Integrating Levels of Hierarchical Organization in Porous Organic Molecular Materials

Porous organic molecular materials(POMMs)are an emergent class of molecular-based materials characterized by the formation of extended porous frameworks,mainly held by non-covalent interactions.POMMs represent a variety of chemical families,such as hydrogen-bonded organic frameworks,porous organic salts,porous organic cages,C-H···πmicroporous crystals,supramolecular organic frameworks,π-organic frameworks,halogen-bonded organic framework,and intrinsically porous molecular materials.In some porous materials such as zeolites and metal organic frameworks,the integration of multiscale has been adopted to build materials with multifunctionality and optimized properties.Therefore,considering the significant role of hierarchy in porous materials and the growing importance of POMMs in the realm of synthetic porous materials,we consider it appropriate to dedicate for the first time a critical review covering both topics.Herein,we will provide a summary of literature examples showcasing hierarchical POMMs,with a focus on their main synthetic approaches,applications,and the advantages brought forth by introducing hierarchy.

Outstanding Lithium Storage Performance of a Copper-Coordinated Metal-Covalent Organic Framework as Anode Material for Lithium-Ion Batteries

Metal-covalent organic frameworks(MCOF)as a bridge between covalent organic framework(COF)and metal organic framework(MOF)possess the characteristics of open metal sites,structure stability,crystallinity,tunability as well as porosity,but still in its infancy.In this work,a covalent organic framework DT-COF with a keto-enamine structure synthesized from the condensation of 3,3'-dihydroxybiphenyl diamine(DHBD)and triformylphloroglucinol(TFP)was coordinated with Cu^(2+)by a simple post-modification method to a obtain a copper-coordinated metal-covalent organic framework of Cu-DT COF.The isomerization from a keto-enamine structure of DT-COF to a enol-imine structure of Cu-DT COF is induced due to the coordination interaction of Cu^(2+).The structure change of Cu-DT COF induces the change of the electron distribution in the Cu-DT COF,which greatly promotes the activation and deep Li-storage behavior of the COF skeleton.As anode material for lithium-ion batteries(LIBs),Cu-DT COF exhibits greatly improved electrochemical performance,retaining the specific capacities of 760 mAh g^(-1)after 200 cycles and 505 mAh g^(-1)after 500 cycles at a current density of 0.5 A g^(-1).The preliminary lithium storage mechanism studies indicate that Cu^(2+)is also involved in the lithium storage process.A possible mechanism for Cu-DT COF was proposed on the basis of FT-IR,XPS,EPR characterization and electrochemical analysis.This work enlightens a novel strategy to improve the energy storage performance of COF and promotes the application of COF and MCOF in LIBs.

Effects of Functional Organic Materials on Morphological Indexes,Quality and Yield of Watermelon

[Objectives]This study was conducted to explore suitable organic compound application models for watermelon growth.[Methods]With watermelon hybrid material"M22×P18"as the test material,the effects of four functional organic materials,namely garlic straw treatment(T_(1)),onion straw treatment(T_(2)),garlic straw+sheep manure treatment(T_(3))and onion straw+chicken manure treatment(T_(4)),on the morphological indexes,yield and quality of watermelon were investigated.[Results]Different functional organic materials had different effects on morphological indexes,yield and quality of watermelon.The morphological indexes,nutritional quality indexes and yield of watermelon treated with garlic straw and sheep manure compound(T_(3))and onion straw and chicken manure compound(T_(4))were significantly higher than those treated simply with garlic straw(T_(1))and onion straw(T_(2)),and T_(3)performed relatively better.Compared with treatment T_(2),T_(3)showed a stem diameter,vine length and leaf number increasing by 43.05%,46.69%and 40.77%respectively,central sugar and side sugar contents increasing by 11.72%and 21.90%respectively,and a yield increasing by 42.91%,with significant differences from T_(2).[Conclusions]This study provides technical support for high-quality and high-yielding cultivation of watermelon.

Effects of Functional Organic Materials on Fresh Weight,Quality,Single-melon Weight and SPAD Value of Watermelon

[Objectives]This study was conducted to explore a functional organic material formula suitable for watermelon cultivation with high quality,high yield and high efficiency.[Methods]Four treatments were set in the experiment,namely four functional organic materials,garlic straw treatment(T_(1)),onion straw treatment(T_(2)),garlic straw+sheep manure treatment(T_(3))and onion straw+chicken manure treatment(T_(4)),to investigate the effects of different functional organic materials on fresh weight,quality,single-melon weight and SPAD value of watermelon.[Results]The effects of different functional organic materials on fresh weight,quality,single-melon weight and SPAD value of watermelon were quite different.The fresh weight,quality,single-melon weight and SPAD value of watermelon were higher in treatment T_(3)applying garlic straw and sheep manure and treatment T_(4)applying onion straw and chicken manure than in treatment T_(1)applying garlic straw and treatment T_(2)applying onion straw.Specifically,the fresh weight of whole plant was the highest in treatment T_(3),followed by treatment T_(4),and the values of the two treatments increased by 12.83%and 5.94%respectively compared with treatment T_(1);the weight of single melon was the highest in treatment T_(3),followed by treatment T_(4),and the values of the two treatments increased by 42.45%and 31.77%respectively compared with treatment T_(2);and the SPAD values of treatments T_(3)and T_(4)were significantly higher than those of treatments T_(1)and T_(2),and the value of treatment T_(3)was the largest.[Conclusions]This study provides theoretical support for the popularization and application of fertilization techniques combining organic fertilizers and reduced chemical fertilizers for watermelon.

Towards green asphalt materials with lower emission of volatile organic compounds: A review on the release characteristics and its emission reduction additives

Recently, researchers in the road field are focusing on the development of green asphalt materials with loweremission of volatile organic compounds (VOCs). The characterization methodology of asphalt VOCs and theinfluencing factors on VOCs release have always been the basic issue of asphalt VOCs emission reduction research.Researchers have proposed a variety of asphalt VOCs characterization methodologies, which also have mutuallyirreplaceable characteristics. Asphalt VOCs volatilization is affected by many factors. In this study, asphalt VOCscharacterization methodologies were summarized, including their advantages, disadvantages, characteristics andapplicable requirements. Subsequently, the influencing factors of VOCs release, such as asphalt types and environment conditions, are summarized to provide theoretical support for the emission reduction research. Theclassification and mechanism of newly-development asphalt VOCs emission reduction materials are reviewed. Thereduction efficiencies are also compared to select better materials and put forward the improvement objective ofnew materials and new processes. In addition, the prospects about development of VOCs release mechanism ofasphalt materials during the full life cycle and feasibility research of high-efficiency composite emission reductionmaterials in the future were put forward.

Decomposition of Different Organic Materials and Variation of Active Organic Carbon and Nitrogen Contents in Tobacco-planted Soil

The oilseed cake, vetch, rapeseed straw, wheat straw and corn straw were buried in tobacco-planted soil. The decomposition rates, the variation of active organic C and N contents in the residues and the relationship between active organic C and N contents and decomposition rate were investigated. The results showed the decomposition rates of different organic materials were all high in the early period and then low in the late period. Among the organic materials, the decomposition rates ranked as oilseed cake 〉 vetch 〉 wheat straw and rapeseed straw 〉 corn straw. The decomposition rate was positively related to total N content （P〈0.01）, but was negatively related to the active organic C/N ratio （P〈0.01）. However, there was no significant relationship between decomposition ratio and active organic C content. With the proceeding of decomposition, the active organic C content and the total N content in rapeseed straw, vetch, wheat straw and corn straw all trended to increase, but the active organic C/N ratio trended to decrease. However, the variation of active organic C content, total N content and active organic C/N ratio in oilseed cake was on the contrary.

Effects of Combined Application of Water Retaining Agents and Organic Materials on Water Holding Characteristics of Yellow Brown Soils in Hilly Areas

[Objective] The aim was to reduce fertilizer and water losses caused by surface runoffs in rainy season and provide scientific references for soil moisture in arid season. [Method] The application proportion of complex water-holding organic materials was determined by multi-factor mixture experiment and the curve changes of soil moisture characters were tested to analyze water-holding capacity and water availability of soils. [Result] The initial moisture content of soil with different mixture proportions improved in varying degrees. For example, when water-retention agents reached 0.4% and 0.6% of soil weight, soil moisture contents were 69.0% and70.5%, respectively, which showed significant differences with the control（S0.0）. Soil dehydration terms in different treatments all extended, prolonging in the range of4.6-14 d. [Conclusion] The applications of water-retention agent and organic material would improve water-holding capacity of hills and low mountains, and initial moisture content and dehydration cycle tend to be volatile upon mixture proportion. Therefore,it is necessary to adjust soil fertility, crop species, and irrigation to meet crop demands on fertilizer and water.

Application of New Slope Greening Technology——Reinforced Organic-Material and Plant Seeds Spraying

The research introduced the flowchart of organic-material and plant seeds spraying and a case of ＆quot;Dasi＆quot; Highway, the highway from Daxing to Sinan in Guizhou Province, a part of a National Highway from Hangzhou to Ruili, cal ed Hangrui Highway, slope protection. The flowchart included slope cleaning, net preparation, anchor fixation, adding vegetation-growth plate, spraying organic materi-als, coverage of non-woven fabrics, and maintenance. The technique is proved much efficient in protecting and greening road sideslopes consisting of weathered rocks or hard rocks, which provides a solution for abrupt slope greening technology.

Decomposition characteristics of organic materials and their effects on labile and recalcitrant organic carbon fractions in a semi-arid soil under plastic mulch and drip irrigation

Labile organic carbon （LC） and recalcitrant organic carbon （RC） are two major fractions of soil organic carbon （SOC） and play a critical role in organic carbon turnover and sequestration. The aims of this study were to evaluate the variations of LC and RC in a semi-arid soil （Inner Mongolia, China） under plastic mulch and drip irrigation after the application of organic materials （OMs）, and to explore the effects of OMs from various sources on LC and RC by probing the decomposition characteristics of OMs using in-situ nylon mesh bags burying method. The field experiment included seven treatments, i.e., chicken manure （CM）, sheep manure （SM）, mushroom residue （MR）, maize straw （MS）, fodder grass （FG）, tree leaves （TL） and no OMs as a control （CK）. Soil LC and RC were separated by Huygens D＇s method （particle size-density）, and the average soil mass recovery rate and carbon recovery rate were above 95%, which indicated this method was suitable for carbon pools size analysis. The LC and RC contents significantly （P〈0.01） increased after the application of OMs. Moreover, LC and RC contents were 3.2%-8.6% and 5.0%-9.4% higher in 2016 than in 2015. The applications of CM and SM significantly increased （P〈0,01） LC content and LC/SOC ratio, whereas they were the lowest after the application of TL. However, SOC and RC contents were significantly higher （P〈0.01） after the applications of TL and MS. The correlation analysis indicated the decomposition rate of OMs was positively related with LC content and LC/SOC ratio. In addition, lignin, polyphenol, WOM （total water-soluble organic matter）, WHA （water-soluble humic acid）, HSL （humicdike substance） and HAL （humic acid-like） contents in initial OMs played important roles in SOC and RC. In-situ nylon mesh bags burying experiment indicated the decomposition rates of CM, SM and MS were significantly higher than those of MR, FG, and TL. Furthermore, MS could result in more lignin derivatives, WHA, and HAL polymers in shorter time during the decomposition process. In conclusion, the application of MS in the semi-arid soil under a long-term plastic mulch and drip irrigation condition could not only improve soil fertility, but also enhance soil carbon sequestration.

Aggregate stability and associated C and N in a silty loam soil as affected by organic material inputs

To make recycling utilization of organic materials produced in various agricultural systems, five kinds of organic materials were applied in a field test, including crop straw （CS）, biogas residue （BR）, mushroom residue （MR）, wine residue （WR）, pig manure （PM）, with a mineral fertilizer （CF） and a no-fertilizer （CK） treatment as a control. Our objectives were： i） to quantify the effects of organic materials on soil C and N accumulation; ii） to evaluate the effects of organic materials on soil aggregate stability, along with the total organic carbon （TOC）, and N in different aggregate fractions; and iii） to assess the relationships among the organic material components, soil C and N, and C, N in aggregate fractions. The trial was conducted in Wuqiao County, Hebei Province, China. The organic materials were incorporated at an equal rate of C, and combined with a mineral fertilizer in amounts of 150 kg N ha^-1, 26 kg P ha^-1 and 124 kg K ha-1 respectively during each crop season of a wheat-maize rotation system. The inputted C quantity of each organic material treatment was equivalent to the total amount of C contained in the crop straw harvested in CS treatement in the previous season. TOC, N, water-stable aggregates, and aggregate-associated TOC and N were investigated. The results showed that organic material incorporation increased soil aggregation and stabilization. On average, the soil macroaggregate proportion increased by 14%, the microaggregate proportion increased by 3%, and mean-weight diameter （MWD） increased by 20%. TOC content followed the order of PM〉WR〉MR〉BR〉CS〉CK〉CF; N content followed the order WR〉PM〉MR〉BR〉CS〉CF〉CK. No significant correlation was found between TOC, N, and the quality of organic material. Soil silt and clay particles contained the largest part of TOC, whereas the small macroaggregate fraction was the most sensitive to organic materials. Our results indicate that PM and WR exerted better effects on soil C and N accumulation, followed by MR and BR, suggesting that organic materials from ex situ farmland could promote soil quality more as compared to straw returned in situ.

An imine-linked covalent organic framework as the host material for sulfur loading in lithium–sulfur batteries

Lithium–sulfur(Li–S) batteries have high theoretical specific capacity, providing new opportunities for the next generation of secondary battery. Covalent organic framework(COF) as a new porous crystalline material has been used as the host material in Li–S battery to improve the cell's cycling stability. In this paper, an imine-linked TAPB-PDA-COF was applied as the host material for sulfur loading(60%) in Li–S battery. The TAPB-PDA-COF has a beehive-like morphology with high thermal stability(up to 500 ℃).In the electrochemical experiment, the performance of the composite cathode with acetylene black(AB) and super-P(S-P) as the conductive additives was studied individually. The initial discharge capacity under 0.2 A/g current density was 991 mAh/g and 1357 mAh/g for TAPB-PDA-COF/S@A-B and TAPB-PDACOF/S@S-P, respectively. The better result of S-P based cathode than A-B could be due to the better conductivity of the S-P, as proved by the EIS results. When further increased the current density to 2 A/g,the S-P based composite cathode can still deliver a comparable initial discharge capacity of 630 and 274 mAh/g capacity remained after 940 cycles. This results will inspire researchers develop more suitable conductive additives together with the host materials for high performance Li–S battery.

Selective extraction and separation of Fe,Mn oxides and organic materials in river surficial sediments

In order to investigate the adsorption mechanism of trace metals to surficial sediments （SSs）, a selective extraction procedure was improved in the present work. The selective extraction procedure has been proved to selectively remove and separate Fe, Mn oxides and organic materials （OMs） in the non-residual fraction from the SSs collected in Songhua River, China. After screening different kinds of conventional extractants of Fe and Mn oxides and OMs used for separation of heavy metals in the soils and sediments, NH2OH .HCl （0.1 mol/L） ＋ HNO3 （0.1 mol/L）, （NH4）2C2O4 （0.2 mol/L） ＋ H2C2O4 （pH 3.0）, and 30% of H2O2 were respectively applied to selectively extract Mn oxides, Fe/Mn oxides and OMs. After the extraction treatments, the target components were removed with extraction efficiencies between 86.09%--3.36% for the hydroxylamine hydrochloride treatment, 80.63%- 101.09% for the oxalate solution extraction, and 94.76%-102.83% for the hydrogen peroxide digestion, respectively. The results indicate that this selective extraction technology was effective for the extraction and separation ofFe, Mn oxides and OMs in the SSs, and important for further mechanism study of trace metal adsorption onto SSs.

Adsorption of Cu(Ⅱ) on humic acids derived from different organic materials

The adsorption of Cu（Ⅱ） from aqueous solution onto humic acid （HA） which was isolated from cattle manure （CHA）, peat （PHA）, and leaf litter （LHA） as a function of contact time, pH, ion strength, and initial concentration was studied using the batch method. X-ray absorption spectroscopy （XAS） was used to examine the coordination environment of the Cu（ll） adsorbed by HA at a molecular level. Moreover, the chemical compositions of the isolated HA were characterized by elemental analysis and solid-state 13C nuclear magnetic resonance spectroscopy （NMR）. The kinetic data showed that the adsorption equilibrium can be achieved within 8 h. The adsorption kinetics followed the pseudo-second-order equation. The adsorption isotherms could be well fitted by the Langmuir model, and the maximum adsorption capacities of Cu（ll） on CHA, PHA, and LHA were 229.4,210.4, and 197.7 mg g-1, respectively. The adsorption of Cu（Ⅱ） on HA increased with the increase in pH from 2 to 7, and maintained a high level at pH〉7. The adsorption of Cu（Ⅱ） was also strongly influenced by the low ionic strength of 0.01 to 0.2 mol L-1 NaNO3, but was weakly influenced by high ionic strength of 0.4 to 1 mol L-1 NaNO3. The Cu（Ⅱ） adsorption on HA may be mainly attributed to ion exchange and surface complexation. XAS results revealed that the binding site and oxidation state of Cu adsorbed on HA surface did not change at the initial Cu（Ⅱ） concentrations of 15 to 40 mg L 1. For all the Cu（Ⅱ） adsorption samples, each Cu atom was surrounded by 40/N atoms at a bond distance of 1.95 A in the first coordination shell. The presence of the higher Cu coordination shells proved that Cu（Ⅱ） was adsorbed via an inner-sphere covalent bond onto the HA surface. Among the three HA samples, the adsorption capacity and affinity of CHA for Cu（Ⅱ） was the greatest, followed by that of PHA and LHA. All the three HA samples exhibited similar types of elemental and functional groups, but different contents of elemental and functional groups. CHA contained larger proportions of methoxyl C, phenolic C and carbonyl C, and smaller proportions of alkyl C and carbohydrate C than PHA and LHA. The structural differences of the three HA samples are responsible for their distinct adsorption capacity and affinity toward Cu（Ⅱ）. These results are important to achieve better understanding of the behavior of Cu（Ⅱ） in soil and water bodies in the presence of organic materials.

Photodetectors based on two-dimensional materials and organic thin-film heterojunctions

High-performance photodetectors are expected to open up revolutionary opportunities in many application fields, such as environment monitoring, military, optical communication and biomedical science. Combining two-dimensional materials(which have tunable optical absorption and high carrier mobility) with organic materials(which are abundant with low cost, high flexibility and large-area scalability) to form thin-film heterojunctions, high-responsivity photodetectors could be predicted with fast response speed in a wide spectra region.In this review, we give a comprehensive summary of photodetectors based on two-dimensional materials and organic thin-film heterojunctions, which includes hybrid assisted enhanced devices, single-layer enhanced devices, vertical heterojunction devices and tunable vertical heterojunction devices. We also give a systematic classification and perspectives on the future development of these types of photodetectors.

Recent progress in organic redox flow batteries:Active materials,electrolytes and membranes

Redox flow batteries （RFBs） have great potentials in the future applications of both large scale energy storage and powering the electrical vehicle. Critical challenges including low volumetric energy density. high cost and maintenance greatly impede the wide application of conventional RFBs based on inorganic materials. Redox-active organic molecules have shown promising prospect in the application of RFBs, benefited from their low cost, vast abundance, and high tunability of both potential and solubility. In this review, we discuss the advantages of redo~ active organic materials over their inorganic compart and the recent progress of organic based aqueous and non-aqueous RFBs. Design considerations in active materi- als, choice of electrolytes and membrane selection in both aqueous and non-aqueous RFBs are discussed. Finally. we discuss remaining critical challenges and suggest future directions for improving organic based RFBs.

Effect of Organic Materials on Speciation of Copper inSoil Solution

Incubation of two soils, a red soil derived from granodiorte and a fluvo-aquic soil from alluvial deposit,with rice straw, Chinese milk vetch and pig manure under submerged condition were conducted to study thespecies of Cu in soil solutions as affected by the organic materials. The organic materials increased totalsoluble Cu by raising dissolved organic carbon (DOC) in soil solution when the solution pH values were belowthe range in which Cu deposited quickly. When the solution pH rose to this range, the increase of DOCdid not raise total soluble Cu. Total soluble Cu in all the treatments dropped with incubation time. Afteradding organic materials labile Cu dropped with incubation time and decreased sharply in the pH range ofCu precipitation. Addition of organic materials enhanced slowly labile Cu but depressed the ratio of labileCu to total soluble Cu. Slowly labile Cu decreased with incubation time. Stepwise multiple linear regressionanalysis showed that total soluble Cu was positively correlated with Eh and DOC (P=0.0025), labile Cuwas negatively correlated with pH (P=0.011 8), and slowly labile Cu was positively correlated with Eh andDOC (P=0.002 2). Both the labile and slowly labile Cu were correlated with total soluble Cu at extremelysignificant levels.

Characterization methods of organic electrode materials

The development of novel organic electrode materials is of great significance for improving the reversible capacity and cycle stability of rechargeable batteries.Before practical application,it is essential to characterize the electrode materials to study their structures,redox mechanisms and electrochemical performances.In this review,the common characterization methods that have been adopted so far are summarized from two aspects:experimental characterization and theoretical calculation.The experimental characterization is introduced in detail from structural characterization,electrochemical characterization and electrode reaction chara cterization.The experimental purposes and working principles of various experimental characterization methods are briefly illustrated.As the auxilia ry means,theoretical calculation provides the theoretical basis for characterizing the electrochemical reaction mechanism of organic electrode materials.Through these characterizations,we will have a deep understanding about the material structures,electrochemical redox mechanisms,electrochemical properties and the relationships of structure-property.It is hoped that this review would help researchers to select the suitable characterization methods to analyze the structures and performances of organic electrode materials quickly and effectively.

High-performance asymmetric small molecular donor materials based on indenothiophene for solution-processed organic solar cells

Two novel asymmetric organic small molecules of IT(2FBT-T3Cz)_2and IT(2FBT-TT3Cz)_2with an indenothiophene(IT)central donor core,fluorinated benzothiadiazole(2FBT)as acceptor and 3-carbazole(Cz)unit as terminal group were designed and synthesized as the donor materials in organic solar cells(OSCs).The thermal,optical absorption,electrochemical property,hole–electron mobility,film morphology were thoroughly studied.Using PC_(71)BM as an electron acceptor,without any additive and thermal annealing(TA)treatment,the IT(2FBT-T3Cz)_2-based cells showed a promising power conversion efficiency(PCE)of5.81%and the IT(2FBT-TT3Cz)_2-based cells exhibited a PCE of 4.39%.Our results demonstrate that the IT-based asymmetric small molecules can be developed as a promising class of donor materials for highperformance OSCs.

Electronic structure engineering in organic thermoelectric materials

Electronic structures, which play a key role in determining electrical and optical properties of π-conjugated organic materials, have attracted tremendous interest. Efficient thermoelectric (TE) conversion of organic materials has rigorous requirements on electronic structures. Recently, the rational design and precise modulation of electronic structures have exhibited great potential in exploring state-of-the-art organic TE materials. This review focuses on the regulation of electronic structures of organic materials toward efficient TE conversion. First, we present the basic knowledge regarding electronic structures and the requirements for efficient TE conversion of organic materials, followed by a brief introduction of commonly used methods for electronic structure characterization. Next, we highlight the key strategies of electronic structure engineering for high-performance organic TE materials. Finally, an overview of the electronic structure engineering of organic TE materials, along with current challenges and future research directions, are provided.

Two-dimensional organic cathode materials for alkali-metal-ion batteries

With the increasing demand for large-scale battery systems in electric vehicles（EVs） and smart renewable energy grids, organic materials including small molecules and polymers utilized as electrodes in rechargeable batteries have received increasing attraction. In recent years, two-dimensional（2D） organic materials possessing planar layered architecture exhibit optional chemical modification, high specific surface area as well as unique electrical/magnetic properties, which have been emerging as the promising functional materials for wide applications in optoelectronics, catalysis, sensing, etc. Integrating with high-density redox-active sites and hierarchical porous structure, significant achievements in 2D organic materials as cathode materials for alkali-metal-ion batteries have been witnessed. In this review, the recent progress in synthetic approaches, structure analyses, electrochemical characterizations of 2D organic materials as well as their application in alkali-metal-ion batteries containing lithium ion battery（LIB）, lithium sulfur battery（LSB）, lithium air battery（LAB） and sodium ion battery（SIB） are summarized systematically,and their current challenges including cycling stability and electron conductivity for cathode materials in battery fields are also discussed.