terrestrial humic-like component(C3)and tyrosine-like component(C4).In general,C1 increased after water regulation,while C2 and C3 increased after sediment regulation,indicating that the water and sediment released by the dam have different effects on CDOM compositions.Under the impacts of the dam,source of CDOM in the lower Yellow River is mainly autochthonous related to microbial activities,and is regulated by the terrestrial input during WSRS period.Sediment resuspension inhibits microbial activities and reduces the production of autochthonous CDOM.Overall,human activities especially WSRS,as exemplified here,significantly alter the quality and quantity of CDOM in the lower Yellow River,affecting CDOM dynamics and biogeochemical processes in the estuarine environment.

Key Physical Factors Affecting Spatial-temporal Variation of Labile Organic Carbon Fractions by Biochar Driven in Mollisols Region of Northeast China

Biochar is widely used to improve soil physical properties and carbon sequestration. However, few studies focuse on the impact of maize stalk biochar on labile organic carbon(LOC) pool and the relationship between physical properties and LOC fractions. A field positioning experiment was performed in Mollisols region of Northeast China to evaluate the influence of maize stalk biochar on the spatial distribution and temporal changes of physical properties and LOC fractions. Maize stalk biochar treatments included C1(1.5 kg·hm^(-2)), C2(3 kg·hm^(-2)), C3(15 kg·hm^(-2)), C4(30 kg·hm^(-2)), and CK(0). The results showed that maize stalk biochar increased soil water contents(SWC) and soil porosity(SP), but reduced bulk density(BD). Maize stalk biochar reduced dissolved organic carbon(DOC) contents in the 0-20 cm soil layer, ranging from 0.25 g·kg^(-1) to 0.31 g·kg^(-1) in harvest period, while increased in the 20-40 cm soil layer. In addition, the application of biochar had a significant impact on the spatial distribution and temporal change of SWC, BD, SP, DOC, hot-water extractable carbon(HWC), acid hydrolyzed organic carbon(AHC Ⅰ, Ⅱ), and readily oxidized organic carbon(ROC). High amounts of maize stalk biochar up-regulated the contents of soil organic carbon SOC, HWC, AHC Ⅰ, AHC Ⅱ, and ROC. In addition, SWC and SP were the key physical factors to affect LOC fractions. In conclusions, maize stalk biochar could improve physical properties, and then influence LOC fractions, and maize stalk biochar could be used as an organic amendment for restoring degraded soils governed by their rates of addition.

An Explosive Organic/Inorganic Hybrid: Synthesis and Thermal Property of Octa(2,4-dinitrophenyl)silsesquioxane

Octaphenylsilsesquioxane(OPhS) was prepared by a modifying method and a new core-shell nanocomposite, octa(2,4-dinitrophenyl)silsesquioxane, [(R_2PhSiO_ 1.5)_8, R=—NO_2, ODNPhS], was synthesized by nitration of OPhS in a mixed acid solution of nitric and sulfuric acids at about 60 ℃. Their molecular structures were determined by DRIFTS, 1H NMR, 13C NMR spectra analysis. The thermal analysis shows that ODNPhS is an explosive that detonates at about 420 ℃.

Thixotropic composite hydrogels based on agarose and inorganic hybrid gellants

Water can be used as oxidant in conjunction with metal particles to form metal-water propellant to increase the energy of propellant.For this application,water needs to be stored in form of solid and capable of becoming liquid when use.Stable and thixotropic hydrogel has good potential as water-retaining material and oxidant of metal-based propellant.In this study,we prepared organic/inorganic composite hydrogels by combining inorganic gellants hectorite and fumed silica with organic gellant agarose,respectively.The total content of the gellants can be reduced to less than 2%by adding agarose.The influence of agarose on water content,phase transition temperature,centrifugal stability and other basic physical properties of composite hydrogels were discussed.The results show that the composite hydrogels have better thixotropy and stability than pure inorganic hydrogels,and the gel-sol transformation can be realized by applying shear force or heating to the phase transition temperature.The composite hydrogels have good shear thinning ability and improved mechanical stability.Fumed silica/agarose hydrogels have better physical stability,while the thixotropy and shear thinning ability of hectorite/agarose hydrogels are better.

Construction of all-organic low dielectric polyimide hybrids via synergistic effect between covalent organic framework and cross-linking structure

Polyimide(PI)is a promising electronic packaging material,but it remains challenging to obtain an all-organic PI hybrid film with decreased dielectric constant and loss without modifying the monomer.Herein,a series of allorganic PI hybrid films were successfully prepared by introducing the covalent organic framework(COF),which could induce the formation of the cross-linking structure in the PI matrix.Due to the synergistic effects of the COF fillers and the cross-linking structure,the PI/COF hybrid film containing 2 wt%COF exhibited the lowest dielectric constant of 2.72 and the lowest dielectric loss(tanδ)of 0.0077 at 1 MHz.It is attributed to the intrinsic low dielectric constant of COF and a large number of mesopores within the PI.Besides,the cross-linking network of PI prevents the molecular chains from stacking and improves the fraction of free volume(FFV).The molecular dynamics simulation results are well consistent with the dielectric properties data.Furthermore,the PI/COF hybrid film with 5 wt%COF showed a significant enhancement in breakdown strength,which increased to 412.8 kV/mm as compared with pure PI.In addition,the PI/COF hybrid film achieve to reduce the dielectric constant and thermal expansion coefficient(CTE).It also exhibited excellent thermal,hydrophobicity,and mechanical performance.The all-organic PI/COF hybrid films have great commercial potential as next-generation electronic packaging materials.

Copper-organic Framework Constructed from Rod-shaped Secondary Building Units with Selective Sorption Property

One novel metal-organic framework [Cu2（L）（μ3-OH）]n（1, H3L = [1,1＇：3＇,1＇＇-terphenyl]-4,4＇＇,5＇-tricarboxylic acid） has been synthesized and characterized by single-crystal powder X-ray diffraction, IR and thermogravimetric analyses. Complex 1 crystallizes in orthorhombic crystal system, space group Pbca with a = 21.573（19）, b = 5.404（5）, c = 33.78（3） ？, C21H（12）O7Cu2, Mr = 503.39, V = 3938（6） A^3, Z = 8, Dc = 1.698 g·cm^-3, μ = 2.202 mm^-1, F（000） = 2016, 1.531〈θ〈25.009°, λ（Mo Kα） = 0.71073 A, T = 293（2） K, the final R = 0.0448 and wR = 0.1002. The structure of complex 1 is a three-dimensional（3D） framework based on infinite rod-shaped secondary building units and can be simplified as kgd topology. The gas adsorption measurements for N2, CO2, H2O, CH3OH and CH3CH2OH have been done. Fortunately, the selective sorption of CO2 over N2 was found at 195 K.

Stability and optoelectronic property of low-dimensional organic tin bromide perovskites

The toxicity and degradation of hybrid lead-halide perovskites hinder their extensive applications.It is thus of great importance to explore non-toxic alternative materials with excellent stability and optoelectronic property.We investigate the atomic structures and optoelectronic properties of non-toxic organic tin bromide perovskites(OTBP)with one/zerodimensional(1D/0D)structures by first-principles calculations.The calculated atomic structures show that the 1D/0D OTBPs are stable and the structure of inorganic octahedra in 0D is higher order than that in 1D.Moreover,the origination of exceptional purity emitting light in experiments is explained based on the calculated electronic structure.

Organic geochemical and petrographic characteristics of the Cambrian-Ordovician organic-rich marine shales in Scandinavia

This work used organic geochemistry and organic petrology to study the depositional environment,organic matter characteristics,and thermal maturity of the Cambrian-Ordovician organic-rich marine shales in the Baltic Basin.The main macerals in Cambrian samples include alginite,bituminite and solid bitumen,while zooclastic macerals become the major proportion of organic matter in the Ordovician samples.As the maturity increase,solid bitumen becomes abundant and dispersed.Semifusinite-like maceral was observed only in Furongian of well DBH15/73,which probably indicates the local intrusion of Permo-Carboniferous dolerite dikes.The programmed pyrolysis results show that immature,early mature,and over-mature samples are developed.However,the data of high-uranium Furongian samples were greatly altered by igneous intrusives from local dikes.HIo calculation model is simulated based on pyrolysis data and fitted according to the least-square fitting method.The simulated fitting HIo:400mg HC/g TOC(369.5 mg HC/g TOC,430.5 mg HC/g TOC as 95%confidence bounds)is within the worldwide marine shale HI_(o)and indicates a marine anoxia and transgressive sea with shallow water column(organofacies B).

Magnetic Property of a Three-dimensional Copper Metal-organic Framework

A copper metal-organic framework（MOF） compound based on 2,5-thiophenedicarboxylic acid（H2 TDC） ligand, namely Cu（TDC）（H2 O）？DMA（1, DMA = N,N？-dimethylacetamide）, has been synthesized in gram-scale via a one-pot solvothermal route in a high yield of 81.3%. Single-crystal X-ray analysis reveals that the structure of 1 features a three-dimensional（3D） open framework constructed by TDC interconnecting 1D chains of [-Cu（COO）（H2 O）Cu-]n. Thermal property was investigated by TG-MS. The magnetic measurements indicate the existence of weak antiferromagnetic interactions between the Cu2＋ centers in 1.

基于过程解耦和工质物性的有机朗肯循环性能分析

通过对有机朗肯循环工作过程的拆分解耦,利用工质物性中的临界温度、偏心因子结合循环参数推导其热力学性能表征式,进而建立循环的热力学模型,并借助该模型分析循环参数对循环热力学性能评价指标的影响规律。研究结果显示:当蒸发温度升高时,循环热效率会增大,但其净输出功和效率先增大,然后再降低;当冷凝温度升高时,循环的热效率、净输出功和效率都会下降;当过热度升高时,循环的净输出功和效率随过之降低,而循环的热效率随之增大。基于工质物性引入雅各布数,循环的净输出功和热效率随雅各布数的增大分别呈现出增大和减小的趋势,而临界温度越高热效率随之升高。

纳米SiO_(2)复合粒子/有机硅低聚物透明超疏水复合涂层的制备及其性能

将Stöber法制备的胶体SiO_(2)粒子溶液与粉体SiO_(2)粒子进行物理共混得到SiO_(2)复合粒子溶液,以三乙氧基甲基硅烷(MTES)与正硅酸乙酯(TEOS)为前驱体制备的酸性有机硅低聚物为黏结剂,使用3-氨丙基三甲氧基硅(KH540)与全氟癸基三甲基氧硅(PFDT)对其进行改性,通过喷涂法在玻璃基底上制备出SiO_(2)复合粒子/酸性有机硅低聚物复合透明超疏水涂层。考察了SiO_(2)复合粒子、酸性有机硅低聚物、KH540及PFDT对复合涂层的影响。结果表明,当SiO_(2)复合粒子溶液由粒径为110 nm的胶体SiO_(2)粒子溶液与粒径为50 nm的粉体SiO_(2)粒子(其用量为胶体SiO_(2)粒子溶液质量的1%)组成、SiO_(2)复合粒子溶液与酸性有机硅稀释液质量比为4∶1、KH540与PFDT的添加量(以混合液总质量计,下同)均为1%时,制备的复合涂层在可见光波长范围内透光率可达88%,静态接触角达155°,在800目砂纸上磨损60 cm后仍能保持超疏水性能,具有良好的自清洁性。

反式聚异戊二烯/有机黏土复合材料的形状记忆性能

以反式聚异戊二烯(TPI)为基体,通过加入有机黏土(OC)制备了TPI/OC纳米复合材料(TPICNs)。通过X射线衍射、差示扫描量热、动态力学分析和扫描电子显微镜等手段分别考察了TPICNs的结晶情况、形状记忆性能、力学性能和微观形貌。结果表明,随着OC用量的增加,TPICNs的结晶度、拉伸强度和形状回复率均先增大后减小;当OC用量为1.2份(质量)时,TPICNs的拉伸强度最大且展现出最好的形状记忆行为;TPICNs断面处结晶颗粒分布均匀。

NASA技术转移中的知识产权管理及对公共研究机构的启示

聚焦公共研究机构的知识产权管理问题,以美国国家航空航天局(NASA)为研究对象,对其成熟的技术转移体系背后的国家法律支持以及知识产权管理政策和规范进行分析,重点关注其机构知识产权所有权归属、技术转移机制/流程和内部技术转移机构设置、角色和职责设计、技术许可商业化流程及技术转移的收益分配和奖励。公共研究机构可以从NASA成功的经验中获得如下启示:在遵循国家法律政策的基础上,完善知识产权所有权归属和使用权的相关规定,探索新的举措;建立更规范且操作性强的技术转移业务流程,针对技术批露、知识产权申请预评估与申请决策、技术商业化决策等管理关键环节构建有效管理机制;从业务流程出发建立更清晰的部门和岗位职责设置,重视专业人才队伍培养和引进;从建立知识产权管理平台、完善利益分配和奖励制度等角度构建科学的知识产权管理政策体系,以促进技术转移活动的开展。

凋落物输入变化对黄河三角洲柽柳人工林土壤有机碳及其组分的影响

为探究凋落物输入变化对土壤有机碳库的影响,明确凋落物对森林生态系统土壤碳循环的作用,以黄河三角洲滨海盐碱地柽柳人工林为研究对象,通过设置添加凋落物(LA)、去除凋落物(LR)和对照(CK)3种处理方法,分析凋落物不同输入变化对土壤理化性质、土壤有机碳及其组分的影响。结果表明:凋落物添加和去除处理影响土壤理化性质的变化,与对照相比,添加凋落物降低了土壤密度和含盐量,增加了土壤含水量和养分(全氮、全磷、全钾),而去除凋落物则相反。3种处理对土壤有机碳(SOC)及其储量以及活性有机碳组分的影响一致,均表现为LA处理影响最大,LR处理影响最小,其中LA处理比CK增加了SOC质量分数及储量,但增加不显著;LR处理则显著降低了SOC质量分数及其储量,土层深度(d)0<d≤10 cm土层,LR处理比CK处理的SOC质量分数及其储量分别显著降低了34.93%、12.66%,10 cm<d≤20 cm土层,LR处理比CK处理的SOC质量分数及其储量分别显著降低了24.27%、16.13%。LA处理的土壤SOC及可溶性有机碳(DOC)、易氧化有机碳(EOC)、微生物量碳(MBC)质量分数均出现明显的表聚现象,而LR处理影响则不显著,且DOC和MBC则出现随土层深度增加而增大的趋势。土壤惰性有机碳(ROC)质量分数在不同土层间存在差异,0<d≤10 cm土层,各处理表现为LA>CK>LR,10 cm<d≤20 cm土层,各处理则表现为CK>LA>LR,而在CK和LR处理出现随土层增加而增加的趋势,偏于向土层下方积累。土壤密度(BD)与SOC及其各组分呈负相关,而土壤含水量(WC)、全氮、全磷与SOC及EOC、MBC、DOC质量分数呈极显著正相关(P<0.01)。因此,不同处理方式及不同土层深度的土壤密度、全氮质量分数和土壤含水量是影响SOC及组分变化的主要环境因子。

农村集体经济组织成员资格认定的逻辑脉络及其展开

农村集体经济组织成员资格认定是农村集体产权制度改革的基础性工作,集体所有权主体的确定是该问题研究的逻辑起点。集体所有权不具有共有和总有等所有权构造类型的特征,同时投资关系说和类比国有资本授权经营体制论都不能对农村集体经济组织的产生渊源进行合理解释。在民法规范语境下,应将农村集体经济组织确定为集体所有权主体。就成员资格和成员权利的关系而言,两者相伴而生,成员资格实质上是从权利主体角度对成员权的描述,为成员权在主体面向的表达。基于此,集体成员资格认定的法律实质是对农民所享有的集体经济组织成员权予以确权。我国农村传统经营方式决定了农户是基本经营单位,从逻辑上应当将家庭成员与以家庭为单位取得权益的关系确定为按份共有,集体经济组织成员权主体应为集体经济组织成员而非农户。城乡二元体制导致户籍这一本质上与成员权利取得不具因果关系的因素被纳入认定标准之中,其证明作用不应被忽视。在传统路径下,应构建以出生事实为核心、其他亲缘关系为辅助的主体判断路径,同时明确列举其他除外情形,形成正反双向的认定机制。在农村集体产权制度改革背景下,基于股权类型设置,集体固有成员与股份经济合作社股东在范围上并非完全一致,未来应以恢复农村集体经济组织和集体成员权的私法属性为目标,分阶段对农村集体经济组织成员权制度进行渐进性改革。

磷肥有机替代、秸秆还田对土壤化学性质和棉花产量及其构成的影响

新疆有机肥资源丰富,探索磷肥有机替代、秸秆还田的外源肥料投入对土壤化学变化、棉花产量及其构成的影响,为深入了解当前棉田肥力和确定棉花减磷增效的技术服务着力点提供参考依据。经国家灰漠土肥力与肥料效益监测基地5年田间微区定位试验,在膜下滴灌条件下设置7个施肥处理,T1:不施肥,T2:不施磷,T3:常规施化肥磷100%,T4:有机肥磷替代25%化肥磷,T5:有机肥磷替代50%化肥磷,T6:化肥磷100%+25%有机肥磷,T7:化肥磷100%+秸秆还田。于2022年采集土壤样品,探明不同比例磷肥有机替代、秸秆还田对土壤化学性质、磷素有效性特征和棉花产量及其构成的影响。研究结果表明:(1)在外源肥料投入量(有机肥和化肥)均为等氮磷用量的条件下,磷肥有机替代、秸秆还田有利于加速土壤养分转化,增加土壤速效养分、全量养分含量。速效氮、有效磷、速效钾含量增幅分别在3.0%~25.3%、29.2%~120.1%、70.1%~99.1%之间,各速效养分含量依次与外源肥料投入后增量最高的T6、T5、T5处理相比,年均分别增长3.12、1.69、30.75 mg·kg^(-1)。全氮、全磷、全钾含量增幅分别在21.1%~43.9%、1.59%~41.3%、9.3%~33.6%之间,各全量养分含量依次与外源肥料投入后增量最高的T6、T6、T5处理相比,年均分别增长0.04、0.05、1.36 g·kg^(-1)。整体上有机替代、增施有机肥和秸秆还田对促进土壤养分的转化效果比单施化肥好,且长期施用有机肥的效应优于秸秆还田。(2)耕层土壤有机质含量随有机肥替代量的增加而增加,50%的有机替代其有机质含量显著最高(12.21 g·kg^(-1)),年均增长0.4 g·kg^(-1),最小增量T1~T2与最大增量T1~T5相比,增加1.04~3.44 g·kg^(-1),增幅为11.86%~39.22%,总体表现为正效应。相对较高的土壤pH和盐含量是限制棉花高效生产的主要因素,有机肥和秸秆还田对土壤pH和含盐量整体起到降低的作用,最大降幅pH的T1与T5、盐含量T5与T3相比分别下降3.07%、24.48%,总体表现为负效应。配施有机肥和秸秆还田增强了土壤供氮能力和磷素活化能力,土壤磷活化系数从1.52%提升到2.78%。由于受新疆石灰性土壤自然特性及气候条件限制,综合C/N、C/P、N/P表明,灰漠土有机质处于缺乏状态。(3)磷肥有机替代和秸秆还田均能够维持或促进棉花增产,在密度为24万株·hm^(-2)的试验种植模式下,连续5年常规施肥、25%的有机替代、50%的有机替代、增施有机肥、秸秆还田其籽棉产量分别达4173.13、4196.72、4805.10、5035.51、4830.98 kg·hm^(-2),综合土壤养分指标、肥料投入、棉花产量分析,50%的有机替代在节约磷肥用量的前提下对棉花增产效果最佳,与T1、T2、T3相比,分别显著增产20.49%、18.62%、15.14%。因此,研究认为当下应用50%的有机替代技术,即施磷(P_(2)O_(5))60 kg·hm^(-2)和配施羊粪9784 kg·hm^(-2),较为可行。

Wittig反应实验的绿色化改进

传统的有机化学实验教学中,大多侧重实验技能的训练,设置实验内容时对实验安全性、经典性和可重复性等因素考虑较多,而对反应的绿色化、新方法和新技能等重视程度不够。为此,经典的有机反应也需要不断改进,本文将需要在大量有机溶剂中进行的传统Wittig反应改进为无溶剂的固相研磨反应,使得合成方法更加简单、绿色、安全和高效。设计合成了3个不同推拉型(D-π-A)二苯乙烯结构分子,优化了反应条件,测定了它们的光谱性质,并对其进行比较,讨论其构性关系,不仅引入绿色化学理念,而且对知识进行扩展,增加了实验的新颖性、探索性和趣味性,提升了学生创新能力。

有机纤维增强水泥基复合材料研究进展

目前有机纤维作为增强体被用于水泥基复合材料成为研究的热点。阐述了有机纤维对水泥基复合材料性能影响的研究进展。首先,介绍了不同种类有机纤维的性能,阐述了不同有机纤维对水泥基复合材料性能的影响,并分析了增强增韧机理。其次,分析了有机纤维性能对水泥基复合材料性能的影响。最后,对今后的进一步研究提出了建议。