CN110358102A - A kind of polyacid Base Metal organic frame crystalline material, preparation method and its catalyze and synthesize application to benzene a kind of jade class compound - Google Patents
A kind of polyacid Base Metal organic frame crystalline material, preparation method and its catalyze and synthesize application to benzene a kind of jade class compound Download PDFInfo
- Publication number
- CN110358102A CN110358102A CN201910641308.7A CN201910641308A CN110358102A CN 110358102 A CN110358102 A CN 110358102A CN 201910641308 A CN201910641308 A CN 201910641308A CN 110358102 A CN110358102 A CN 110358102A
- Authority
- CN
- China
- Prior art keywords
- crystalline material
- dimensional
- trz
- copper
- benzene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C46/00—Preparation of quinones
- C07C46/02—Preparation of quinones by oxidation giving rise to quinoid structures
- C07C46/06—Preparation of quinones by oxidation giving rise to quinoid structures of at least one hydroxy group on a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
- B01J2231/76—Dehydrogenation
- B01J2231/763—Dehydrogenation of -CH-XH (X= O, NH/N, S) to -C=X or -CX triple bond species
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J2531/16—Copper
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/14—All rings being cycloaliphatic
- C07C2602/26—All rings being cycloaliphatic the ring system containing ten carbon atoms
- C07C2602/28—Hydrogenated naphthalenes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to technical field of catalytic chemistry, more particularly to a kind of polyacid Base Metal organic frame crystalline material, preparation method and its catalyze and synthesize application to benzene a kind of jade class compound, the material can be used as heterogeneous catalysis, in catalysis alkyl phenolic, alkoxy benzene and 2- methyl naphthalene oxidative synthesis are mutually coped with to be had excellent catalytic properties in the reaction of benzene a kind of jade, especially in catalysis 2, 3, 6- oxidation of trimethylphenol synthesis 2, 3, in the reaction of 5- trimethylbenzene a kind of jade, in 10-20min, the complete conversion of substrate almost may be implemented, the yield of benzene a kind of jade is up to 96%-99%, and its transformation frequency is also up to 300-600h‑1；Furthermore the catalyst may be reused, and all there is no variations for structure and catalytic activity；The preparation process of the material is simple, product purity is high, has potential application prospect in catalytic field.
Description
Technical field
The invention belongs to technical field of catalytic chemistry, and in particular to the system of a kind of polyacid Base Metal organic frame crystalline material
Preparation Method and its catalysis oxidation alkyl phenol, alkoxy benzene and 2- methyl naphthalene are efficiently synthesized the application of 1,4-benzoquinone class compound.
Background technique
1,4-benzoquinone class compound is the important intermediate for synthetic drug, health care product and fine chemicals, in many lifes
Important function is play in object system.The synthesis material (such as phenol, aromatic hydrocarbons) of selective oxidation low-oxidation-state is prepared to benzene a kind of jade
The main path of class compound.Traditional method for oxidation usually using stoichiometry metal onidiges (CrO3, MnO2, V2O5)
And strong acid solution, but the generation of the by-product of invariably accompany a large amount of harmful wastes and excessive oxidation.Ring is used in the reaction
The O of border close friend2Or H2O2Oxidant has been to be concerned by more and more people.Currently, some transition metal salts or complex,
O2Or H2O2Under the conditions of, as the catalyst for aoxidizing various phenol and alkoxy aromatic hydrocarbons, such as copper chloride, Co- schiff bases complex,
Titan silicate, three oxygen rhenium of methyl, ruthenium and compound of iron etc..But these catalyst there are stability selection poor, to benzene a kind of jade
The problems such as low and oxidant utilization efficiency of property is low.Therefore, high activity, the high selection for synthesizing 1,4-benzoquinone class compound are developed
Property and stable catalyst are still a significant challenge.
Polyoxometallate (abbreviation polyacid, POMs) is since it is with good redox property and stability,
Certain application value is shown in the liquid phase oxidation of various organic matters.In catalysis alkyl phenolic/arene oxidizing at corresponding quinone
Aspect, the heteropoly acid H of structure with KegginnXM12O40(M=W or Mo；X=P or Si；N=3or 4) and Transition metal substituted
Heteropoly acid such as TBA4H[γ-PW10V2O40] and TBA8[{γ-SiW10Ti2O36(OH)2}2(μ-O)2] it has been used as homogeneous catalysis
Agent (Shimizu, M., Orita, H., Hayakawa, T., Takehira, K., Tetrahedron Lett.1989,30,471-
474；Ivanchikova,I.D.；Maksimchuk,N.V.；Maksimovskaya,R.I.；Maksimov,G.M.；
Kholdeeva, O.A.ACS Catal.2014,4,2706-2713), it is shown that preferable catalytic activity.Although these are homogeneously urged
Agent catalytic activity usually with higher, but the separation of catalyst and recycling and the purifying of product still suffer from compared with
Big difficulty.Therefore, heterogeneous polyacid catalyst of the exploitation for synthesizing 1,4-benzoquinone class compound be still one there is an urgent need to
The project of research.
One strategy for effectively obtaining heterogeneous polyacid catalyst is to play polyacid in conjunction with metal-organic framework material
Construct the polyacid Base Metal organic framework materials (POMOF) of crystallization, which, which can not only integrate polyacid and metal, machine frame
Both frame materials advantage can also improve the structural stability and thermal stability of this composite material.Up to the present, some
POMOF material be catalyzed ester-type hydrolysis, chemical warfare agent degradation, sulfide oxidation, in terms of show it is higher
Catalytic activity and good stable circulation can (Du, D.Y., Qin, J.S., Li, S.L., Su, Z.M., Lan, Y.Q.,
Chem.Soc.Rev.2014,43, 4615-4632；Zhong,X.H.,Lu,Y.,Luo,F.,Liu,Y.W.,Li,X.H.,Liu,
S.X.,Chem.Eur. J.2018,24,3045-3051).But there are no POMOF crystalline materials to be used for oxidation of alkyl so far
The document report of the corresponding quinones of the substrate selectivity synthesis of phenol or other low-oxidation-states, therefore research and develop the more of novel structure
Acidic group metal organic frame crystalline material is used for high activity and synthesizes 1,4-benzoquinone class compound with high selectivity, is very necessary
's.
Summary of the invention
It is an object of the invention to synthesize a kind of polyacid Base Metal organic frame (POMOF) crystalline material, while providing crystalline substance
The preparation method of body material, synthesized POMOF material can be used as efficient catalyst for catalysis alkyl phenolic, alkylbenzene and
2- methyl naphthalene oxidative synthesis is to benzene a kind of jade class compound, and the catalyst can be reused.
Technical solution of the present invention:
A kind of polyacid Base Metal organic frame crystalline material, chemical formula are H [CuII(ttb)(H2O)3]2[CuII(ttb)
Cl]2[PW12O40]·4H2O and [ClCu6 I(trz)4][ClCu5 I(trz)4]2[CuII(H2O)][PW12O40]；Wherein, Httb=
1- (tetrazolium -5- base) -4- (triazol-1-yl) benzene, trz=1,2,4- triazoles.
The polyacid Base Metal organic frame crystalline material belongs to monoclinic system；
When ligand is Httb, the space group of crystalline material 1 is P21/ n, cell parameter are β=99.2120 (10) °,
When ligand is trz, the space group of crystalline material 2 is C2/c, and cell parameter is β=113.765 (3) °,
Include independent [PW in half of crystallography in asymmetric cell in crystalline material 112O40]3–Ion, two divalent
Copper ion, 1- (tetrazolium -5- base) -4- (triazol-1-yl) benzene ligand (ttb) of two deprotonations, a chloride ion and two
Crystalline water molecules；Two copper ions have different configurations, and one is the octoploids structures of hexa-coordinate, and another kind is pentacoordinate
Tetragonal pyramid configuration；Being connected between copper ion by ttb ligand and forming two kinds of structural units is two core { Cu respectively2(ttb)2And
{ the Cu of four cores4(ttb)4}；Subunit { the Cu of double-core first2(ttb)2One-dimensional by sharing copper ion interconnection generation
Structure, adjacent one-dimensional chain further through four cores subunit { Cu4(ttb)4Be connected with each other, it is generated along c-axis direction two-dimensional wavy
Metal complex layer, the wave crest and trough of adjacent wavy two-dimensional layer meet, and forms one-dimensional channels, [PW12O40]3–Anion
It is filled in as bidentate ligand and forms three-dimensional polyacid Base Metal organic frame in one-dimensional channels；
There are half of [PW in the asymmetric cell of crystalline material 212O40]3-Ion, 8 points 5 copper ions, six 1,2,
4- Triazole ligand (trz), 1 point 5 chloride ion and half of water of coordination molecule；There are three types of different for 8 points 5 copper ion tools
Coordination configuration, the respectively triangle of the plane triangle configuration of three-fold coordination, the plane square configuration of four-coordination and pentacoordinate are double
Bore configuration；The subunit of four cores and eight cores is constituted between copper ion by trz ligand；Subunit { the Cu of each four core4
(trz)4Cl } with the subunit { Cu of four eight cores8(trz)8Be connected, and the subunit { Cu of each eight core8(trz)8And four
Subunit { the Cu of four cores4(trz)4Cl } and four eight cores subunit { Cu8(trz)8Be connected, form two-dimensional grid-like gold
Metal complex layer, adjacent two-dimensional layer are packed together in parallel, form the three-dimensional porous frame with one-dimensional zigzag channel,
[PW12O40]3–Anion is filled in these one-dimensional channels by Cu-O interaction as ten tooth ligands, forms three-dimensional
Polyacid Base Metal organic frame.
The preparation method of a kind of polyacid Base Metal organic frame crystalline material, synthesizes to obtain, preparation side using hydro-thermal method
Method specifically comprises the following steps:
1) presoma K is synthesized by conventional method4[PW11VVO40]·xH2O and H3PW12O42·xH2O (Domaille,
P.J.,Inorg.Synth.,John Wiley&Sons.:1990；Vol.27,96-104；John,C.B. J.,
Inorg.Synth.,John Wiley&Sons.:1939；Vol.1,132-133)；
2-1) by K4[PW11VVO40]·xH2O is dissolved in water, and copper (II) salt and Httb is then added, wherein K4
[PW11VVO40]·xH2O, the ratio between amount of substance of copper (II) salt and Httb is 1:4-4.5:2.3；After stirring 0.5h, with dilute salt
PH is adjusted to 2.0-2.8 by acid to be continued to stir 0.5h, is then transferred into ptfe autoclave 180 DEG C of heating in an oven about
It after 6 days, is slowly cooled to room temperature, obtains green blocky crystalline material, washed and drying to obtain three-dimensional POMOF material.
2-2) by K4[PW11VVO40]·xH2O is dissolved in water, and copper (II) salt and trz is then added, wherein K4
[PW11VVO40]·xH2O, the ratio between amount of substance of copper (II) salt and 1,2,4- triazole is 1.2:7-7.5:11.5；Stir 0.5h
Afterwards, pH is adjusted to 1.4-1.6 with dilute hydrochloric acid to continue to stir 0.5h, is then transferred into ptfe autoclave in an oven
It after 180 DEG C are heated about 5 days, is slowly cooled to room temperature, obtains brownish black bulk crystalline material, washed and drying to obtain is three-dimensional
POMOF material；
The step 2-2) in K4[PW11VVO40]·xH2O is by H3PW12O42·xH2O and ammonium metavanadate replacement.
A kind of polyacid Base Metal organic frame crystalline material is arrived in selective oxidation alkyl phenol, alkoxy benzene and 2- methyl naphthalene
Accordingly to the catalytic applications of benzene a kind of jade class compound, operate as follows:
The isometric in the mixed solvent of the acetonitrile and water that catalyst, substrate and internal standard compound naphthalene are added to, is heated under stirring
After 60 DEG C, aqueous hydrogen peroxide solution is added.0.2 μ L supernatant is drawn with micro gas phase sample introduction needle, is carried out using gas chromatograph
Analysis.Wherein, catalyst, substrate, internal standard compound and H2O2Molar ratio be 0.005-0.03:1:1:1-5, concentration of substrate is
0.5M。
Beneficial effects of the present invention:
(1) POMOF material of the present invention can be used as efficient conjunction of the heterogeneous catalysis catalysis to benzene a kind of jade class compound
At especially in the reaction of catalysis 2,3,6-TMP (TMP) synthesis 2,3,5- trimethylbenzene a kind of jade (TMBQ), in 10-
20min may be implemented to convert TMP completely and high yield obtain TMBQ (96%-99%).
(2) for POMOF material of the present invention in the reaction of catalysis TMP synthesis TMBQ, transformation frequency is up to 300-
600h-1, this is also highest turn in the reaction for the heterogeneous catalysis system catalysis TMP synthesis TMBQ based on polyacid being currently known
Change frequency.
(3) after ten circulations, structure and catalytic activity remain to maintain initial POMOF material of the present invention
State and level.And at dynamics areas (when conversion ratio is less than 20%), catalyst still maintains excellent after 5 circulations
Catalytic activity.
(4) POMOF material of the present invention shows that excellent catalytic performance, catalytic performance are derived from Keggin ion
With the synergistic effect between Cu- organic frame.
(5) POMOF material of the present invention determines that its structure, structure novel are first by Advances in crystal X-ray diffraction
Example is for being catalyzed the POMOF crystalline material of TMP synthesis TMBQ.
Detailed description of the invention
Fig. 1 (a) is the asymmetric cell of crystalline material 1 of the present invention, (b) two core subunit { Cu in crystalline material 12
(ttb)2, (c) four core subunit { Cu in crystalline material 14(ttb)4, two core subunit { Cu (d) are based in crystalline material 12
(ttb)2One-dimensional chain structure, (e) two-dimensional layer in crystalline material 1, (f) polyacid Base Metal three-dimensional in crystalline material 1 is organic
Frame structure.
Fig. 2 (a) is the asymmetric cell of crystalline material 2 of the present invention, (b) four core subunit { Cu in crystalline material 24
(trz)4, (c) eight core subunit { Cu in crystalline material 28(trz)8, (d) the two-dimensional metallic complex in crystalline material 2
Layer (e) occupies one-dimensional channels with Keggin ion in (f) crystalline material 2 and constructs three-dimensional polyacid Base Metal organic framework,
(g) in crystalline material 2 polyoxoanion coordination mode.
Fig. 3 (a) is the infrared spectroscopy of crystalline material 1 of the present invention, (b) infrared spectroscopy of crystalline material 2 of the present invention.
Fig. 4 (a) is the X-ray powder diffraction figure of crystalline material 1 of the present invention, (b) the X-ray powder of crystalline material 2 of the present invention
Last diffraction pattern.
Fig. 5 (a) is that the volume ratio of acetonitrile and water is catalyzed the influence of TMP oxidation, (b) body of acetonitrile and water to crystalline material 1
Product compares the influence that crystalline material 2 is catalyzed TMP oxidation.
Fig. 6 is the influence of the crystalline material 1 and 2 pair catalysis TMP oxidation susceptibility of ten times of amounts.
Fig. 7 (a) and (b) are the circulation experiment result that crystalline material 1 and 2 is catalyzed TMP oxidation respectively.
Fig. 8 (a) and (b) are the X-ray powder diffraction spectrogram of the catalysis reaction of crystalline material 1 and 2 front and back respectively, (c) and
(d) infrared spectrum of the catalysis of crystalline material 1 and 2 front and back.
Fig. 9 is the influence that radical scavenger is catalyzed TMP oxidation to crystalline material 1 and 2.
Figure 10 is the UV-visible spectrum that crystalline material 1 is added before and after hydrogen peroxide.
Figure 11 is the raman spectrum that crystalline material 1 is added before and after hydrogen peroxide.
Figure 12 is the reaction mechanism of crystalline material catalysis TMP oxidative synthesis TMBQ.
Specific embodiment
Below will by specific embodiment, the present invention is described in further detail, but herein only for explain the present invention and
It is non-to be used to limit the present invention.
Embodiment 1:
Polyacid Base Metal organic frame crystalline material H [CuII(ttb)(H2O)3]2[CuII(ttb)Cl]2[PW12O40]·
4H2The preparation method of O, the specific steps are as follows:
1) presoma K is synthesized by conventional method4[PW11VVO40]·xH2O(Domaille,P.J.,Inorg.
Synth.,John Wiley&Sons.:1990；Vol.27,96-104)；
2)K4[PW11VVO40]·xH2O (0.3g ,~0.1mmol) is dissolved in 10mL water, and CuCl is then added2·2H2O
(0.0682g, 0.40mmol) and Httb (0.0491g, 0.23mmol), continues to stir 0.5h, adjusts pH to 2.0- with dilute hydrochloric acid
2.8, continue stir 0.5h after, be transferred in ptfe autoclave, in an oven 180 DEG C heating about 6 days after, Slow cooling
To room temperature, green blocky crystalline material is obtained, yield is about 52% (based on K4[PW11VVO40]·xH2O)。
The 0.0682g CuCl2·2H2O can be by 0.0767g CuCl2·2H2O or 0.0998~0.1124g
CuSO4·5H2O or 0.0966~0.1087g CuNO3·3H2O replacement.
Embodiment 2:
Polyacid Base Metal organic frame crystalline material [ClCu6 I(trz)4][ClCu5 I(trz)4]2[CuII(H2O)]
[PW12O40] preparation method, the specific steps are as follows:
1) presoma K is synthesized by conventional method4[PW11VVO40]·xH2O(Domaille,P.J.,Inorg.
Synth.,John Wiley&Sons.:1990；Vol.27,96-104)；
2)K4[PW11VVO40]·xH2O (0.35g ,~0.12mmol) is dissolved in 10mL water, and Cu is then added
(OAc)2·H2O (0.1497g, 0.75mmol) and trz (0.0794g, 1.15mmol) continues to stir 0.5h, be adjusted with dilute hydrochloric acid
PH to 1.4-1.6, continue stir 0.5h after, be transferred in ptfe autoclave in an oven 180 DEG C heating about 5 days after,
It is slowly cooled to room temperature, obtains brownish black bulk crystalline material, yield is about 61% (based on K4[PW11VVO40]·xH2O)。
The 0.1497g Cu (OAc)2·H2O can be by 0.1398g Cu (OAc)2·H2O or 0.1194~0.1279g
CuCl2·2H2O replacement.
Embodiment 3:
Polyacid Base Metal organic frame crystalline material [ClCu6 I(trz)4][ClCu5 I(trz)4]2[CuII(H2O)]
[PW12O40] preparation method, the specific steps are as follows:
1) presoma H is synthesized by conventional method3PW12O42·xH2O(John,C.B.J.,Inorg.Synth., John
Wiley&Sons.:1939；Vol.1,132-133)；
2)H3PW12O42·xH2O (0.32g ,~0.12mmol) is dissolved in 10mL water, and Cu (OAc) then is added2·H2O
(0.1497g, 0.75mmol) and trz (0.0794g, 1.15mmol), continues to stir 0.5h, adjusts pH to 1.4- with dilute hydrochloric acid
1.6, continue stir 0.5h after, be transferred in ptfe autoclave in an oven 180 DEG C heating about 5 days after, Slow cooling
To room temperature, brownish black bulk crystalline material is obtained, yield is about 31% (based on K4[PW12O40]·xH2O)。
The 0.1497g Cu (OAc)2·H2O can be by 0.1398g Cu (OAc)2·H2O or 0.1194~0.1279g
CuCl2·2H2O replacement.
Product in above-described embodiment is detected, the chemical formula for obtaining POMOF material is H [CuII(ttb)
(H2O)3]2[CuII(ttb)Cl]2[PW12O40]·4H2O and [ClCu6 I(trz)4][ClCu5 I(trz)4]2[CuII(H2O)]
[PW12O40].Wherein, Httb=1- (tetrazolium -5- base) -4- (triazol-1-yl) benzene, trz=1,2,4- triazoles.The present invention mentions
Crystal structure such as Fig. 1 and 2. of the POMOF material of confession
The product in above-described embodiment is detected using infrared spectroscopy, Fig. 3 is two POMOF materials of the invention
Infrared spectrogram, show the W-O of polyoxoaniont、W-Ob、W-Oc、W-OaAnd P-OaEigen vibration absorption peak, Yi Jipei
The characteristic absorption peak of body molecule and hydrone.
The product in above-described embodiment is detected using X-ray powder diffraction, Fig. 4 is two POMOF of the present invention
The X-ray powder diffraction spectrogram of material, the theoretical map that wherein experimental patterns and based single crystal diffraction are fitted is almost the same, card
The bright sample for property test is pure.
The present invention using the selective oxidation of 2,3,6-TMP (TMP) as model reaction, has evaluated above-mentioned first
Activity of the prepared crystalline material as heterogeneous catalysis, catalytic oxidation route are as follows in embodiment:
It is detected using catalytic result of the gas-chromatography to crystalline material prepared in Examples 1 and 2, table 1 summarizes
Corresponding catalytic result, hydrogen peroxide is oxidant, in 10-20min, TMP may be implemented and convert completely, corresponding 2,3,
5- trimethyl reaches 96%-99% to the selectivity of benzene a kind of jade (TMBQ), and transformation frequency (TOF) is 300h–1And 600h–1。
It is examined using the optimum reaction condition that gas-chromatography prepares crystalline material catalysis TMP oxidation to Examples 1 and 2
It surveys, table 2 summarizes influence of the different solvents to the catalysis TMP oxidation of POMOF material, and acetonitrile is optimum solvent as the result is shown；Fig. 5 is
The influence of TMP oxidation is catalyzed to POMOF material for the volume ratio of acetonitrile and water, as the result is shown when acetonitrile and water are isometric,
The catalytic effect of POMOF material is best；Table 3 summarizes influence of the dosage of hydrogen peroxide to the catalysis TMP oxidation of POMOF material,
Optimum amount is 1.0mmol as the result is shown；Table 4 summarizes influence of the reaction temperature to the catalysis TMP oxidation of POMOF material, as a result
Show that optimum temperature is 60 DEG C.
Crystalline material is prepared as the application prospect of heterogeneous catalysis to Examples 1 and 2 using gas-chromatography to examine
Survey, Fig. 6 be after the dosage of catalyst system all materials increases 10 times POMOF material catalysis TMP oxidation as a result, result is aobvious
Show in 25min, POMOF material still can be catalyzed 90% or more TMP conversion, the selectivity of TMBQ also reach 90% with
On.
It is detected using the circulation result that gas-chromatography prepares crystalline material catalysis TMP oxidation to Examples 1 and 2, Fig. 7
As by the catalytic result of 10 circulations, catalyst its catalytic activity after 10 circulations is still maintained at higher as the result is shown
Level.
Crystalline material catalysis reaction fore-and-aft stability is prepared to Examples 1 and 2 using XRD and infrared spectroscopy to detect,
Fig. 8 is that the X-ray powder diffraction comparison diagram of POMOF material catalysis reaction front and back and infrared comparison diagram, comparing result are shown
There is no variations before and after catalysis for the structure of POMOF material.
It is carried out using the free radical capture experimental result that gas-chromatography prepares crystalline material catalysis TMP oxidation to embodiment 1
Detection, Fig. 9 are the reaction result that different radical scavengers are added, the results showed that POMOF material is catalyzed TMP oxidative synthesis
There may be oxygen radicals and carbon radicals for the process of TMBQ, i.e., aoxidize TMP by free radical mechanism.
Prepared by crystalline material in H to embodiment 1 using UV-visible spectrum and Raman spectrum2O2Under the conditions of the mistake that is formed
Oxidation polyacid compound is detected, and Figure 10 is that UV-visible spectrum before and after micro hydrogen peroxide is added, and Figure 11 is
Micro hydrogen peroxide front and back raman spectrum is added, the results showed that POMOF material can be that peroxide is more by hydrogen peroxide oxidation
Sour species catalysis TMP oxidation.
Figure 12 gives the mechanism that crystalline material catalysis TMP of the present invention is oxidized to TMBQ, includes free radical mechanism and generation
Oxygen transfer mechanism two parts of peroxyl species.
Prepared by crystalline material to Examples 1 and 2 using gas-chromatography and is catalyzed the synthesis of other substrate oxidations to the result of benzene a kind of jade
It is detected, table 5 summarizes the catalytic result of different alkyl phenols, alkoxy benzene and 2- methyl naphthalene, as the result is shown POMOF material pair
Different alkyl phenols can show relatively good catalytic activity, and palkoxy benzene and 2- methyl naphthalene can also show certain urge
Change activity.
1 POMOF material of table is catalyzed TMP oxidative synthesis TMBQ
Influence of 2 different solvents of table to POMOF material catalysis TMP oxidative synthesis TMBQ
Influence of the dosage of 3 hydrogen peroxide of table to POMOF material catalysis TMP oxidative synthesis TMBQ
Influence of 4 reaction temperature of table to POMOF material catalysis TMP oxidative synthesis TMBQ
5 POMOF material of table is catalyzed different substrate oxidations and synthesizes accordingly to benzene a kind of jade
Various heterogeneous catalysis catalytic activity of the table 6 in recent years for TMP oxidation compare
Claims (5)
1. a kind of polyacid Base Metal organic frame crystalline material, which is characterized in that the polyacid Base Metal organic frame crystalline material
Chemical formula is H [CuII(ttb)(H2O)3]2[CuII(ttb)Cl]2[PW12O40]·4H2O and [ClCu6 I(trz)4][ClCu5 I
(trz)4]2[CuII(H2O)][PW12O40]；Wherein, Httb=1- (tetrazolium -5- base) -4- (triazol-1-yl) benzene, trz=1,2,
4- triazole；
The polyacid Base Metal organic frame crystalline material belongs to monoclinic system；
When ligand is Httb, the space group of crystalline material 1 is P21/ n, cell parameter are β=99.2120 (10) °,
When ligand is trz, the space group of crystalline material 2 is C2/c, and cell parameter is β=113.765 (3) °,
Include independent [PW in half of crystallography in asymmetric cell in crystalline material 112O40]3–Ion, two cuprics from
Son, 1- (tetrazolium -5- base) -4- (triazol-1-yl) benzene ligand (ttb) of two deprotonations, a chloride ion and two crystallizations
Hydrone；Two copper ions have different configurations, and one is the octoploids structure of hexa-coordinate, another kind is the four directions of pentacoordinate
Bore configuration；Being connected between copper ion by ttb ligand and forming two kinds of structural units is two core { Cu respectively2(ttb)2He Sihe
{ Cu4(ttb)4}；Subunit { the Cu of double-core first2(ttb)2By sharing the one-dimensional structure of copper ion interconnection generation,
Adjacent one-dimensional chain further through four cores subunit { Cu4(ttb)4Be connected with each other, two-dimensional wavy gold is generated along c-axis direction
Metal complex layer, the wave crest and trough of adjacent wavy two-dimensional layer meet, and form one-dimensional channels, [PW12O40]3–Anion conduct
Bidentate ligand, which is filled in, forms three-dimensional polyacid Base Metal organic frame in one-dimensional channels；
There are half of [PW in the asymmetric cell of crystalline material 212O40]3-Ion, 8 points 5 copper ions, six 1,2,4- tri-
Nitrogen azoles ligand (trz), 1 point 5 chloride ion and half of water of coordination molecule；There are three types of different coordinations for 8 points 5 copper ion tools
The trigonal biyramid structure of configuration, respectively the plane triangle configuration of three-fold coordination, the plane square configuration of four-coordination and pentacoordinate
Type；The subunit of four cores and eight cores is constituted between copper ion by trz ligand；Subunit { the Cu of each four core4
(trz)4Cl } with the subunit { Cu of four eight cores8(trz)8Be connected, and the subunit { Cu of each eight core8(trz)8And four
Subunit { the Cu of four cores4(trz)4Cl } and four eight cores subunit { Cu8(trz)8Be connected, form two-dimensional grid-like gold
Metal complex layer, adjacent two-dimensional layer are packed together in parallel, form the three-dimensional porous frame with one-dimensional zigzag channel,
[PW12O40]3–Anion is filled in these one-dimensional channels by Cu-O interaction as ten tooth ligands, forms three-dimensional
Polyacid Base Metal organic frame.
2. the preparation method of a kind of polyacid Base Metal organic frame crystalline material, which is characterized in that it synthesizes to obtain using hydro-thermal method,
Include the following steps:
1) presoma K is synthesized by conventional method4[PW11VVO40]·xH2O and H3PW12O42·xH2O；
2-1) by K4[PW11VVO40]·xH2O is dissolved in water, and copper (II) salt and Httb is then added, wherein K4[PW11VVO40]·
xH2O, the ratio between amount of substance of copper (II) salt and Httb is 1:4-4.5:2.3；After stirring 0.5h, pH is adjusted to dilute hydrochloric acid
2.0-2.8 continue stir 0.5h, be then transferred into ptfe autoclave in an oven 180 DEG C heating about 6 days after, slowly
It is cooled to room temperature, obtains green blocky crystalline material, washed and drying to obtain three-dimensional POMOF material；
2-2) by K4[PW11VVO40]·xH2O is dissolved in water, and copper (II) salt and trz is then added, wherein K4[PW11VVO40]·
xH2O, the ratio between amount of substance of copper (II) salt and 1,2,4- triazole is 1.2:7-7.5:11.5；After stirring 0.5h, dilute hydrochloric acid is used
PH is adjusted to 1.4-1.6 to continue to stir 0.5h, is then transferred into ptfe autoclave 180 DEG C of heating about 5 in an oven
It after it, is slowly cooled to room temperature, obtains brownish black bulk crystalline material, washed and drying to obtain three-dimensional POMOF material.
3. preparation method according to claim 2, which is characterized in that the step 2-2) in K4[PW11VVO40]·xH2O
By H3PW12O42·xH2O and ammonium metavanadate replacement.
4. preparation method according to claim 2 or 3, which is characterized in that copper (II) salt is copper acetate or chlorination
Copper.
5. a kind of polyacid Base Metal organic frame crystalline material is in selective oxidation alkyl phenol, alkoxy benzene and 2- methyl naphthalene to phase
The catalytic applications to benzene a kind of jade class compound answered, which is characterized in that steps are as follows:
The isometric in the mixed solvent of the acetonitrile and water that catalyst, substrate and internal standard compound naphthalene are added to, is heated to 60 DEG C under stirring
Afterwards, aqueous hydrogen peroxide solution is added；With micro gas phase sample introduction needle Aspirate supernatant, analyzed using gas chromatograph；Wherein,
Catalyst, substrate, internal standard compound and H2O2Molar ratio be 0.005-0.03:1:1:1-5, concentration of substrate is 0.5M.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910641308.7A CN110358102B (en) | 2019-07-16 | 2019-07-16 | Polyacid-based metal organic framework crystal material, preparation method and application of polyacid-based metal organic framework crystal material in catalytic synthesis of hydroquinone compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910641308.7A CN110358102B (en) | 2019-07-16 | 2019-07-16 | Polyacid-based metal organic framework crystal material, preparation method and application of polyacid-based metal organic framework crystal material in catalytic synthesis of hydroquinone compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110358102A true CN110358102A (en) | 2019-10-22 |
| CN110358102B CN110358102B (en) | 2021-04-20 |
Family
ID=68219701
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910641308.7A Active CN110358102B (en) | 2019-07-16 | 2019-07-16 | Polyacid-based metal organic framework crystal material, preparation method and application of polyacid-based metal organic framework crystal material in catalytic synthesis of hydroquinone compounds |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110358102B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112778536A (en) * | 2021-01-18 | 2021-05-11 | 太原科技大学 | Dawson type polyacid-based metal-BBPTZ organic framework material and preparation method and application thereof |
| CN112808311A (en) * | 2020-12-14 | 2021-05-18 | 华南理工大学 | Zirconium-based metal organic framework material and preparation method and application thereof |
| CN113174055A (en) * | 2021-04-27 | 2021-07-27 | 吉林大学 | Porous ion super-molecular framework material, preparation method and application |
| CN114395133A (en) * | 2021-12-03 | 2022-04-26 | 常州大学 | Isopoly-vanadic acid coordination polymer catalyst and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107188241A (en) * | 2017-05-27 | 2017-09-22 | 大连理工大学 | A kind of Evans Showell types polyacid and the compound of alkaline-earth metal and preparation method thereof and catalytic applications |
| JP2017185469A (en) * | 2016-04-08 | 2017-10-12 | 国立大学法人静岡大学 | Burned body of polyoxomethalate compound, photocatalyst and method for manufacturing burned body of polyoxomethalate compound |
| CN107243361A (en) * | 2017-07-11 | 2017-10-13 | 东北师范大学 | A kind of preparation method and application of polyacid Base Metal organic backbone nanocrystalline catalyst |
| WO2018202420A1 (en) * | 2017-05-05 | 2018-11-08 | Exxonmobil Chemical Patents Inc. | Polyoxometalates comprising noble metals and carboxylate-based capping groups and metal clusters thereof |
| CN108948100A (en) * | 2018-07-16 | 2018-12-07 | 哈尔滨理工大学 | The preparation and application of two kinds of three-dimensional pseudorotaxane type polyacid Base Metal organic framework materials |
| CN109876865A (en) * | 2019-04-02 | 2019-06-14 | 哈尔滨理工大学 | A kind of preparation of the polyacid Base Metal organic frame of intercalation configuration and catalytic performance |
-
2019
- 2019-07-16 CN CN201910641308.7A patent/CN110358102B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017185469A (en) * | 2016-04-08 | 2017-10-12 | 国立大学法人静岡大学 | Burned body of polyoxomethalate compound, photocatalyst and method for manufacturing burned body of polyoxomethalate compound |
| WO2018202420A1 (en) * | 2017-05-05 | 2018-11-08 | Exxonmobil Chemical Patents Inc. | Polyoxometalates comprising noble metals and carboxylate-based capping groups and metal clusters thereof |
| CN107188241A (en) * | 2017-05-27 | 2017-09-22 | 大连理工大学 | A kind of Evans Showell types polyacid and the compound of alkaline-earth metal and preparation method thereof and catalytic applications |
| CN107243361A (en) * | 2017-07-11 | 2017-10-13 | 东北师范大学 | A kind of preparation method and application of polyacid Base Metal organic backbone nanocrystalline catalyst |
| CN108948100A (en) * | 2018-07-16 | 2018-12-07 | 哈尔滨理工大学 | The preparation and application of two kinds of three-dimensional pseudorotaxane type polyacid Base Metal organic framework materials |
| CN109876865A (en) * | 2019-04-02 | 2019-06-14 | 哈尔滨理工大学 | A kind of preparation of the polyacid Base Metal organic frame of intercalation configuration and catalytic performance |
Non-Patent Citations (5)
| Title |
|---|
| CHAI DONGFENG 等: "Polyoxometalate-based metal-organic frameworks for boosting electrochemical capacitor performance", 《CHEMICAL ENGINEERING JOURNAL》 * |
| HAIYAN AN 等: "Hybrid dimers based on metal-substituted Keggin polyoxometalates (metal = Ti, Ln) for cyanosilylation catalysis", 《DALTON TRANSACTIONS 》 * |
| T. A. TRUBITSYNA 等: "Kinetics and Mechanism of the Oxidation", 《KINETICS AND CATALYSIS》 * |
| ZHAO XIUXIA 等: "Polyoxometalate-Based Metal–Organic Frameworks as Visible-Light-Induced Photocatalysts", 《INORGANIC CHEMISTRY》 * |
| 吴永川 等: "铜基框架囊包多酸晶态材料的制备与电催化性能", 《齐齐哈尔大学学报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112808311A (en) * | 2020-12-14 | 2021-05-18 | 华南理工大学 | Zirconium-based metal organic framework material and preparation method and application thereof |
| CN112778536A (en) * | 2021-01-18 | 2021-05-11 | 太原科技大学 | Dawson type polyacid-based metal-BBPTZ organic framework material and preparation method and application thereof |
| CN112778536B (en) * | 2021-01-18 | 2022-09-27 | 太原科技大学 | Dawson type polyacid-based metal-BBPTZ organic framework material and preparation method and application thereof |
| CN113174055A (en) * | 2021-04-27 | 2021-07-27 | 吉林大学 | Porous ion super-molecular framework material, preparation method and application |
| CN113174055B (en) * | 2021-04-27 | 2023-08-18 | 吉林大学 | Porous ion supermolecular framework material, preparation method and application |
| CN114395133A (en) * | 2021-12-03 | 2022-04-26 | 常州大学 | Isopoly-vanadic acid coordination polymer catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110358102B (en) | 2021-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110358102A (en) | A kind of polyacid Base Metal organic frame crystalline material, preparation method and its catalyze and synthesize application to benzene a kind of jade class compound | |
| Cui et al. | Rigid versus semi-rigid bis (imidazole) ligands in the assembly of two Co (II) coordination polymers: structural variability, electrochemical properties and photocatalytic behavior | |
| Tan et al. | Cluster-organic framework materials as heterogeneous catalysts for high efficient addition reaction of diethylzinc to aromatic aldehydes | |
| Uematsu et al. | Molybdenum-doped α-MnO 2 as an efficient reusable heterogeneous catalyst for aerobic sulfide oxygenation | |
| Wang et al. | Effect of flexible bis-pyridyl-bis-amide ligands and dicarboxylates on the assembly and properties of multifunctional Cu (II) metal–organic coordination polymers | |
| Li et al. | Copper-containing polyoxometalate-based metal–organic frameworks as highly efficient heterogeneous catalysts toward selective oxidation of alkylbenzenes | |
| Ma et al. | Polyoxometalate-based metal–organic coordination networks for heterogeneous catalytic desulfurization | |
| Gutierrez et al. | New application of decaniobate salt as basic solid in the synthesis of 4 H-pyrans by microwave assisted multicomponent reactions | |
| Liang et al. | Synthesis and structure of a bismuth-cobalt bimetal coordination polymer for green efficient photocatalytic degradation of organic wastes under visible light | |
| Dou et al. | Imidazole-induced self-assembly of polyoxovanadate cluster organic framework for efficient Knoevenagel condensation under mild conditions | |
| Shi et al. | A molybdate-incorporated cooperative catalyst: High efficiency in the assisted tandem catalytic synthesis of cyclic carbonates from CO2 and olefins | |
| CN109772459A (en) | A kind of chirality polyacid Base Metal organic framework materials and its preparation method and application | |
| Ren et al. | Three POM-based coordination polymers: hydrothermal synthesis, characterization, and catalytic activity in epoxidation of styrene | |
| Yu et al. | Assembly of co-bimb-polyoxotungstate hybrids: from 1D chain to 3D framework influenced by the charge of Keggin anions | |
| Shi et al. | A novel photosensitizing decatungstate-based MOF: Synthesis and photocatalytic oxidation of cyclohexane with molecular oxygen | |
| Xiao et al. | Three new compounds based on similar molybdenum–vanadium clusters and several types of copper complexes | |
| Cong et al. | Two unusual 3D honeycomb networks based on Wells–Dawson arsenomolybdates with d 10 transition-metal-pyrazole connectors | |
| Gao et al. | Two novel Zn (II) coordination polymers constructed by the same dicarboxylate and different bis-imidazole as co-ligand: syntheses, crystal structures and properties | |
| Manna et al. | Fixing CO2 under Atmospheric Conditions and Dual Functional Heterogeneous Catalysis Employing Cu MOFs: Polymorphism, Single-Crystal-to-Single-Crystal (SCSC) Transformation and Magnetic Studies | |
| Guo et al. | Structural influences of arsenic–vanadium clusters and transition metal complexes on final structures of arsenic–vanadium-based hybrids | |
| Guo et al. | The synthesis and characterization of three organic–inorganic hybrids based on different transition metal complexes and {As 8 V 14 O 42 (H 2 O)} clusters | |
| Niu et al. | Ionothermal synthesis, structure and optical properties of three new organic–inorganic hybrid imidazolium bromoplumbate complexes | |
| Gao et al. | Supramolecular Assembly Based on Octamolybdate and Triazole Derivative: Crystal Structure and Catalytic Application in Olefin Epoxidation | |
| CN103977839B (en) | A kind of ionic organic metal tungstates epoxidation catalyst and preparation method thereof | |
| CN107199051A (en) | A kind of copper heterogeneous catalyst of pyridine coordination and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |