Porous framework materials for energy&environment relevant applications:A systematic review

Carbon peaking and carbon neutralization trigger a technical revolution in energy&environment related fields.Development of new technologies for green energy production and storage,industrial energy saving and efficiency reinforcement,carbon capture,and pollutant gas treatment is in highly imperious demand.The emerging porous framework materials such as metal–organic frameworks(MOFs),covalent organic frameworks(COFs)and hydrogen-bonded organic frameworks(HOFs),owing to the permanent porosity,tremendous specific surface area,designable structure and customizable functionality,have shown great potential in major energy-consuming industrial processes,including sustainable energy gas catalytic conversion,energy-efficient industrial gas separation and storage.Herein,this manuscript presents a systematic review of porous framework materials for global and comprehensive energy&environment related applications,from a macroscopic and application perspective.

Microscopic mechanism of plasmon-mediated photocatalytic H_(2) splitting on Ag-Au alloy chain

Alloy nanostructures supporting localized surface plasmon resonances has been widely used as efficient photocatalysts,but the microscopic mechanism of alloy compositions enhancing the catalytic efficiency is still unclear.By using time-dependent density functional theory(TDDFT),we analyze the real-time reaction processes of plasmon-mediated H_(2) splitting on linear Ag-Au alloy chains when exposed to femtosecond laser pulses.It is found that H_(2) splitting rate depends on the position and proportion of Au atoms in alloy chains,which indicates that specially designed Ag-Au alloy is more likely to induce the reaction than pure Ag chain.Especially,more electrons directly transfer from the alloy chain to the anti-bonding state of H_(2),thereby accelerating the H_(2) splitting reaction.These results establish a theoretical foundation for comprehending the microscopic mechanism of plasmon-induced chemical reaction on the alloy nanostructures.

Applications of metal–organic frameworks for green energy and environment: New advances in adsorptive gas separation, storage and removal

The separation of gas molecules with similar physicochemical properties is of high importance but practically entails a substantial energy penalty in chemical industry. Meanwhile, clean energy gases such as H_2 and CH_4 are considered as promising candidates for the replacement of traditional fossil fuels. However, the technologies for the storage of these gases are still immature. In addition, the release of anthropogenic toxic gases into the atmosphere is a worldwide threat of growing concern. Both in academia and industry, considerable research efforts have been devoted to developing advanced porous materials for the effective and energy-efficient separation, storage, or capture of the related gases. In contrast to conventional inorganic porous materials such as zeolites and activated carbons, metal–organic frameworks(MOFs) are considered as a type of promising materials for gas separation and storage. In this contribution, we review the recent research advance of MOFs in some relevant applications, including CO_2 capture, O_2 purification, separation of light hydrocarbons, separation of noble gases, storage of gases(CH_4,H_2, and C_2 H_2) for energy, and removal of some gaseous air pollutants(NH_3, NO_2, and SO_2). Finally, an outlook regarding the challenges of the future research of MOFs in these directions is given.

Nitrogen rejection from low quality natural gas by pressure swing adsorption experiments and simulation using dynamic adsorption isotherms

In order to remove N_(2) from low quality natural gas,a mathematical model has been established by Aspen adsorption,using the CH_(4)-selective sorbent silicalite-1 pellets.The dynamic adsorption isotherm was first simulated by breakthrough simulation of a CH_(4)/N_(2) mixture at different adsorption pressures and feed flow rates based on breakthrough experiments.The resulting simulated CH_(4) dynamic adsorption amounts were very close to the experimental data at three different adsorption pressures(100,200,and 300 kPa).Moreover,a single-bed,three-step pressure swing adsorption(PSA)experiment was performed,and the results were in good agreement with the simulated data,further corroborating the accuracy of the gas dynamic adsorption isotherm obtained by the simulation method.Finally,based on the simulated dynamic adsorption isotherm of CH_(4) and N_(2),a four-bed,eight-step PSA process has been designed,which enriched 75%(vol)CH_(4) and 80%(vol)CH_(4) to 95%(vol)and 99%(vol),and provided 99%(vol)recovery.

Genome-wide analyses on transcription factors and their potential microRNA regulators involved in maize male fertility

Anther development is a programmed biological process crucial to plant male reproduction. Genomewide analyses on the functions of transcriptional factor(TF) genes and their microRNA(miRNA) regulators contributing to anther development have not been comprehensively performed in maize. Here, using published RNA-Seq and small RNA-Seq(sRNA-Seq) data from maize anthers at ten developmental stages in three genic male-sterility(GMS) mutants(ocl4, mac1, and ms23) and wild type W23, as well as newly sequenced maize anther transcriptomes of ms7-6007 and lob30 GMS mutants and their WT lines, we analyzed and found 1079 stage-differentially expressed(stage-DE) TF genes that can be grouped into six(premeiotic, meiotic, postmeiotic, premeiotic-meiotic, premeiotic-postmeiotic, and meiotic-postmeiotic clusters) expression clusters. Functional enrichment combined with cytological and physiological analyses revealed specific functions of genes in each expression cluster. In addition, 118 stage-DE miRNAs and99 miRNA-TF gene pairs were identified in maize anthers. Further analyses revealed the regulatory roles of zma-miR319 and zma-miR159 as well as ZmMs7 and ZmLOB30 on ZmGAMYB expression. Moreover,ZmGAMYB and its paralog ZmGAMYB-2 were demonstrated as novel maize GMS genes by CRISPR/Cas9 knockout analysis. These results extend our understanding on the functions of miRNA-TF gene regulatory pairs and GMS TF genes contributing to male fertility in plants.

Amorphous iron-nickel phosphide nanocone arrays as efficient bifunctional electrodes for overall water splitting

The synthesis of low-cost and highly active electrodes for both oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)is very important for water splitting.In this work,the novel amorphous iron-nickel phosphide(FeP-Ni)nanocone arrays as efficient bifunctional electrodes for overall water splitting have been in-situ assembled on conductive three-dimensional(3D)Ni foam via a facile and mild liquid deposition process.It is found that the FeP-Ni electrode demonstrates highly efficient electrocatalytic performance toward overall water splitting.In 1 M KOH electrolyte,the optimal FeP-Ni electrode drives a current density of 10 mA cm^(-2) at overpotential of 218 mV for the OER and120 mV for the HER,and can attain such current density for 25 h without performance regression.Moreover,a two-electrode electrolyzer comprising the FeP-Ni electrodes can afford 10 mA cm^(-2) electrolysis current at a low cell voltage of 1.62 V and maintain long-term stability,as well as superior to that of the coupled RuO_(2)/NFk Pt/C/NF cell.Detailed characterizations confirm that the excellent electrocatalytic performances for water splitting are attributed to the unique 3D morphology of nanocone arrays,which could expose more surface active sites,facilitate electrolyte diffusion,and benefit charge transfer and also favorable bubble detachment behavior.Our work presents a facile and cost-effective pathway to design and develop active self-supported electrodes with novel 3D morphology for water electrolysis.

Efficient electrocatalytic conversion of N_(2) to NH_(3) using oxygen-rich vacancy lithium niobate cubes

Instead of the energy-intensive Haber-Bosch process,the researchers proposed a way to produce ammonia using water and nitrogen as feedstock,powered by electricity,without polluting the environment.Nevertheless,how to design efficient electrocatalyst for electrocatalytic nitrogen reduction reaction(NRR)is still urgent and challenging.Herein,a strategy is proposed to adjust the morphology and surface electronic structure of electrocatalyst by optimizing material synthesis method.LiNbO3(lithium niobate,LN)cubes with oxygen-rich vacancy and regular morphology were synthesized by hydrothermal synthesis and followed molten salt calcination process,which were used for electrocatalytic NRR under mild conditions.Compared with LN nanoparticles synthesized by solid phase reaction,LN cubes exhibit better NRR performance,with the highest ammonia yield rate(13.74μg.h^(-1).mg^(-1))at the best potential of-0.45V(vs.reversible hydrogen electrode,RHE)and the best Faradaic efficiency(85.43%)at-0.4 V.Moreover,LN cubes electrocatalyst also demonstrates high stability in 7 cycles and 18 h current-time tests.Further investigation of the reaction mechanism confirmed that the structure of oxygen vacancy could adjust the electronic structure of the electrocatalyst,which was conducive to the adsorption and activation of N_(2) molecule and also increased the ECSA of electrocatalyst,thus providing more active sites for the NRR process.

Ultrafine tuning of the pore size in zeolite A for efficient propyne removal from propylene

The removal of trace propyne(C_(3)H_(4))from propyne/propylene(C_(3)H_(4)/C_(3)H_(6))mixtures is a technical and challenging task during the production of polymer-grade propylene in view of their very similar size and physical properties.While some progress has been made,it is still very challenging to use some highly stable and commercially available porous materials via an energy-efficient adsorptive separation process.Herein,we report the ultrafine tuning of the pore apertures in type-A zeolites for the highly efficient removal of trace amounts of C_(3)H_(4)from C_(3)H_(4)/C_(3)H_(6)mixtures.The resulting ion-exchanged zeolite 5 A exhibits a large C_(3)H_(4)adsorption capacity(2.3 mmol g^(-1)under 10^(-4)MPa)and high C_(3)H_(4)/C_(3)H_(6)selectivity at room temperature,which were mainly attributed to the ultrafine-tuned pore size that selectively blocks C_(3)H_(6)molecules,while maintaining the stro ng adsorption of C_(3)H_(4)at low pressure region.High purity of C_(3)H_(6)(>99.9999%)can be directly obtained on this material under ambient conditions,as demonstrated by the experimental breakthrough curves obtained for both 1/99 and 0.1/99.9(V V)C_(3)H_(4)/C_(3)H_(6) mixtures.

Selective adsorption of propene over propane on Li-decorated poly(triazine imide)

Solid adsorbents that simultaneously have high selectivity and uptake capacity are highly promising as alternatives to conventional cryogenic distillation of propene/propane(C_(3)H_(6)/C_(3)H_(8)) separation.Coordinatively unsaturated metal sites(CUS) plays a vital role in selective adsorption of olefins over paraffins.Ultrathin poly(triazine imide)(PTI) nanosheets can reach rapid gas adsorption equilibrium,due to its large surface-tovolume ratio.In this work,combining the advantages of the CUS and the PTI nanosheets,Li CUSs were introduced into the PTI nanosheets for C_(3)H_(6)/C_(3)H_(8) separation.Density functional theory(DFT) calculations demonstrated the thermodynamic feasibility of incorporating Li CUSs into the PTI nanosheets.These highly exposed Li CUSs were predicted to have a higher adsorption affinity toward C_(3)H_(6) than C_(3)H_(8).Using the DFTderived force field parameters,we further performed grand canonical Monte Carlo(GCMC) simulations to investigate C_(3)H_(6)/C_(3)H_(8) adsorption on the Li–PTI complexes slit pore model with different pore widths(H).We found that the Li–PTI complexes display considerable C_(3)H_(6)/C_(3)H_(8) selectivity(4.2–7.9) under relevant conditions.Moreover,the Li–PTI complexes slit pore have large C_(3)H_(6) working capacities(1.5–4.0 mmol g-1),superior to those calculated for the most of adsorbent materials that have been reported.The Li–PTI complexes with slit pore architecture show potential as C_(3)H_(6)/C_(3)H_(8) separation materials.

Influence of Different Fertilization Levels on Maize Yield and Fertilizer Effect Based on the "3414" Experimental Design Scheme

In order to provide scientific basis for rational fertilization of maize under different soil quality and fertility,the effect of combined application of NPK on yield and fertilizer effect of different maize varieties was studied by using "3414" experimental design scheme in this paper. The results showed that there were significant differences in ear length,ear diameter,barren ear tip length,kernel number per spike,kernel weight and yield among different fertilization treatments. Fertilization can improve the agronomic characters of maize and increase the yield.The yield increase of maize in two experimental plots( MHQ and HZY) was 11. 0%-64. 3% and 0. 2%-61. 9%,respectively. There was obvious interaction effect among nitrogen,phosphorus and potassium fertilizers,the yield of maize was the highest at the level of medium nitrogen,medium phosphorus and medium potassium fertilization,and the fertilizer effect was in the order of N > P_2O_5> K_2O. The results of curve fitting showed that the recommended application rates of N,P2_O_5 and K_2O in MHQ plot were 373. 7,74. 8 and 79. 9 kg/ha,respectively; the recommended application rates of N,P_2O_5 and K_2O in HZY plot were 419. 7,75 and 75 kg/ha,respectively.

Enhanced properties of solid solution (CeZr)O_2 modified with metal oxides for catalytic oxidation of low-concentration methane

The solid solution （CeZr）02 catalyst was synthesized, and it was modified with metal oxides by incipient impreg- nation. Morphology and structure were characterized by X-ray diffraction, transmission electron microscope, ni- trogen ad/desorption and H2-temperature program reduction techniques. The catalytic properties of methane oxidation were also investigated. The results showed that solid solution possessed a mesoporous structure and exhibited excellent catalytic performance. The activity of solid solution was improved effectively by nickel dop- ing, and the optimal loading is 15 wt%. The stability of （CeZr）02 and modified （CeZr）02 indicated that the struc- ture of pristine solid solution played a key role in promoting molecules diffusion and spatial confining oxide particle sintering.

Effects of Fruticosa potentilla L. on Expression of Glucose and Lipid Metabolism Key Enzymes and Hormones in T2DM Rats

[Objectives]To study the effects of Fruticosa potentilla L.on the expression of key enzymes and hormones related to glucose and lipid metabolism in T2DM rats.[Methods]The ethyl acetate fraction of 95%methanol extract of F.potentilla(MEE)was administered orally to the T2DM rats,and the level of glucose and expression of insulin,resistin,leptin,glucokinase(GK)and glucose-6-phosphatase(G-6-Pase)in the rats were measured and detected.[Results]In the T2DM rats administered with MEE,the postprandial blood glucose level decreased,the expression levels of resistin,leptin and G-6-Pase were down-regulated,and the expression levels of insulin and GK were up-regulated(P<0.05,P<0.01).[Conclusions]F.potentilla can reduce effectively postprandial blood glucose level,regulate the expression of a variety of enzymes and hormones related to glucose and lipid metabolism and recover partially the insulin level in T2DM rats to achieve resistance to T2DM.

Advances in Research of Chemical Components and Pharmacological Effects of Platycladus orientalis Leaves

Platycladi Cacumen(Platycladus orientalis leaf)is a traditional Chinese medicine with a variety of medicinal values,and its efficacy has been recorded by many ancient books.Its chemical components mainly include flavonoids,volatile oil,tannins and so on.Pharmacological studies have confirmed that P.orientalis leaves have various pharmacological effects such as antibacterial,anti-oxidant,anti-tumor,hair growth promoting and hemostatic effects.Through review of the research on the chemical components and pharmacological effects of P.orientalis leaves,this study is intended to provide reference for the research,development and utilization of P.orientalis.

Lattice strain induced by trace Pt single atoms in nickel for accelerating industrial hydrogen evolution

Strategically designing the electrocatalytic system and cleverly inducing strain is an effective approach to balance the cost and activity of Pt-based electrocatalysts for industrial-scale hydrogen production.Herein,we present a unipolar pulsed electrodeposition(UPED) strategy to induce strain in the Ni lattice by introducing trace amounts of Pt single atoms(SAs)(0.22 wt%).The overpotential decreased by 183 mV at 10 mA cm^(-2) in 1.0 M KOH after introducing trace amounts of Pt_(SAs).The industrial electrolyzer,assembled with Pt_(SAs)Ni cathode and a commercial NiFeO_(x) anode,requires a cell voltage of 1.90 V to attain 1 A cm^(-2) of current density and remains stable for 280 h,demonstrating significant potential for practical applications.Spherical aberration corrected scanning transmission electron microscopy(AC-STEM),X-ray absorption(XAS),and geometric phase analysis(GPA) indicate that the introduction of trace amounts of Pt SAs induces tensile strain in the Ni lattice,thereby altering the local electronic structure and coordination environment around cubic Ni for enhancing the water decomposition kinetics and fundamentally changing the reaction pathway.The doping-strain strategy showcases conformational relationships that could offer new ideas to construct efficient hydrogen evolution reaction(HER) electrocatalysts for industrial hydrogen production in the future.

Reversed ethane/ethylene adsorption in a metal–organic framework via introduction of oxygen

Separation of ethane from ethylene is a very important but challenging process in the petrochemical industry.Finding an alternative method would reduce the energy needed to make 170 million tons of ethylene manufactured worldwide each year.Adsorptive separation using C2H6-selective porous materials to directly produce high-purity C2H4 is more energy-efficient.We herein report the"reversed C2H6/C2H4 adsorption"in a metal–organic framework Cr-BTC via the introduction of oxygen on its open metal sites.The oxidized Cr-BTC(O2)can bind C2H6 over C2H4 through the active Cr-superoxo sites,which was elucidated by the gas sorption isotherms and density functional theory calculations.This material thus exhibits a good performance for the separation of 50/50 C2H6/C2H4 mixtures to produce 99.99%pure C2H4 in a single separation operation.

CH4/N2 separation on methane molecules grade diameter channel molecular sieves with a CHA-type structure

Samples of methane molecules grade diameter channel CHA-type molecular sieves(Chabazite-K, SAPO-34 and SSZ-13) were investigated using the adsorption separation of CH4/N2 mixtures. The isotherms recorded for CH4 and N2 follow a typical type-Ι behavior, which were fitted well with the Sips model(R2>0.999) and the selectivity was calculated using IAST theory. The results reveal that Chabazite-K has the highest selectivity(SCH4/N= 5.5).2 SSZ-13 has the largest capacity, which can adsorb up to a maximum of 30.957 cm3·g-1(STP) of CH4, due to it having the largest pore volume and surface area, but the lowest selectivity(SCH4/N2= 2.5). From the breakthrough test, we can conclude that SSZ-13 may be a suitable candidate for the recovery of CH4 from low concentration methane(CH4<20%) based on its larger pore volume and higher CH4 capacity. Chabazite-K is more suited to the separation of high concentration methane(CH4>50%) due to its higher selectivity.

Separation of CO_2/CH_4 and CH_4/N_2 mixtures using MOF-5 and Cu_3(BTC)_2

In this paper we used MOF-5 and Cu3（BTC）2 to separate CO2/CH4 and CI-I4/N2 mixtures under dynamic conditions. Both materials were synthesized and pelletized, thus allowing for a meaningful characterization in view of process scale-up. The materials were characterized by X-ray diffraction （XRD） and scanning electron microscopy （SEM）. By performing breakthrough experiments, we found that Cu3（BTC）2 separated CO2/CH4 slightly better than MOF-5. Because the crystal structure of Cu3 （BTC）2 includes unsaturated accessible metal sites formed via dehydration, it predominantly interacted with CO2 molecules and more easily captured them. Conversely, MOF-5 with a suitable pore size separated CH4/N2 more efficiently in our breakthrough test.

Shaping of metal-organic frameworks through a calcium alginate method towards ethylene/ethane separation

The separation of ethylene and ethane is a crucial,challenging and cost-intensive process in chemical engineering.Metal-organic frameworks(MOFs)are a class of novel porous adsorbents used for the separation of ethylene/ethane mixtures.However,MOFs are normally crystalline powders that cause multiple problems,such as dust,abrasion and heat/mass loss,as well as significant pressure drops on the adsorption bed resulting in a sudden stop in production.To solve these issues,we have prepared four different sphere-shaped adsorbents,including Mg-gallate,Co-gallate,MUV-10(Mn)and MIL-53(Al)using a calcium alginate method to achieve excellent ethylene/ethane separation performance.The performance of the sphere-shaped adsorbents has been validated using mechanical strength measurements,powder X-ray diffraction,scanning electron microscopy,thermogravimetric analysis,gas adsorption isotherms and dynamic breakthrough experiments.The excellent mechanical strength of these sphere-shaped adsorbents meets the criteria for industrial application in gas separation.Thus,the energy consumption and operating cost will be further reduced in the ethylene production process.We believe that this shaping method will open a prosperous route to the development of MOFs toward higher technology levels and their commercial application.

CO_2/CH_4 and CH_4/N_2 separation on isomeric metal organic frameworks

Two isomeric metal-organic frameworks(MOFs) with 2-dimensional(2D) and 3-dimensional(3D) topologies both comprised of Cu(Ⅱ) and OTf(OTf = trifluoromethanesulfonate) ions were synthesized and characterized.The CO_2,CH_4 and N_2 adsorption properties of the two isomeric MOFs were investigated from 263 K to 298 K at0.1 MPa.The results showed that the 2D MOF exhibited a higher selectivity for CO_2 from CO_2/CH_4 and CH_4from CH_4/N_2 compared to the 3D MOF,even though it possessed a lower surface area and pore volume.The higher adsorption heats of gases on the 2D MOF inferred the strong adsorption potential energy in the layered MOFs.Dynamic separation experiments using CO_2/CH_4 and CH_4/N_2 mixtures on the two MOFs proved that the2 D MOF had a longer elution time than the 3D MOF as well as better separation abilities.

Enhancement effect of Mn doping on Co_(3)O_(4)derived from Co-MOF for toluene catalytic oxidation

The design of Co-Mn composite oxides catalysts derived from MOF is significant for catalytic combustion of toluene.Here,a series of M-CoaMnfbOx,with enhanced catalytic properties compared with that of MCo_(3)O_(4),were successfully prepared through pyrolysis of Mn-doped Co-MOF.The as-synthesized MCo1Mn1Ox(Co:Mn=1:1)exhibits an optimal catalytic activity with 90%toluene conversion reached at227℃,which benefits from the increase of Co^(3+),Oadsand the synergistic effect between Mn and Co.According to the analysis of the in situ diffuse reflectance infrared Fourier transform spectroscopy,toluene could be degraded easier on M-Co1Mn1Oxwith lower activation energy than M-Co_(3)O_(4).The main intermediate products are benzaldehyde,benzoic acid,anhydride,and maleate species.Those findings reveal the value of Mn doping for improved activity of toluene oxidation on MOF derived Co_(3)O_(4),which provide a feasible method for the construction of toluene-oxidation catalysts.