CN107473268B - A kind of bismuth tungstate nano cluster compound and its preparation method and application - Google Patents
A kind of bismuth tungstate nano cluster compound and its preparation method and application Download PDFInfo
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- CN107473268B CN107473268B CN201710711519.4A CN201710711519A CN107473268B CN 107473268 B CN107473268 B CN 107473268B CN 201710711519 A CN201710711519 A CN 201710711519A CN 107473268 B CN107473268 B CN 107473268B
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Abstract
The present invention relates to a kind of huge { Bi6And { Ce6Four poly- unit [W of cluster bridging Lindqvist type14CeIV 6O61]14–The bismuth tungstate nano cluster compound of insertion, chemical formula are as follows: Na16(NH4)10H8{(W14CeIV 6O61)[W3Bi6CeIII 3(H2O)3O14(α‑BiW9 O33)3]2}·38H2O belongs to monoclinic system,C2/C space group, cell parameter area=34.540 (5),b=31.408 (4),c=41.760 (6),α=90.00o,β=109.152 (2) o,γ=90.00º,V=42796(11)Å3,Z=4,R 1=0.1169,wR 2=0.2864.This nanometer of cluster compound is to utilize simple raw material Na using a step self assembly strategy2WO4·2H2O、NaAc·3H2O、Bi(NO3)3·5H2O and (NH4)2Ce(NO3)6Under aqueous conditions made from reaction.Research is found: this nanometer of cluster compound has excellent proton conductivity of phosphoric acid at-40-30 DEG C, can be used for preparing the conductive material under cryogenic conditions.
Description
Technical field
The invention belongs to polyoxometallate technical field of chemical material preparation, and in particular to a kind of huge { Bi6And
{Ce6Four poly- unit [W of cluster bridging Lindqvist type14CeIV 6O61]14–The bismuth tungstate nano cluster compound of insertion, preparation method and
Its application in terms of preparing low-temperature conductive material.
Background technique
In recent years, economic fast development quicklys increase the demand for energy in global range, causes the energy increasingly
Shortage is especially severely limited in the use of some renewable energy such as petroleum and gas.Therefore, in reasonable development
While using the energy, finding fungible energy source becomes the task of top priority.And fuel cell, as a kind of fungible energy source, it is opened
Sending out and using will be a tempting selection.Scientists paid great efforts study it is new non-volatile and be easy to plus
The solid electrolyte of work improves the performance of fuel cell, makes it have higher energy density and longer cycle life.Cause
This, the proton conductives material such as organic polymer, inorganic material, metal organic frame/Porous coordination polymer and covalent organic frame
Material is rapidly developed.In contrast, for the research of polyoxometallate proton conducting material also in initial stage.Multi-metal oxygen
Hydrochlorate is usually early transition metal ion (the usually Mo by highest valence stateVI、WVI、VV、NbV、TaV) obtained by oxygen atom bridging
A kind of Polyoxometallate arrived, unique oxygen-enriched surface, controllable nano-scale, strong bronsted acid, quickly
Electric charge transfer and " pseudoliquid stage " behavior impart their potential proton conducting abilities.From Nakamura in 1979 et al.
Have found the first polyoxometallic acid salt material H with electrical conductive behavior3PM12O40·29H2O (M=MoVI、WVI) after (referring to
O.Nakamura, T.Kodama, I.Ogino, et al.Chem.Lett.1979,8,17-18), polyoxometallate proton is led
Electric material is attracted wide attention and is largely explored.For example, 2011, Wei Meilin Keggin-type heteropolyanion [PM12O40
]3–It is reacted with transition metal ions and organic molecule isonicotinic acid, is successfully prepared two oversubscription subframes based on heteropolyanion
{[M(H2O)8][H(H2O)2.5](HINO)4(PMo12O40)}n(M=CoII、NiII) (referring to M.L.Wei, P.F.Zhuang,
H.H.Li,et al.Eur.J.Inorg.Chem.2011,1473–1478).Proton conductive test result shows this multi-metal oxygen
Silicate material has good proton conductivity 1.42-when relative humidity is (RH) 98%, temperature range is 85-100 DEG C
2.83×10–3S cm–1.Then, Wu Qing silver seminar finds Dawson type H9P2W15V3O62·28H2O is in room temperature and 75%RH item
Higher proton conductivity 3.64 × 10 is shown under part–2S cm–1(referring to X.Tong, X.Wu, Q.Wu, et al.Dalton
Trans.2012,41,9893–9896).2014, the chivalrous project of Liu's art be combined into an example it is organic-the three-dimensional oversubscription of inorganic hybridization
Sub- proton conductor [Sm (H2O)5(CO2CH2NH3)2][Al(OH)6Mo6O18]·10H2O (referring to J.Miao, Y.W.Liu, Q.Tang,
Et al.Dalton Trans.2014,43,14749-14755), it is by Anderson type reduction-state polyoxometallic acid salt anionic [Al
(OH)6Mo6O18]3-With coordination cation [Sm (H2O)5(gly)2]3+It is formed by electrostatic interaction and hydrogen bond action.Supermolecule frame
A large amount of hydrone ensures that the material has excellent proton conductivity 4.53 × 10 in frame–3S cm–1(80 DEG C, 95%RH).
2015, Zheng Shou added seminar and is prepared for polyoxometallate-organic ligand supermolecule that five rare core nickel clusters of an example replace
Nanotube [H2en]4[Ni5(OH)3(trzS)3(en)(H2O)(B-α-PW9O34)]·6H2O (en=ethylenediamine,
H2TrzS=1H-1,2,4-triazole-3-thiol), conductivity of the Supramolecular Network at 85 DEG C, 98%RH reaches 2.4
×10–4S cm–1, (referring to G.J.Cao, J.D.Liu, T.T.Zhuang, et al.Chem.Commun.2015,51,2048-
2051).Then, which reports the tungstogermanate [Ln of two high core rare earth insertion again27Ge10W106O406(OH)4
(H2O)24]59–(Ln=LaIII、CeIII) and [{ M (pip)2}2{Ln29Ge10W106O406(OH)4(H2O)28}]49-–(M=CuII、
NiII、CoII, pip=piperazine), and have studied they in 20-85 DEG C of sections ionic conductivity (referring to Z.Li,
X.-X.Li,T.Yang,et al.Angew.Chem.Int.Ed.2017,56,2664–2669).However, on the one hand, report at present
The polyoxometallate conductive material in road is concentrated mainly on tungsten/molybdenum oxygen hydrochlorate that the transition metal of small size includes, and to tool
The research for the polyoxometallate cluster compound for having the rare earth of nanoscale to replace is less；On the other hand, reported multi-metal oxygen
Hydrochlorate conductive material did not studied the electrical conductive behavior under low temperature anhydrous condition also.It is well known that fuel cell technology not only needs
Conducting electrolyte has high electrical conductivity when medium temperature works, while being also required to when lower temperature such as room temperature is even subzero
Also good electric conductivity is showed.Therefore, the electrical conductive behavior of research polyoxometallic acid salt material at low temperature is anticipated with most important theories
Justice and reference value.
Summary of the invention
It is an object of that present invention to provide a kind of huge { Bi6And { Ce6Four poly- unit of cluster bridging Lindqvist type
[W14CeIV 6O61]14–Bismuth tungstate nano cluster compound of insertion and its preparation method and application.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of huge { Bi6And { Ce6Four poly- unit [W of cluster bridging Lindqvist type14CeIV 6O61]14–The bismuth wolframic acid of insertion
Salt nanometer cluster compound, chemical formula are as follows: Na16(NH4)10H8{(W14CeIV 6O61)[W3Bi6CeIII 3(H2O)3O14(α-BiW9O33)3
]2}·38H2O。
Above-mentioned huge { Bi6And { Ce6Four poly- unit [W of cluster bridging Lindqvist type14CeIV 6O61]14–The bismuth tungsten of insertion
Silicate nanometer cluster compound is obtained using a step self-assembling method, and preparation method specifically comprises the following steps:
Under agitation by Na2WO4·2H2O and NaAc3H2O is dissolved into distilled water, then will be dissolved in hydrochloric acid
In Bi (NO3)3·5H2O is added in above-mentioned solution, and pH is adjusted to 5.2-5.4, and (NH is added after stirring 20-30min4)2Ce
(NO3)6, continue 20-30min of stirring at room temperature, be subsequently placed in 120-160min of heating in 90 ± 5 DEG C of water-baths, take out, be cooled to
Room temperature, filtering, filtrate stand to yellow needle-like crystals (ten days or so) are precipitated, filter again, drying at room temperature is received to get to target
Rice cluster compound.
Specifically, the Na2WO4·2H2O、NaAc·3H2O、Bi(NO3)3·5H2O、(NH4)2Ce(NO3)6And distilled water
Molar ratio be 3.056-3.660 ︰, 3.858 ︰, 0.295 ︰, 0.252-0.286 ︰ 1111.
Above-mentioned huge { Bi6And { Ce6Four poly- unit [W of cluster bridging Lindqvist type14CeIV 6O61]14–The bismuth tungsten of insertion
Application of the silicate nanometer cluster compound in terms of preparing proton conducting material, especially in terms of preparing low-temperature protonic conductive material
Potential application.
The present invention uses a step self assembly strategy, by the sodium tungstate of certain mol ratio, sodium acetate, bismuth nitrate and cerous nitrate
Ammonium reacts under aqueous conditions has obtained the novel huge { Bi of an example6And { Ce6Four poly- unit of cluster bridging Lindqvist type
[W14CeIV 6O61]14–The bismuth tungstate nano cluster compound of insertion.In the reaction, a step self-assembling reaction of simple raw material is advantageous
In the changeable poly-tungstate segment of construction structure, and its aggregation is further promoted to form big cluster.BiIIIAtom has lone pair electrons
Stereochemical effect, on the one hand can prevent the bismuth tungstates building unit to form saturation, on the other hand, BiIIIAtom from
Sub- radius is larger, contributes to form flexile coordination mode to connect different bismuth tungstates segments, induce high core cluster and
The formation of high polymer.Ce with higher electronegativityIVIon not only acts as the effect of charge compensation, and can by bonding and
Bridging function plays stabilization to the structure of nanometer cluster compound.W:Bi (12.5:1) relatively large molar ratio in starting material
Possibility is provided with more tungsten and miscellaneous more tungsten anionic moieties to construct.
Target nanometer cluster compound of the present invention has good low-temperature protonic electric conductivity, this is to polyoxometallate nano-cluster
The research for closing the proton conductive behavior of object is of great significance, and is huge polyoxometallate nanometer cluster compound as new low temperature
The feasibility of proton conducting material provides experimental basis.Compared to the prior art, the present invention has the advantage that
1) huge { Bi provided by the invention6And { Ce6Four poly- unit [W of cluster bridging Lindqvist type14CeIV 6O61]14–It is embedding
The crystal structure characteristic of the bismuth tungstate nano cluster compound entered can accurately be determined by X-ray single crystal diffraction；
2) huge { Bi provided by the invention6And { Ce6Four poly- unit [W of cluster bridging Lindqvist type14CeIV 6O61]14–It is embedding
The bismuth tungstate nano cluster compound entered is obtained using a step self-assembling method of simple raw material, simple and easy, and cost is relatively low, has
Potential application prospect；
3) huge { Bi provided by the invention6And { Ce6Four poly- unit [W of cluster bridging Lindqvist type14CeIV 6O61]14–It is embedding
The bismuth tungstate nano cluster compound entered has excellent proton conductive under the conditions of low-temperature anhydrous；
4) huge { Bi provided by the invention6And { Ce6Four poly- unit [W of cluster bridging Lindqvist type14CeIV 6O61]14–It is embedding
The bismuth tungstate nano cluster compound entered is finds and prepares low-temperature protonic conductive material and provide experimental basis and theoretical reference.
Detailed description of the invention
In Fig. 1, (a) is the molecular structure of target nanometer cluster compound, (b) is the simplification figure of target nanometer cluster compound, (c)
For the multi-metal oxygen cluster { [W of " spread the wings hawk " shape in target nanometer cluster compound3Bi6CeIII 3(H2O)3O14]2[CeIV 6O8], (d) it is
Target nanometer cluster compound { W3Bi6CeIII 3(H2O)3O14Segment, it is (e) { the Ce of target nanometer cluster compound6Cluster；
In Fig. 2, (a) is the Magnetic Properties of Three-Dimensional Supramolecular Complex structure chart of target nanometer cluster compound, (b) is free in target nanometer cluster compound
Crystalline water molecules and NH4 +Layout viewing of the ion in three-dimensional accumulation cavity；(c)-(n) is to dissociate in target nanometer cluster compound
Crystalline water molecules and NH4 +Hydrogen bond action in ion between oxygen atom and oxygen atom and oxygen atom and nitrogen-atoms；
Fig. 3 is the infrared spectrogram of target nanometer cluster compound, shows ν (W-O in target nanometer cluster compoundt)、ν(W–Ob)
With ν (W-Oc), the eigen vibration absorption band of Bi-O and hydrone；
Fig. 4 is the thermogravimetric curve of target nanometer cluster compound, shows weightless process Master Home in the crystallization water, water of coordination, NH4 +
Ion and H+Ion lose and skeleton in tungsten oxide distillation；
Fig. 5 is the XPS spectrum figure of Ce, W and Bi atom in target nanometer cluster compound, shows that+3 and+4 valences are presented in Ce, W is presented+6
Valence, Bi presentation+trivalent；
In Fig. 6, (a) is Nyquist figure of the target nanometer cluster compound in-40-30 DEG C of temperature ranges, (b) is received for target
The Arrhenius fitted figure of the proton conductive of rice cluster compound, finds out the proton conductive of target nanometer cluster compound with temperature in figure
Degree is increased and is quicklyd increase, and shows that its proton conductive is larger to temperature dependency；
In Fig. 7, it (b) is target nanometer that (a), which is Nyquist figure of the target nanometer cluster compound at 25 DEG C under different humidity,
The relational graph of cluster compound proton conductivity and humidity at 25 DEG C.
Specific implementation method
Below by way of specific embodiment, the invention will be further described, but protection scope of the present invention is not limited to
This.
Embodiment 1:
A kind of huge { Bi6And { Ce6Four poly- unit [W of cluster bridging Lindqvist type14CeIV 6O61]14–The bismuth wolframic acid of insertion
Salt nanometer cluster compound, chemical formula are as follows: Na16(NH4)10H8{(W14CeIV 6O61)[W3Bi6CeIII 3(H2O)3O14(α-BiW9O33)3
]2}·38H2O。
Above-mentioned huge { Bi6And { Ce6Four poly- unit [W of cluster bridging Lindqvist type14CeIV 6O61]14–The bismuth tungsten of insertion
Silicate nanometer cluster compound is obtained by a step self-assembling method of simple raw material, and preparation method specifically comprises the following steps:
Under agitation, by 1.207g (3.660mmol) Na2WO4·2H2O and 0.525g (3.858mmol) NaAc
3H2O is dissolved into 20mL distilled water, then will be dissolved in 1mL hydrochloric acid solution (6mol L–1) in 0.143g (0.295mmol)
Bi (NO3)3·5H2O is added drop-wise to dropwise in above-mentioned solution, with 6mol L–1Sodium hydroxide solution pH is transferred to 5.4.Stirring
0.157g (0.286mmol) (NH is added after 25min4)2Ce(NO3)6, continue to stir 25min at room temperature, be placed in 90 DEG C of water-baths
140min is heated, takes out, is cooled to room temperature, is filtered, filtrate stands ten days or so precipitation yellow needle-like crystals, filters again, brilliant
Body drying at room temperature to get arrive target nanometer cluster compound.
Embodiment 2:
A kind of huge { Bi6And { Ce6Four poly- unit [W of cluster bridging Lindqvist type14CeIV 6O61]14–The bismuth wolframic acid of insertion
Salt nanometer cluster compound, chemical formula are as follows: Na16(NH4)10H8{(W14CeIV 6O61)[W3Bi6CeIII 3(H2O)3O14(α-BiW9O33)3
]2}·38H2O。
Above-mentioned huge { Bi6And { Ce6Four poly- unit [W of cluster bridging Lindqvist type14CeIV 6O61]14–The bismuth tungsten of insertion
Silicate nanometer cluster compound is obtained by a step self-assembling method of simple raw material, and preparation method specifically comprises the following steps:
Under agitation, by 1.008g (3.056mmol) Na2WO4·2H2O and 0.525g (3.858mmol) NaAc
3H2O is dissolved into 20mL distilled water, then will be dissolved in 1mL hydrochloric acid solution (6mol L–1) in 0.143g (0.295mmol)
Bi (NO3)3·5H2O is added drop-wise to dropwise in above-mentioned solution, with 6mol L–1Sodium hydroxide solution pH is transferred to 5.4.Stirring
0.157g (0.286mmol) (NH is added after 25min4)2Ce(NO3)6, continue to stir 25min at room temperature, be placed in 90 DEG C of water-baths
140min is heated, takes out, is cooled to room temperature, is filtered, filtrate stands ten days or so precipitation yellow needle-like crystals, filters again, brilliant
Body drying at room temperature to get arrive target nanometer cluster compound.
Embodiment 3:
A kind of huge { Bi6And { Ce6Four poly- unit [W of cluster bridging Lindqvist type14CeIV 6O61]14–The bismuth wolframic acid of insertion
Salt nanometer cluster compound, chemical formula are as follows: Na16(NH4)10H8{(W14CeIV 6O61)[W3Bi6CeIII 3(H2O)3O14(α-BiW9O33)3
]2}·38H2O。
Above-mentioned huge { Bi6And { Ce6Four poly- unit [W of cluster bridging Lindqvist type14CeIV 6O61]14–The bismuth tungsten of insertion
Silicate nanometer cluster compound is obtained by a step self-assembling method of simple raw material, and preparation method specifically comprises the following steps:
Under agitation, by 1.207g (3.660mmol) Na2WO4·2H2O and 0.525g (3.858mmol) NaAc
3H2O is dissolved into 20mL distilled water, then will be dissolved in 1mL hydrochloric acid solution (6mol L–1) in 0.143g (0.295mmol)
Bi (NO3)3·5H2O is added drop-wise to dropwise in above-mentioned solution, with 6mol L–1Sodium hydroxide solution pH is transferred to 5.4.Stirring
0.138g (0.252mmol) (NH is added after 25min4)2Ce(NO3)6, continue to stir 25min at room temperature, be placed in 90 DEG C of water-baths
140min is heated, takes out, is cooled to room temperature, is filtered, filtrate stands ten days or so precipitation yellow needle-like crystals, filters again, brilliant
Body drying at room temperature to get arrive target nanometer cluster compound.
The crystalline substance for the target nanometer cluster compound that the present invention is prepared above-described embodiment using X-ray single crystal diffraction technology
Body structure is determined and characterizes, and cell parameter is as follows:
Nanometer cluster compound Na16(NH4)10H8{(W14CeIV 6O61)[W3Bi6CeIII 3(H2O)3O14(α-BiW9O33)3]2}·
38H2O is monoclinic system, space group C2/c, cell parameterα
=90.00 °, β=109.152 (2) °, γ=90.00 °,Z=4, R1=0.1169, wR2=0.2864.
The structure of target nanometer cluster compound is described as follows: its molecular structure includes one more with 2.2 × 2.9nm size
Oxometallate nanometer cluster anions { (W14CeIV 6O61)[W3Bi6CeIII 3(H2O)3O14(α-BiW9O33)3]2}34–, 16 Na+From
Son, 10 [NH4]+Ion, 8 H+Ion and 38 crystalline water molecules.This nanometer of cluster compound { (W14CeIV 6O61)[W3Bi6CeIII 3
(H2O)3O14(α-BiW9O33)3]2}34–(see a, b in Fig. 1) is by three three vacant Keggin-type [α-BiW9O33]9–Segment, two
Three omission Lindqvist type [W3O13]8–Segment and two capped three omission Lindqvist types [W4O16]8–Segment passes through one
The multi-metal oxygen cluster { [W of " spread the wings hawk " shape3Bi6CeIII 3(H2O)3O14]2[CeIV 6O8] assemble (see c in Fig. 1), it should
Multi-metal oxygen cluster is by two { W3Bi6CeIII 3(H2O)3O14Segment and [a CeIV 6O8]({Ce6) cluster constitute (see d in Fig. 1,
e).As far as we know, this nanometer of cluster compound is current maximum bismuth tungstates Rare Earth Derivatives, while being also the first scarce comprising three
The poly-tungstate rare earth nano cluster compound of position Keggin, three omission Lindqvist and capped three omission Lindqvist units.It should
Nanometer cluster compound also can be regarded as by the trimerization unit [W of two three vacant Keggin-types3Bi6CeIII 3(H2O)3O14(α-
BiW9O33)3]10–With a poly- unit [W of novel three omission Lindqvist type four14CeIV 6O61]14–Composition.Lindqvist type
Four poly- unit [W14CeIV 6O61]14–It is by two three omissions and two capped three omissions Lindqvist subunits by one
High core rare earth cluster { CeIV 6O32}({Ce6) connection obtains.As far as we know, both more vacant Lindqvist units exist
It is reported for the first time in rare earth polyoxometallate chemistry.{Ce6Six Ce in clusterIVAtom is located at octahedral vertex position
It sets.When we are by CeIVAtom is simplified to four connecting nodes, when O atom is as bridge, { Ce6Cluster can simplify into one it is closed
{ the Ce of irregular dodecahedron6O8Cage.In this nanometer of cluster compound, it is former that heteroatomic Bi is independently served as except three crystallography
Sub (Bi1, Bi2, Bi3) outside, six crystallography independently have Bi atom (Bi4-Bi9) the assembling cluster of bridging function, and respectively
Single cap trigone column configuration (Bi4, Bi6-Bi8) of seven coordinations of distortion is shown, the pentagonal pyramid (Bi5) and pentacoordinate of hexa-coordinate are flat
Face pentagon configuration (Bi9).The cluster compound also includes the independent Ce ion of seven crystallography, shows seven coordinations of distortion respectively
Single cap octahedron (CeIII1), double cap triangular prism (Ce of eight-coordinateIV2, CeIV5–CeIV7) the anti-rib in single cap four directions being coordinated with nine
Column configuration (CeIII3, CeIII4).Hydrone and NH rich in target nanometer cluster compound4 +Ion, on the one hand, nano-cluster yin
Surface oxygen atoms and free crystalline water molecules and NH in ion4 +Ion forms hydrogen bond, and adjacent nanometer cluster anions are borrowed
Help hydrogen bond action to form Magnetic Properties of Three-Dimensional Supramolecular Complex frame (see a in Fig. 2).On the other hand, free hydrone and NH4 +Ion is in three-dimensional heap
Ordered arrangement in product hole, and by between adjacent crystalline water molecules and crystalline water molecules and crystalline water molecules and nitrogen-atoms
Hydrogen bond action form one-dimensional hydrogen bond chain (see b-n in Fig. 2).These hydrogen bond actions not only contribute to firm Magnetic Properties of Three-Dimensional Supramolecular Complex frame
Frame also provides channel for proton conductive conduction.
The present invention characterizes the infrared spectroscopy (see Fig. 3) of target nanometer cluster compound and heat analysis behavior (see Fig. 4).
Its infrared spectroscopy is in 939,893,862,831,793 and 729cm–1There is characteristic peak in position, be attributed to three omission Keggin and
ν (W-the O of Lindqvist framet)、ν(W–Ob) and ν (W-Oc) asymmetric stretching vibration.With Bi2O3Infrared spectroscopy
(526cm–1There is a strong absworption peak at place) it compares, 521cm in target nanometer cluster compound–1The absorption peak at place can belong to ν (Bi-O)
Vibration.In addition, in 3442 and 1626cm–1There is strong absorption band in place, shows in the cluster compound containing coordination or the crystallization water
Molecule.The thermal analysis curve of target nanometer cluster compound can be divided into two step weightlessness processes.The first step DEG C weightlessness from 25 to 300 is
3.24% (theory 3.19%), corresponding to losing for 38 crystalline water molecules and 6 water of coordination molecule.Second step from 300 to
1000 DEG C of weightlessness are 2.55%, lose (theory 1.34%) and partial oxidation tungsten corresponding to 10 amino molecules and 18 protons
Distillation.
The present invention by x-ray photoelectron spectroscopy (XPS) to the valence state of Ce, W and Bi atom in target nanometer cluster compound into
It has gone research (see Fig. 5).The XPS signal of Ce appears in 885.85,898.93 and 903.37eV, corresponds to Ce3+The presence of ion；
Characteristic signal positioned at 882.21 and 916.38eV proves Ce4+The presence of ion.The XPS signal of W appears in 37.28 Hes
35.18eV is attributed to W 4f respectively5/2With W 4f7/2Energy level shows the presence of+6 valence W.The XPS signal of Bi is located at 164.28 Hes
158.98eV being respectively belonging to Bi 4f5/2With Bi 4f7/2Energy level, it was demonstrated that Bi is+trivalent.
To inquire into whether target nanometer cluster compound has proton conductivity of phosphoric acid, we pass through test mesh by two-probe me- thod
The AC impedance of mark nanometer cluster compound studies its proton conductive, and has carried out the anhydrous condition at-40-30 DEG C for the first time
The research of the proton conduction behavior of lower research polyoxometallate nanometer cluster compound.Proton conductivity by formula σ=(1/R) ×
(l/S) determination, l and S are respectively the length and cross-sectional area of sample, and R value is resistance, are obtained by ac impedance measurement.Proton
The activation energy of conductivityaArrhenius σ can be passed throughT=A × exp (- Ea/kBT) fitting obtains, and works as EaWhen greater than 0.5eV, matter
Subconductivity behavior can be attributed to vehicle type electrical conduction mechanism, on the contrary then be Grotthuss type electrical conduction mechanism.Test result shows:
Proton conductivity of the target nanometer cluster compound at -40 DEG C is 4.91 × 10–7S cm–1, when temperature is increased to 30 DEG C, matter
Subconductivity rate is increased rapidly to 8.26 × 10–4S cm–1(see Fig. 6 a).It can be seen that the proton conductivity of target nanometer cluster compound
To temperature dependence with higher.Arrhenius fitting is in a linear relationship, and fitting obtains the activation energy of proton conductivitya
For 0.677eV (see Fig. 6 b), it can be attributed to vehicle type electrical conduction mechanism, this mainly contains largely with target nanometer cluster compound
Hydrone and NH4 +Ion is related.In addition, the proton conductivity of target nanometer cluster compound at room temperature is with humidity in environment
The increase of (from 50% to 90%) and be gradually increased (from 2.64 × 10–4S cm–1To 2.4 × 10–3S cm–1) (see Fig. 7).From with
Upper test result can be seen that target nanometer cluster compound has excellent proton conductivity of phosphoric acid at-40-30 DEG C, can be used for preparing matter
Subconductivity material especially prepares the proton conducting material under cryogenic conditions.
Claims (4)
1. a kind of bismuth tungstate nano cluster compound, which is characterized in that the chemical formula of this nanometer of cluster compound are as follows: Na16(NH4)10H8
{(W14CeIV 6O61)[W3Bi6CeIII 3(H2O)3O14(α-BiW9 O33)3]2}·38H2O。
2. the preparation method of bismuth tungstate nano cluster compound described in claim 1, which comprises the steps of:
Under agitation by Na2WO4·2H2O and NaAc3H2O is dissolved into distilled water, the Bi that then will be dissolved in hydrochloric acid
(NO3)3·5H2O is added in above-mentioned solution, and pH is adjusted to 5.2-5.4, and (NH is added after stirring 20-30 min4)2Ce(NO3)6,
Continue 20-30 min of stirring at room temperature, be subsequently placed in 120-160min of heating in 90 ± 5 DEG C of water-baths, take out, be cooled to room temperature,
Filtering, filtrate stand to be precipitated yellow needle-like crystals, filter again, drying at room temperature to get arrive target nanometer cluster compound；
The Na2WO4·2H2O、NaAc·3H2O、Bi(NO3)3·5H2O、(NH4)2Ce(NO3)6Molar ratio with distilled water is
3.056-3.660 ︰, 3.858 ︰, 0.295 ︰, 0.252-0.286 ︰ 1111.
3. bismuth tungstate nano cluster compound described in claim 1 is preparing the application in proton conducting material.
4. bismuth tungstate nano cluster compound as claimed in claim 3 is preparing the application in proton conducting material, which is characterized in that
The nanometer cluster compound is potential low-temperature protonic conductive material.
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