Co-liquefaction of Cotton Seed and Flos Populi in Sub-critical Water/Ethanol Solvent for Bio-oil with Medical Stone Based Additives

The co-liquefaction behaviors of cotton seed(CS)and flos populi(FP)were investigated in the sub-critical water/ethanol mixed solvent using the medical stone(MS)based additives.Oil products were characterized using FTIR,GC-MS,1HNMR,and 13CNMR techniques.The test results showed that the synergistic effect of co-liquefaction was obvious when the ratio of cotton seed and flospopuli was 1:1 without additives.The additives,such as 12-phosphotungstic acid(PW12),HZSM-5,PW12/HZSM-5 and modified medical stone(MS),PW12/MS,Ni/MS,Co/MS,Mo/MS and Co-Mo/MS,could increase the bio-oil yield;and the modified MS resulted in higher liquefied oil yield than that achieved by MS.Furthermore,additives such as Ni/MS,Mo/MS,and Co-Mo/MS also could increase the yield of aliphatic hydrocarbons in liquefied oil.The addition of Co-Mo/MS could lead to a highest liquefied oil yield of 28.8%,while the additive of PW12/HZSM-5 could result in a highest total conversion of 81.6%.Results also revealed that additives,such as PW12/MS,PW12,PW12/HZSM-5,Ni/MS,Co/MS,Mo/MS,and Co-Mo/MS,could increase the H2 production and decrease the CO2 production in gas products.

Biomimetic design of highly flexible metal oxide nanofibrous membranes with exceptional mechanical performance for superior phosphopeptide enrichment

Developing free-standing and mechanical robust membrane materials capable of superior enrichment of phosphopeptides for analyzing and identifying the specific phosphoproteome of cancer cells is significant in understanding the molecular mechanisms of cancer development and exploring new therapeutic approaches,but still a significant challenge in materials design.To this end,we firstly constructed highly flexible ZrTiO_(4) nanofibrous membranes(NFMs)with excellent mechanical stability through a cost-effective and scalable electrospinning and subsequent calcination technique.Then,to further increase the enrichment capacity of the phosphopeptide,the biomimetic TiO_(2)@ZrTiO_(4) NFMs with root hair or leaf like branch microstructure are developed by the hydrothermal post-synthetic modification of ZrTiO_(4) NFMs through growing unfurling TiO_(2) nanosheets onto the ZrTiO_(4) nanofibers.Importantly,remarkable flexibility and mechanical stability enable the resulting TiO_(2)@ZrTiO_(4) NFMs excellent practicability,while the biomimetic microstructure allows it outstanding enrichment ability of the phosphopeptide and identification ability of the specific phosphoproteins in the digest of cervical cancer cells.Specifically,6770 phosphopeptides can be enriched by TiO_(2)@ZrTiO_(4) NFMs(2205 corresponding phosphoproteins can be identified),and the value is much higher than that of ZrTiO_(4) NFMs(6399 phosphopeptides and 2132 identified phosphoproteins)and commercial high-performance TiO_(2) particles(4525 phosphopeptides and 1811 identified phosphoproteins).These results demonstrate the super ability of TiO_(2)@ZrTiO_(4) NFMs in phosphopeptide enrichment and great potential for exploring the pathogenesis of cancer.

Al-containing Ge-rich IWV:rapid synthesis via interzeolite transformation and application in Baeyer-Villiger oxidation

Ge-containing Lewis acidic zeolites are typically synthesized using a conventional hydrothermal strategy from amorphous silica sources,through a long time-and energy-consuming approach limiting their wide applications.This study reports a rapid synthesis strategy for a series of IWV aluminogermanosilicate zeolites(T-x-Al)with a wide range of Si/Ge molar ratios(5–15)by interzeolite transformation of dealuminated FAU(DA-FAU).Notably,Ge-rich IWV could be obtained with crystallization time as short as one day by the equimolecular Si/Ge ratio gel.The effect of synthetic parameters was investigated and the obtained T-x-Al samples were characterized by XRD,SEM,EDS,ICP,^(29)Si and^(27)Al MAS NMR,FTIR,and N_(2)physisorption analyses.Compared with a previously reported IWV germanosilicate(H-3),T-x-Al displayed a better catalytic activity in Baeyer-Villiger(BV)oxidation,attributed to the presence of the active framework Ge sites with the assistance of the extraframework Al species.The cyclic catalysis tests revealed that the presence of framework Al species contributed to the stability of the T-x-Al.Specifically,T-x-Al,with 14-membered ring(MR)supercages,outperformed the typical 12-MR Sn-beta catalyst in the BV oxidation of large ketone-like 2-admantanone,indicating a promising potential application in the macromolecular catalytic process.

Efficient C_(2) Hydrocarbons and CO_(2) Adsorption and Separation in a Multi-site Functionalized MOF

A multi-site functionalized microporous metal-organic framework(MOF),H[Zn2(BDP)0.5(ATZ)3]·0.5 H_(2)O·0.5DMF(1),was synthesized through mixed ligands strategy.The pore surface of complex 1 was modified by uncoordinated carboxylate O atoms,phenyl and pyridyl rings as well as-NH_(2) groups,which strengthen interactions with C2H6,C_(2)H_(4) and CO_(2) molecules and lead to efficiently selective C2H6,C_(2)H_(4) and CO_(2) uptake over CH_(4).The selective adsorption mechanism was discussed deeply based on Grand Canonical Monte Carlo(GCMC)simulations.It is expected that this study will provide a new perspective for the rational design and synthesis of MOFs with efficient gas adsorption and separation performance.

Holey graphene oxide-templated construction of nano nickel-based metal–organic framework for highly efficient asymmetric supercapacitor

Metal–organic frameworks(MOFs)with redox-active metal sites and controllable crystalline structures make it possible to access the merits of highly-efficient electrode materials in electrochemical energy storage systems.However,most MOFs suffer from low capacitance and poor cycling stability that largely thwart their application.Herein,we present the holey graphene oxide(HGO)template strategy to prepare nano two-dimensional Ni(BDC)with HGO as both template and capping agent(denoted as Ni(BDC)-HGOx,x=10,20,30,and 40 according to the added HGO amount).Structural analyses reveal that HGO can significantly inhibit the Ni(BDC)agglomeration,thus offering a high ion-accessible surface area.Ni(BDC)-HGO30 with well-exposed active sites exhibits a high capacitance of 1,115.6 F·g^(−1) at 1 A·g^(−1) in 6 M KOH aqueous,1.8 times that of bulk Ni(BDC).An asymmetric supercapacitor with Ni(BDC)-HGO30 as a positive electrode and activated carbon as the opposing electrode delivers an energy density of 52.5 W·h·kg^(−1) and a power density up to 18.0 kW·kg−1,with 92.5%capacitance retention after 10,000 cycles.Galvanostatic intermittent titration technique and in situ electrochemical–Raman measurements were exploited to elucidate the electrochemical behavior of Ni(BDC)-HGO30.These results pave the way for the development of rationally tuned MOF materials for enhancing supercapacitor performances.

In situ rapid versatile method for the preparation of zirconium metal-organic framework filters

The development of the rapid preparation of highly stable metal-organic framework(MOF)-based devices provides the possibility of meeting the increasing demands of MOF in industrial applications.However,MOFs experience poor processability and stable high-valence-metal(Ⅳ)-based MOFs favor forming either thermodynamically stable metal hydroxides or oxides during their growth and nucleation,which hinders their practical applications.Herein,we present a versatile deep eutectic solvent(DES)-assisted hot pressing method to in situ rapidly prepare six distinct zirconium-based MOF nanocrystals on fibers(denoted as Zr-MOFilters)within 20 min.A small amount of DES promotes MOF precursor contact and accelerates Zr-MOF growth.Temperature and pressure facilitate the formation of Zr-MOFs onto desired substrates.In situ1H nuclear magnetic resonance spectra and time-dependent Fourier-transform infrared spectra were conducted to elucidate the growth of Zr-MOF nanocrystals.As a proof-of-concept,the abilities of Zr-MOFilters for Cr_(2)O_(7)^(2−) and micro(nano)plastics removal have been demonstrated.This strategy paves the way for the rapid fabrication of highly stable MOF-based devices and brings MOFs a step closer to practical application.

Dramatic Impact of Auxiliary Ligands on the Dynamic Magnetic Relaxation in Tetranuclear Dy^(III)_(2)Zn^(II)_(2) Single Molecule Magnets

Better understanding the determining factors of dynamic magnetic relaxation in polynuclear lanthanide based single-molecule magnets(SMMs)remains a challenge due to the complexity of such architectures involving interactions between the magnetic centers.To address this issue,two structurally related heterometal Dy^(III)_(2)Zn^(II)_(2) SMMs,[Zn_(2)Dy_(2)(L)_(4)(Ac)_(2)(DMF)(CH_(3)OH)]·CH_(3)OH·2H_(2)O(1)and[Zn_(2)Dy_(2)(L)_(4)(Ac)_(2)(DMF)_(2)]·4CH_(3)CN(2)(H_(2)L=(E)-2-((2-hydroxy-3-methoxybenzylidene)amino)-4-methyphenol,DMF=N,N-dimethylformamide),are introduced and investigated.Through modifying the auxiliary ligands on one Dy^(III) site while retaining that on the other Dy^(III),the intramolecular magnetic interactions and relaxation dynamics in these two heterometallic-Dy^(III)_(2)Zn^(II)_(2) SMMs can be tuned,demonstrating a dramatic change in the magnet relaxation behavior with energy barrier changing from a negligible value for 1 to 305 K for 2.Ab initio calculations reveal that changing the coordination geometries on the Dy^(III) sites can significantly affect the magnetic interactions as well as single-ion anisotropy.

A Unique Solvent-Induced Structural Transformation of Two Acentric [Zn2（H2O）（Hdtim）2] Isomers

Solvent-induced structural transformation was observed in two layered supramolecular isomers of [Zn2（H2O）（Hdtim）2] （H3dtim--4,5-ditetrazoyl-imidazole）. Structural analyses revealed that the two isomers have the similar geometry of Zn, coordination mode of Hdtim2-, and topology. Their structural differences only arise from different arrangement of the layers which seemingly corresponds to cooperative clockwise and counter-clockwise 90° rotation of the adjacent layers. This is a quite unique solvent-dependent supramolecular isomerism in coordination polymers.

Phosphorus-doping-tuned PtNi concave nanocubes with high-index facets for enhanced methanol oxidation reaction

Surface engineering has been found to be an efficient strategy to boost the catalytic performance of noble-metal-based nanocatalysts.In this work,a small amount of P was doped to the surface of PtNi concave cube(P-PtNi CNC).Interestingly,the P-PtNi CNC nanocatalyst shows an enhanced methanol oxidation reaction(MOR)performance with achieving 8.19 times of specific activity than that of comercial Pt/C.The electrochemical in situ Fourier transform infrared spectroscopy(FTIR)results reveal that the surface P doping promotes the adsorption energy of OH,enhancing the resistance against CO poisoning.Therefore,the intermediate adsorbed CO(COads)reacted with adsorbed OH(OHads)through the Langmuir–Hinshelwood(LH)mechanism to generate CO_(2)and release surface active sites for further adsorption.This work provides a promising strategy via the incorporation of non-metallic elements into the PtNi alloys bounded with high-index facets(HIFs)as efficient fuel cell catalysts.

Tunable Nonlinear Optical Property and Photocatalytic Activity on Luminescent Chiral Lanthanide Chains

Five chiral(P2_(1))isostructural lanthanide coordination complexes Ln(pic)_(3)[pic=picolinic acid,Ln=La(1),Gd(2),Nd(3),Sm(4)and Eu(5)]have been hydrothermally generated,featuring one dimensional right-handed 2_(1)helical chains constructed from LnN_(3)O_(6)of square antiprism geometry and N,O-chelated pic−groups,in which 3,4 and 5 have been reported,but we explore undiscovered properties of their own systematically.In special,1 undergoes an abnormal transformation of symmetry as the temperature cooling to 100 K.TG-DSC studies demonstrated that all isologues have good thermal stability with the decomposition temperature up to 400℃.Then,UV-Vis-NIR transmission spectroscopy measurements indicated that they possess a short-wavelength absorption edge onset at 377 nm,corresponding to the optical band gap of 3.29 eV.Meanwhile,powder second harmonic generation(SHG)measurements revealed that the SHG intensity of 1,2,4 and 5 may be about 1.2,2.0,0.9 and 0.75 times that of KH_(2)PO_(4),respectively.Interestingly,1 and 3 exhibit efficient photocatalytic degradation for MB(Methylene Blue)upon UV-light irradiation.Moreover,both 1 and 2 show strong blue luminescence.

A Photo-Responsive Charge-Assisted Hydrogen-Bonded Organic Network with Ultra-Stable Viologen Radicals

Hydrogen-bonded organic networks(HONs)have attracted intense research interest due to their mild synthesis conditions,good solvent processability and strong reproducibility.Most HONs are constructed by electrically neutral organic ligands through intermo-lecular interactions such as weak hydrogen bonding,n-n stacking.But there are a few charge-assisted hydrogen-bonding networks(CAHONs)constructed by oppositely charged organic components.Under hydrothermal conditions,we successfully synthesized a 3D CAHON(H2CV)(H2BTEC)(1)constructed by H2CV(CV=N,N′-4,4′-bipyridine dipropionate)and H4BTEC(H_(4)BTEC=1,2,4,5-benzene-tetracarboxylic acid)through multiple charge-assisted hydrogen bonding.Upon soft X-ray,ultraviolet light or sunlight irradiation under ambient conditions,1 quickly changes from colorless to blue(IP),and kinetic calculations show that its photochromism meets first-order dynamics.Interestingly,the colored crystals IP with long-lived colored radicals will not fade after being placed for more than two months at room temperature in air,owing to the fact that the photogenerated viologen radicals can be stabilized by the abundant hydrogen bonds,the coplanar pyridinium rings and the slow electron-hole recombination.Moreover,1 is a typical direct band gap semiconductor,evidenced by the calculated band gap of 3.24 eV,in agreement with the experimental value of 3.40 eV.In view of its strong colored stability,1 is designed for distinctive inkless printing.