CN108440608A - A kind of hybrid inorganic-organic molybdenum arsenic acid salt crystal and its preparation method and application - Google Patents
A kind of hybrid inorganic-organic molybdenum arsenic acid salt crystal and its preparation method and application Download PDFInfo
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/095—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of organic acids
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/50—Complexes comprising metals of Group V (VA or VB) as the central metal
- B01J2531/52—Antimony
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Abstract
A kind of organic inorganic hybridization molybdenum arsenic acid salt crystal and its preparation method and application, the present invention relates to a kind of organic inorganic hybridization molybdenum arsenic acid salt crystals and its preparation method and application, the purpose of the present invention is to solve the severe reaction conditions of existing preparing ethyl glycol by hydrolysis of ethylene carbonate, be easy to cause pollution, catalyst is not easily recycled the problem of, the present invention is by (NH4)6Mo7O24·4H2O、C10N2H8、NaAsO2And CuCl2·2H2O mixing, is added in distilled water and stirs, and sealing is placed in heating in baking oven again, and room temperature cooling is finally washed with distilled water simultaneously drying at room temperature, that is, completes.Using：Organic inorganic hybridization molybdenum arsenic acid salt crystal is used for ester hydrolysis process under normal pressure as catalyst, and catalyst is easily separated.Crystal prepared by the present invention can make catalyst for being catalyzed ester hydrolysis, do not adsorbed to ester, realize the efficient-decomposition under normal pressure to ester.Applications catalyst preparation field of the present invention.
Description
Technical field
The present invention relates to a kind of hybrid inorganic-organic molybdenum arsenic acid salt crystals and its preparation method and application.
Background technology
Ethylene glycol is a kind of widely used industrial chemicals, and in recent years, market is to the in great demand of ethylene glycol, therefore second two
The preparation process of alcohol causes various countries' most attention, the research and development of new process in the ascendant.Ethylene carbonate Hydrolyze method quilt at present
It is considered the method for most promising industrialized production ethylene glycol, is the hot spot researched and developed both at home and abroad at present.Study carbon
The technique that vinyl acetate Hydrolyze method prepares ethylene glycol has industrial value and practical significance very much, is an environmentally protective chemical mistake
Journey.But ethylene carbonate Hydrolyze method there is severe reaction conditions, be easy to cause pollution, of high cost, catalyst is not easily recycled
Problem.
Invention content
The purpose of the present invention is to solve the severe reaction conditions of existing preparing ethyl glycol by hydrolysis of ethylene carbonate, it is easy
It pollutes, the problem of catalyst is not easily recycled, provides a kind of hybrid inorganic-organic molybdenum arsenic acid salt crystal and preparation method thereof
And application.
A kind of molecular formula of hybrid inorganic-organic molybdenum arsenic acid salt crystal of the present invention is C40H39Cu4As3Mo12N8O52, molecular weight
It is 3093.99, anorthic system, space group p-1, cell parameter is α=103.0960 (10) °, β=109.0700 (10) °, γ=90.3370 (10) °, volumeDensity Dc=2.826Mgcm-3, the molecular number 1, R in structure cell1=0.0546, wR2=0.1450.
A kind of preparation method of hybrid inorganic-organic molybdenum arsenic acid salt crystal of the present invention, is to carry out according to the following steps：
By (NH4)6Mo7O24·4H2O、C10N2H8、NaAsO2、CuCl2·2H2O is mixed with distilled water, obtains mixture, is stirred
20-40min is mixed, reaction kettle interior sealing is subsequently placed in, the reaction kettle of sealing is placed in drying box, it is 4-6 days dry, it is cooled to room
Temperature is washed out simultaneously drying at room temperature, obtains hybrid inorganic-organic molybdenum arsenic acid salt crystal；Wherein (the NH4)6Mo7O24·
4H2O and NaAsO2Molar ratio be 0.19-0.21:1；(NH4)6Mo7O24·4H2O and C10N2H8Molar ratio be 0.345-
0.351:1；(NH4)6Mo7O24·4H2O and CuCl2·2H2The molar ratio of O is 0.269-0.275:1；(NH4)6Mo7O24·4H2O
Mole be 0.64mmol with the volume ratio of distilled water:18mL.
A kind of application of hybrid inorganic-organic molybdenum arsenic acid salt crystal of the present invention refers to preparing second two in ethylene carbonate ester hydrolysis
Application in the production process of alcohol.
The beneficial effects of the invention are as follows：
1, the C that the present invention uses10N2H8Play the role of mineralizer in preparation process, it is 58% to have obtained yield
The hybrid inorganic-organic molybdenum arsenic acid salt crystal of (in terms of molybdenum), hybrid inorganic-organic molybdenum arsenic acid salt crystal show preferably to be catalyzed
Therefore ethylene carbonate hydrolysising property can be applied to field of catalyst preparation.
2, hybrid inorganic-organic molybdenum arsenic acid salt crystal prepared by the present invention can make catalyst for being catalyzed ester hydrolysis, crystal
Type catalyst does not adsorb ester and may be implemented simply to be completely separated, and realizes the efficient-decomposition under normal pressure to ester.
3, the present invention prepares hybrid inorganic-organic molybdenum arsenic acid salt crystal and is not doing grinding and calcination process as catalyst
Under the premise of, the case where having preferable catalytic action to preparing ethyl glycol by hydrolysis of ethylene carbonate under normal pressure, not grinding and roast
Under, it reacts 3 hours, is heated to 95 DEG C, conversion ratio reaches 93%.
Description of the drawings
Fig. 1 is the ellipsoid figure of hybrid inorganic-organic molybdenum arsenic acid salt crystal prepared by embodiment 1；
Fig. 2 is the polyanionic polyhedron figure of hybrid inorganic-organic molybdenum arsenate prepared by embodiment 1；
Fig. 3 is the Cu-As-bipy cation figures of hybrid inorganic-organic molybdenum arsenic acid salt crystal prepared by embodiment 1；
Fig. 4 is the infrared spectrogram of hybrid inorganic-organic molybdenum arsenic acid salt crystal prepared by embodiment 1；
Fig. 5 is the ultraviolet spectrogram of hybrid inorganic-organic molybdenum arsenic acid salt crystal prepared by embodiment 1；
Fig. 6 is the hot weight curve of hybrid inorganic-organic molybdenum arsenic acid salt crystal prepared by embodiment 1.
Specific implementation mode
Technical solution of the present invention is not limited to the specific implementation mode of act set forth below, further include each specific implementation mode it
Between arbitrary combination.
Specific implementation mode one：A kind of molecular formula of hybrid inorganic-organic molybdenum arsenic acid salt crystal of present embodiment is
C40H39Cu4As3Mo12N8O52, molecular weight 3093.99, anorthic system, space group p-1, cell parameter isα=103.0960 (10) °, β=
109.0700 (10) °, γ=90.3370 (10) °, volumeDensity Dc=2.826Mgcm-3, in structure cell
Molecular number 1, R1=0.0546, wR2=0.1450.
Specific implementation mode two：A kind of preparation method of hybrid inorganic-organic molybdenum arsenic acid salt crystal of present embodiment, be by
Following steps carry out：
By (NH4)6Mo7O24·4H2O、C10N2H8、NaAsO2、CuCl2·2H2O is mixed with distilled water, obtains mixture, is stirred
20-40min is mixed, reaction kettle interior sealing is subsequently placed in, the reaction kettle of sealing is placed in drying box, it is 4-6 days dry, it is cooled to room
Temperature is washed out simultaneously drying at room temperature, obtains hybrid inorganic-organic molybdenum arsenic acid salt crystal；Wherein (the NH4)6Mo7O24·
4H2O and NaAsO2Molar ratio be 0.19-0.21:1；(NH4)6Mo7O24·4H2O and C10N2H8Molar ratio be 0.345-
0.351:1；(NH4)6Mo7O24·4H2O and CuCl2·2H2The molar ratio of O is 0.269-0.275:1；(NH4)6Mo7O24·4H2O
Mole be 0.64mmol with the volume ratio of distilled water:18mL.
Hybrid inorganic-organic molybdenum arsenic acid salt crystal prepared by present embodiment can make catalyst and be used to be catalyzed ester hydrolysis, brilliant
Build catalyst does not adsorb ester and may be implemented simply to be completely separated, and realizes the efficient-decomposition under normal pressure to ester.
Specific implementation mode three：Present embodiment is unlike specific implementation mode two：(NH4)6Mo7O24·4H2O with
NaAsO2Molar ratio be 0.2:1.Other are identical with embodiment two.
Specific implementation mode four：Unlike one of present embodiment and specific implementation mode two or three：(NH4)6Mo7O24·4H2O and C10N2H8Molar ratio be 0.35:1.Other are identical as specific implementation mode two or three.
Specific implementation mode five：Unlike one of present embodiment and specific implementation mode two to four：(NH4)6Mo7O24·4H2O and CuCl2·2H2The molar ratio of O is 0.27:1.Other are identical as one of specific implementation mode two to four.
Specific implementation mode six：Unlike one of present embodiment and specific implementation mode two to five：By 0.64mmol
(NH4)6Mo7O24·4H2O、1.83mmolC10N2H8、3.14mmolNaAsO2、2.35mmolCuCl2·2H2O and 18mL distilled water
Mixing.Other are identical as one of specific implementation mode two to five.
Specific implementation mode seven：Unlike one of present embodiment and specific implementation mode two to six：By (NH4)6Mo7O24·4H2O、C10N2H8、NaAsO2、CuCl2·2H2O is mixed with distilled water, obtains mixture, stirs 30min.Other with
One of specific implementation mode two to six is identical.
Specific implementation mode eight：Unlike one of present embodiment and specific implementation mode two to seven：Reaction kettle is poly-
Tetrafluoroethene reaction kettle.Other are identical as one of specific implementation mode two to seven.
Specific implementation mode nine：A kind of application of hybrid inorganic-organic molybdenum arsenic acid salt crystal of present embodiment refers in carbon
Vinyl acetate hydrolysis prepares the application in the production process of ethylene glycol.
Hybrid inorganic-organic molybdenum arsenic acid salt crystal prepared by present embodiment can make catalyst and be used to be catalyzed ester hydrolysis, brilliant
Build catalyst does not adsorb ester and may be implemented simply to be completely separated, and realizes the efficient-decomposition under normal pressure to ester.
Present embodiment prepares hybrid inorganic-organic molybdenum arsenic acid salt crystal as catalyst in the premise for not doing grinding and calcination process
Under, there is preferable catalytic action to preparing ethyl glycol by hydrolysis of ethylene carbonate under normal pressure, in the case of not grinding and roasting, instead
It answers 3 hours, is heated to 95 DEG C, conversion ratio reaches 93%.
Specific implementation mode ten：Present embodiment is unlike specific implementation mode nine：Hybrid inorganic-organic molybdenum arsenic acid
Salt crystal is applied to as catalyst in the production process of preparing ethyl glycol by hydrolysis of ethylene carbonate.Other and specific implementation mode
Nine is identical.
Beneficial effects of the present invention are verified using following embodiment：
Embodiment one：By 0.64mmol (NH4)6Mo7O24·4H2O、1.83mmolC10N2H8、3.14mmolNaAsO2、
2.35mmolCuCl2·2H2O is mixed with 18mL distilled water, obtains mixture, is stirred 30 minutes, is subsequently placed in 30mL polytetrafluoroethyl-nes
The ptfe autoclave of sealing is placed in the drying box that temperature is 160 DEG C by alkene reaction kettle interior sealing, heating 5 days, slowly
It is cooled to room temperature, obtains buff crystal, be washed with distilled water simultaneously drying at room temperature, it is brilliant to obtain hybrid inorganic-organic molybdenum arsenate
Body.
It is computed, the yield of hybrid inorganic-organic molybdenum arsenic acid salt crystal manufactured in the present embodiment is 58% (in terms of molybdenum).It adopts
The elemental analysis of C, H and N of molybdenum arsenic acid salt crystal are carried out with 2400 CHN elemental analysers of U.S. PE Analyzer；Using English
State TJA companies POEMS type ICP plasma chromatographies analyzers (Leeman inductively coupled plasma (ICP)
Spectrometer the metallic element analysis of molybdenum arsenic acid salt crystal) is carried out.Show the change through elemental analysis and ICP test results
Close object molecular formula be：C40H39Cu4As3Mo12N8O52(Mr=3093.99), the theoretical value (%) of each element content：C, 15.53；
H, 1.27；N, 4.50；As, 7.26；Cu, 8.22；Mo, 37.21.Experiment value (%)：C, 19.33；H, 1.25；N, 4.57；As,
7.17；Cu, 8.18；Mo, 37.25.
The present embodiment chooses the hybrid inorganic-organic molybdenum arsenic acid salt crystal that size is 0.20mm × 0.24mm × 0.26mm and exists
German Bruker companies AXS SMART CCD x-ray diffractometers collect diffraction data.Crystal structure SHELXL-97 programs
It is solved with direct method, with complete matrix least square method refine.The position of hydrogen atom is obtained using theoretical plus hydrogen method.The chemical combination
The crystallographic parameter of object is listed in the table below.
Table 1：The crystallographic parameter of hybrid inorganic-organic molybdenum arsenic acid salt crystal
Fig. 1 is the ellipsoid figure of hybrid inorganic-organic molybdenum arsenic acid salt crystal manufactured in the present embodiment, hybrid inorganic-organic molybdenum
Arsenic acid salt crystal is made of Keggin-type polyoxoanion, Cu-As-bipy organic coordination compounds and free hydrone；Fig. 2 is this
The polyanionic polyhedron figure of hybrid inorganic-organic molybdenum arsenic acid salt crystal prepared by embodiment.Keggin-type polyoxoanion
[HAsMo12O40]2-With typical TdSymmetry, polyhedral structure figure are as shown in Figure 2.By central atom As and 12 MoO6
Octahedron composition, wherein every three MoO6Octahedron forms Mo by common edge, nonadjacent oxygen atom3O13Unit, four Mo3O13
Unit forms cage structure by sharing oxygen atom, and central atom As is then at the center of " cage ".
Fig. 3 is the Cu-As-bipy cation figures of hybrid inorganic-organic molybdenum arsenic acid salt crystal manufactured in the present embodiment.Transition
Ni metal is coordinated the metal complex to be formed, AsO with organic ligand bipy4Tetrahedron bridging Cu-bipy metal complexs are free
Outside polyoxoanion.
1730-FTIR types infrared spectrophotometer is produced to hybrid inorganic-organic molybdenum arsenic acid salt crystal using PE companies of the U.S.
Examination of infrared spectrum is carried out, using KBr (SP is pure) tabletting, in 4000-400cm-1It is scanned in wave-number range.Fig. 4 is this reality
The infrared spectrogram for applying the hybrid inorganic-organic molybdenum arsenic acid salt crystal of example preparation, as seen from the figure, in 3441cm-1The absorption peak at place
The eigen vibration peak of hydrogen bond existing between ν (N-H) and polyanionic and organic ligand is attributed in organic ligand bipy,
1653-1524cm-1The absorption peak at place is attributed to the vibration peak of ν in organic ligand (C-N), 1046cm-1The absorption peak at place is attributed to
ν (As-O in polyoxoaniona) absorption peak, 960,903cm-1Absorption peak be attributed to ν (Mo-Ot) absorption peak, 828,
656cm-1Place is attributed to the absorption peak of ν (Mo-O-Mo).
Ultraviolet spectra test is carried out to hybrid inorganic-organic molybdenum arsenic acid salt crystal using UV-2550 spectrometers, in room temperature item
It is scanned within the scope of 200-600nm under part.Fig. 5 is the purple of hybrid inorganic-organic molybdenum arsenic acid salt crystal manufactured in the present embodiment
In the interval range of 200-600nm, there are two absorption peaks as seen from the figure in external spectrum figure.First absorption peak appears in
At 207nm, O should be attributed totThe lotus of p π-d π moves transition in → Mo；Second absorption peak appears in the vicinity 260nm, the suction
It receives peak and is attributed to π-π in organic ligand*Electron transition.
It is poor to be carried out to hybrid inorganic-organic molybdenum arsenic acid salt crystal using the TGA-7 types thermal analyzer of PE companies of U.S. production
Heat analysis is tested, with α-Al2O3It is heated up with the rate of 10 DEG C/min at 0~800 DEG C of room temperature using platinum crucible for object of reference.Fig. 6
For the hot weight curve of hybrid inorganic-organic molybdenum arsenic acid salt crystal manufactured in the present embodiment, as seen from the figure, first step weightlessness process
It is happened between 96-112 DEG C, corresponds to free hydrone, weightless ratio is 0.66% (calculated value 0.58%)；
Second step weightlessness process is happened between 290-350 DEG C, and organic ligand bipy's loses process, and weightless ratio is 20.28% (reason
It is 20.19%) by calculated value；The weightless process of third step is happened between 450-580 DEG C, corresponding to weightless ratio be
10.37% (calculated value 10.46%)；The process should be attributed to hydrone in residue, As2O3And O2Volatilization process.
The toatl proportion of three step weightlessness processes is 31.31%, is consistent substantially with calculated value 31.23%.
The application of molybdenum arsenic acid salt crystal, hybrid inorganic-organic molybdenum arsenic acid salt crystal manufactured in the present embodiment is as catalyst
For being catalyzed ester hydrolysis.
By taking ethylene carbonate as an example, hybrid inorganic-organic molybdenum arsenic acid salt crystal reacts the catalysis of ethylene carbonate ester hydrolysis
Research carries out under normal pressure.For be catalyzed react before, hybrid inorganic-organic molybdenum arsenate crystal catalyst do not have to grinding and
Roasting, ethylene carbonate ester hydrolysis reaction be equipped with magnetic agitation, thermometer, reflux condensate device three-necked flask in carry out,
The aqueous solvent of 4mL, ethylene carbonate 2g, hybrid inorganic-organic molybdenum arsenate crystal catalyst are sequentially added in three-necked flask
0.04g, 95 DEG C of agitating and heating, is reacted under certain bath temperature, after reacting 3 hours, filters out solid catalyst, right
Filtrate is distilled, and with the online measurement product component of gas-matter and content, it is 93% to calculate conversion ratio, is urged with other reported
The catalyst that change hydrolysis prepares ethylene glycol is compared, and catalyst activity improves a lot, in the case where not grinding and roasting, reaction
3 hours, 95 DEG C are heated to, conversion ratio reaches 93%.
Claims (10)
1. a kind of hybrid inorganic-organic molybdenum arsenic acid salt crystal, it is characterised in that the molecule of hybrid inorganic-organic molybdenum arsenic acid salt crystal
Formula is C40H39Cu4As3Mo12N8O52, molecular weight 3093.99, anorthic system, space group p-1, cell parameter isα=103.0960 (10) °, β=109.0700
(10) °, γ=90.3370 (10) °, volumeDensity Dc=2.826Mgcm-3, the molecular number in structure cell
1, R1=0.0546, wR2=0.1450.
2. preparing a kind of method of hybrid inorganic-organic molybdenum arsenic acid salt crystal as described in claim 1, it is characterised in that the party
Method is to carry out according to the following steps：
By (NH4)6Mo7O24·4H2O、C10N2H8、NaAsO2、CuCl2·2H2O is mixed with distilled water, obtains mixture, stirs 20-
40min is subsequently placed in reaction kettle interior sealing, and the reaction kettle of sealing is placed in drying box, 4-6 days dry, is cooled to room temperature, so
Washing and drying at room temperature afterwards, obtain hybrid inorganic-organic molybdenum arsenic acid salt crystal；Wherein (the NH4)6Mo7O24·4H2O with
NaAsO2Molar ratio be 0.19-0.21:1；(NH4)6Mo7O24·4H2O and C10N2H8Molar ratio be 0.345-0.351:1；
(NH4)6Mo7O24·4H2O and CuCl2·2H2The molar ratio of O is 0.269-0.275:1；(NH4)6Mo7O24·4H2O mole with
The volume ratio of distilled water is 0.64mmol:18mL.
3. a kind of preparation method of hybrid inorganic-organic molybdenum arsenic acid salt crystal according to claim 2, it is characterised in that
(NH4)6Mo7O24·4H2O and NaAsO2Molar ratio be 0.2:1.
4. a kind of preparation method of hybrid inorganic-organic molybdenum arsenic acid salt crystal according to claim 2, it is characterised in that
(NH4)6Mo7O24·4H2O and C10N2H8Molar ratio be 0.35:1.
5. a kind of preparation method of hybrid inorganic-organic molybdenum arsenic acid salt crystal according to claim 2, it is characterised in that
(NH4)6Mo7O24·4H2O and CuCl2·2H2The molar ratio of O is 0.27:1.
6. a kind of preparation method of hybrid inorganic-organic molybdenum arsenic acid salt crystal according to claim 2, it is characterised in that will
0.64mmol(NH4)6Mo7O24·4H2O、1.83mmolC10N2H8、3.14mmolNaAsO2、2.35mmolCuCl2·2H2O with
18mL distilled water mixes.
7. a kind of preparation method of hybrid inorganic-organic molybdenum arsenic acid salt crystal according to claim 2, it is characterised in that will
(NH4)6Mo7O24·4H2O、C10N2H8、NaAsO2、CuCl2·2H2O is mixed with distilled water, obtains mixture, stirs 30min.
8. a kind of preparation method of hybrid inorganic-organic molybdenum arsenic acid salt crystal according to claim 2, it is characterised in that anti-
It is ptfe autoclave to answer kettle.
9. such as the application of hybrid inorganic-organic molybdenum arsenic acid salt crystal prepared by claim 1, it is characterised in that the application refers to having
Machine-application of the inorganic hybridization molybdenum arsenic acid salt crystal in the production process of preparing ethyl glycol by hydrolysis of ethylene carbonate.
10. a kind of application of hybrid inorganic-organic molybdenum arsenic acid salt crystal according to claim 9, it is characterised in that organic-
Inorganic hybridization molybdenum arsenic acid salt crystal is applied to as catalyst in the production process of preparing ethyl glycol by hydrolysis of ethylene carbonate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111393485A (en) * | 2020-04-21 | 2020-07-10 | 周口师范学院 | Organic-inorganic hybrid thorium polyacid salt and preparation method and application thereof |
| CN114496587A (en) * | 2022-03-16 | 2022-05-13 | 广东石油化工学院 | Polyacid metal organic framework crystal and preparation method and application thereof |
Citations (1)
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| CN101733163A (en) * | 2009-12-16 | 2010-06-16 | 哈尔滨师范大学 | Method for preparing polyacid crystal catalyst |
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| CN101733163A (en) * | 2009-12-16 | 2010-06-16 | 哈尔滨师范大学 | Method for preparing polyacid crystal catalyst |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111393485A (en) * | 2020-04-21 | 2020-07-10 | 周口师范学院 | Organic-inorganic hybrid thorium polyacid salt and preparation method and application thereof |
| CN111393485B (en) * | 2020-04-21 | 2023-03-14 | 周口师范学院 | Organic-inorganic hybrid thorium polyoxometalate and preparation method and application thereof |
| CN114496587A (en) * | 2022-03-16 | 2022-05-13 | 广东石油化工学院 | Polyacid metal organic framework crystal and preparation method and application thereof |
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