新型二维层状铜磷酸盐氟化物的合成与表征
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摘要
采用改良的氟水热法,以磷酸为溶剂合成了一种新型的二维层状铜磷酸盐氟化物Na_2Cu_2F_2[P_2O_7],并通过粉末X射线衍射、单晶X射线衍射、能谱分析、红外光谱分析、热分析和磁性分析对其晶体结构、化学成分、官能团、热稳定性和磁学性能进行了表征.结果表明:在该化合物中,[Cu_2O_6F_2]二聚体与焦磷酸根[P_2O_7]~(4-)交替连接形成一个平行于(100)面的二维CuPOF层,层中邻近的磁性Cu~(2+)之间具有很强的反铁磁相互作用;此外,由于二聚体型结构的Cu~(2+)之间无法形成自旋阻挫以阻止其自旋的有序排列,在低温时该化合物呈现出长程反铁磁有序.
A new two-dimensional copper phosphate fluoride Na_2 Cu_2 F_2[_P2 O_7] was synthesized using a modified fluorohydrothermal method,with phosphoric acid as the solvent.The crystal structure,chemical composition,functional group,thermal stability and magnetic properties of the compounds were characterized by powder X-ray diffraction,single crystal X-ray diffraction,energy dispersion spectrum analysis,infrared spectroscopy analysis,thermal analysis and magnetic analysis.The results showed that,in the structure of the compound,the[Cu_2 O_6 F_2]dimers and[P_2 O_7]pyrophosphates were alternately connected forming a twodimensional CuPOF layer parallel to(100),and there was a strong antiferromagnetic interaction between the adjacent magnetic Cu~(2+).Magnetic analyses showed that due to no spin frustration could be formed between the two Cu~(2+)of the dimers to prevent their spin ordering,the magnetic susceptibility of the compound had a long range anti-ferromagnetic order at low temperature.
A new two-dimensional copper phosphate fluoride Na_2 Cu_2 F_2[_P2 O_7] was synthesized using a modified fluorohydrothermal method,with phosphoric acid as the solvent.The crystal structure,chemical composition,functional group,thermal stability and magnetic properties of the compounds were characterized by powder X-ray diffraction,single crystal X-ray diffraction,energy dispersion spectrum analysis,infrared spectroscopy analysis,thermal analysis and magnetic analysis.The results showed that,in the structure of the compound,the[Cu_2 O_6 F_2]dimers and[P_2 O_7]pyrophosphates were alternately connected forming a twodimensional CuPOF layer parallel to(100),and there was a strong antiferromagnetic interaction between the adjacent magnetic Cu~(2+).Magnetic analyses showed that due to no spin frustration could be formed between the two Cu~(2+)of the dimers to prevent their spin ordering,the magnetic susceptibility of the compound had a long range anti-ferromagnetic order at low temperature.
引文
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[2] CHUNG S Y,BLOKING J T,CHIANG Y M.Electronically conductive phospho-olivines as lithium storage electrodes[J].Nature Materials,2002,1(2):123-128.
[3] HERLE P S,ELLIS B,COOMBS N,et al.Nano-network electronic conduction in iron and nickel olivine phosphates[J].Nature Materials,2004,3(3):147-152.
[4] MASPOCH D,RUIZ-MOLINA D,VECIANA J.Old materials with new tricks:multifunctional open-framework materials[J].Chemical Society Reviews,2007,36(5):770-818.
[5] GUILLOU N,GAO Q,FORSTER P M,et al.Nickel(Ⅱ)phosphate VSB-5:a magnetic nanoporous hydrogenation catalyst with 24-ring tunnels[J].Angew Chem Int Ed,2001,40(15):2831-2834.
[6] ROTH M,TSEITLIN M,ANGERT N.Compositiondependent electro-optic and nonlinear optical properties of KTP-family crystals[J].Optical Materials,2006,28(1/2):71-76.
[7] HUANG H,YIN S C,NAZAR L F.Approaching theoretical capacity of LiFePO4 at room temperature at high rates[J].Electrochemical and Solid-State Letters,2001,4(10):A170-A172.
[8] YANG M,CUI M Y,ZHANG S Y,et al.Two S=1/2one-dimensional barium copper phosphates showing antiferromagnetic and ferromagnetic intrachain interactions[J].Dalton Transactions,2016,45(8):3319-3326.
[9] ANDERSON J B,KOSTINER E,RUSZALA F A.The crystal structure of Ca3Cu3(PO4)4[J].Journal of Solid State Chemistry,1981,39(1):29-34.
[10] DRILLON M,BELAICHE M,LEGOLL P,et al.1D ferrimagnetism in copper(Ⅱ)trimetric chains:specific heat and magnetic behavior of A3Cu3(PO4)4 with A=Ca,Sr[J].Journal of Magnetism and Magnetic Materials,1993,128(1/2):83-92.
[11] SIMIZU S,FRIEDBERG S A,HAYRI E A,et al.Low dimensional magnetism in the high-Tc superconductor LBa2Cu3O7-y(L=Gd,Ho,Er)heat-capacity study[J].Physical Review B,1987,36(13):7129-7132.
[12] PAUKOV I V,POPOVA M N,KLAMUT J.Lowdimensional magnetism in R2Cu2O5 compounds[J].Physics Letters A,1994,189(1/2):103-108.
[13] ISHII R,GAUTREAUX D,ONUMA K,et al.Lowdimensional structure and magnetism of the quantum antiferromagnet Rb4Cu(MoO4)3 and the structure of Rb4Zn(MoO4)3[J].J Am Chem Soc,2010,132(20):7055-7061.
[14] KARMAKAR D,YAKHMI J V.Spin interactions in mineral libethenite series:evolution of low-dimensional magnetism[J].Journal of Physics:Condensed Matter,2012,24(43):436003.
[15] ZOU Z,ANDERSON P W.Neutral fermion,charge-e boson excitations in the resonating-valence-bond state and superconductivity in La2CuO4-based compounds[J].Physical Review B,1988,37(1):627-630.
[16] LEE S H,KIKUCHI H,QIU Y,et al.Quantum-spinliquid states in the two-dimensional Kagoméantiferromagnets ZnxCu4-x(OD)6Cl2[J].Nature Materials,2007,6(11):853-857.
[17] ZHAO L,LIU W,LIU S,et al.The first anhydrous metal fluorosulfate Na3Fe(SO4)2F2 with layered structure prepared via the interesting“tailor”role of fluorine ions based on Na3Fe(SO4)2[J].Inorganica Chimica Acta,2015,438:191-195.
[18] SHELDRICK G M.A short history of SHELX[J].Acta Crystallographica A,2008,64:112-122.
[19] BRESE N E,O′KEEFFE M.Bond-valence parameters for solids[J].Acta Crystallographica B,1991,47(2):192-197.
[20] ZHOU Y,HUANG Y X,PAN Y,et al.Single-crystal microtubes of a novel apatite-type compound,(Na2.5Bi2.5)(PO4)3(F,OH),with well-faceted hexagonal cross sections[J].CrystEngComm,2009,11(9):1863-1867.
[21] HANUZA J,OWSKA-TRZEBIATOWSKA J B,UKASZEWICZ K.Normal coordinate analysis of M2O7 systems with C2v symmetry(pyrophosphates and-arsenates)intramolecular forces in a urey-bradley-shimanouchi force field[J].Journal of Molecular Structure,1972,13(3):391-403.
[22] SERGHINI IDRISSI M,RGHIOUI L,NEJJAR R,et al.Vibrational spectra of monoclinic diphosphates of formula AMP2O7[J].Spectrochimica Acta Part A:Molecular&Biomolecular Spectroscopy,2004,60(8/9):2043-2052.
[23] BIH H,SAADOUNE I,EHRENBERG H,et al.Crystal structure,magnetic and infrared spectroscopy studies of the LiCryFe1-yP2O7solid solution[J].Journal of Solid State Chemistry,2009,182(4):821-826.
[24] BROUZI K,ENNACIRI A,HARCHARRAS M,et al.Structure and vibrational spectra of a new trihydrate diphosphate,MnNH4NaP2O7·3H2O[J].Journal of Raman Spectroscopy,2004,35:41-46.
[25] KAGEYAMA H,ONIZUKA K,YAMAUCHI T,et al.Anomalous magnetizations in single crystalline SrCu2(BO3)2[J].Journal of the Physical Society of Japan,1999,68(6):1821-1823.
[26] TANG Y,PENG C,GUO W,et al.Octa-Kagomélattice compounds showing quantum critical behaviors:spin gap ground state versus antiferromagnetic ordering[J].J Am Chem Soc,2017,139(40):14057-14060.
[27] SUN W,HUANG Y X,PAN Y M,et al.Synthesis and magnetic properties of centennialite:a new S=1/2Kagoméantiferromagnet and comparison with herbertsmithite and kapellasite[J].Physics&Chemistry of Minerals,2016,43(2):127-136.
[28] PUPHAL P,BOLTE M,SHEPTYAKOV D,et al.Strong magnetic frustration in Y3Cu9(OH)19Cl8:a distorted Kagoméantiferromagnet[J].Journal of Materials Chemistry C,2017,5(10):2629-2635.
[29] SUN W,HUANG Y X,NOKHRIN S,et al.Perfect Kagomélattices in YCu3(OH)6Cl3:a new candidate for the quantum spin liquid state[J].Journal of Materials Chemistry C,2016,4(37):8772-8777.
[30] RIGOL M,SINGH R R.Magnetic susceptibility of the Kagoméantiferromagnet ZnCu3(OH)6Cl2[J].Physical Review Letters,2007,98(20):207204.