CN105195179A - Solid superacid catalyst and preparation method thereof - Google Patents

Solid superacid catalyst and preparation method thereof Download PDF

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CN105195179A
CN105195179A CN201510771286.8A CN201510771286A CN105195179A CN 105195179 A CN105195179 A CN 105195179A CN 201510771286 A CN201510771286 A CN 201510771286A CN 105195179 A CN105195179 A CN 105195179A
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李亚丰
王镇
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Changchun University of Technology
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Abstract

The invention provides a solid superacid catalyst and a preparation method thereof. According to the method, an adopted carrier-ZrO2 is prepared by calcining high-crystalline UIO-66 and analogues. The high-crystalline UIO-66 and the analogues have the characteristics of having same topological structures; each of the high-crystalline UIO-66 and the analogues comprises a clustered ZrO4(OH)4(CO2)12. A calcining result shows that the content of a square phase of obtained ZrO2 is relatively high, and therefore, compared with SO4<2->/ZrO2 catalysts prepared by adopting other preparation methods, the SO4<2->/ZrO2 catalyst prepared by adopting the preparation method provided by the invention has the obvious advantages that (1) the content of sulphur in the catalyst is within 3-20%, and a superacid performance is realized; (2) other metal ions are not required to be introduced to be used as a stabilizer of the square phase ZrO2; and (3) a process flow is short, the device input is small, the operation is easy and convenient, and the preparation method is suitable for mass production.

Description

A kind of solid super acid catalyst and preparation method
Technical field
The present invention relates to a kind of solid super acid catalyst and preparation method.
Background technology
In the petrochemical industry and fine chemicals production in modern times, acid catalyst is occupied an leading position, as: esterification, acylation reaction etc.Sometimes catalyst (as: H is by liquid acid in Chemical Manufacture 2sO 4, HF, H 3pO 4deng).This kind of liquid acid catalytic reaction is carried out under homogeneous phase condition, brings many inconvenience to production, as: catalyst not easily with raw material, product separation, etching apparatuses etc., the discharge of spent acid simultaneously also can bring serious pollution to environment.Solid super-strong acid has the superpower acidity of liquid acid, and the feature such as low corrosion, Heat stability is good, easily separated, recyclable regeneration, therefore the research of solid super-strong acid becomes a focus of catalyst research.1979 Hino [1] report SO 4 2-/ MxOy type solid super-strong acid.Scholars conducts extensive research it in decades, develops a series of SO 4 2-/ MxOy type solid super-strong acid.It has catalytic activity high, selective good, not etching apparatus, easily and product separation, can the feature [2] such as Reusability.With SO in this system 4 2-/ ZrO 2acidity the strongest, also maximum to its research.SO 4 2-/ ZrO 2solid super acid catalyst has high catalytic activity in many acid catalyzed reactions are as esterification, acidylate, alkylation and isomerization etc., hydrothermal stability, product are easy to be separated, the not advantage such as etching apparatus, free from environmental pollution and reusability, therefore more and more obtains the concern of numerous researcher.
ZrO 2(zirconium dioxide) has three kinds of crystalline phases, is monoclinic phase (monoclinic, also referred to as m-phase), Tetragonal (tetragonal, also referred to as t-phase) and Emission in Cubic (cubic, also referred to as c-phase) respectively.In configuration aspects, especially at Zr by the ligancy of O, in monoclinic phase, the O ligancy of Zr is 7, and the O ligancy of Zr is 8 in Tetragonal and Emission in Cubic.There is Volume Changes in phase in version process, material volume during from monoclinic phase to tetragonal phase converting, can be made to shrink 5%, material volume can be made when monoclinic phase changes to expand about 8% by Tetragonal, and this process is reversible phase transition process.Pure ZrO 2at room temperature only have m-phase stable existence, could exist with t-phase at 1200 ° of more than C, and could exist with c-phase at 2300 ° of more than C.ZrO 2own acid-fast alkali-proof and heat endurance is high, has meso-hole structure, specific area and Al 2o 3close, relatively greatly, but being less than zeolite, is therefore excellent carrier.At ZrO 2three kinds of crystalline phases in, monoclinic phase does not have catalytic property substantially, and Tetragonal is relevant to catalysis, and Emission in Cubic is relevant with the solid fuel cell of fast-ionic conductor.
At normal temperatures, pure ZrO 2be m-phase, therefore will obtain the Tetragonal of ambient stable, need ZrO 2carry out namely modification of adulterating.Some metal ions, transition metal ions and rare earth ion are if Ca, Ba, Zn, Ni, Co, Mn, Pt, Pd, W, Mo, Y, Sm, La etc. are for the ZrO of stable Tetragonal 2[3-4].Prepare for utilizing inorganic zirconium salts and stablize Tetragonal ZrO 2, generally take precipitation-immersion method, first Zr salt be precipitated as Zr (OH) 4, be then immersed in the solution of the species of doping, then carry out roasting, cooling obtains stable Tetragonal, be subject to immersing liquid concentration, precipitated liquid concentration, Zr metal precursor in this process, form the impact of Aging Temperature of precipitation pH value, precipitation.Be applied to the Tetragonal ZrO of solid acid alkali catalytic 2be all through metal, transition metal or rare-earth metal modified.Typically industrialized 1% Pt-ZrO 2.The ZrO of the Tetragonal produced by precipitation-immersion method 2, the metal ion of introducing loads to unbodied Zr (OH) by immersion method 4on, this process is subject to the impact of several factors, control procedure relative complex, and due to introduce metal ion and ZrO 2be not the contact between intermolecular/cluster, the decentralization of the metal ion that is introduced and the uniformity are uncontrollable, the ZrO therefore obtained 2degree of crystallinity and phase purity (sometimes containing the ZrO of monoclinic phase 2) be relatively low.
2008, Cavka reported microporous coordination polymer UIO-66 ~ 68 (UIO=UniversityofOslo) of first zirconium base, and its structure is by Zr 6(OH) 4o 4cluster and 12 terephthalic acid (TPA)s, 4,4 '-biphenyl dicarboxylic acid, 4, the microporous coordination polymer with the same topological structure of tetrahedral holes and octahedral voids that 4 '-terphenyl dioctyl phthalate is formed, the general structure after dehydration is ZrOL (L=terephthalic acid (TPA), 4,4 '-biphenyl dicarboxylic acid, 4,4 '-terphenyl dioctyl phthalate) [5].After this, different ligands and functionalization but the zirconium base microporous coordination polymer of same topological structure be in the news out.
(bibliography:
1.M.Hino,K.Arata,Chem.Lett.,1979,(5):477-480.
2.B.M.Reddy,P.M.Sreekanth,V.R.Reddy,J.Mol.Catal.A:Chem.,2005,225:71-78.
3.M.Dapiaggi,F.Maglia,I.Tredici,B.Maroni,G.Borghini,U.Tamburini,J.Phys.Chem.Solids,2010,71,1038-1041.
4.G.Y.Guo,Y.L.Chen,J.SolidStateChem.,2005,178,1675-1682.
5.J.H.Cavka,S.Jakobsen,U.Olsbye,N.Guillou,C.Lamberti,S.Bordiga,andK.P.Lillerud,J.Am.Chem.Soc.,2008,130,13850-13851.）。
Summary of the invention
In order to solve prior art Problems existing, the invention provides a kind of solid super acid catalyst and preparation method.
The invention provides the zirconium dioxide that a kind of solid super acid catalyst is load sulfuric acid, referred to as SO 4 2-/ ZrO 2;
Described ZrO 2zirconium polymerization of olefin using catalyst polymer is prepared through calcining, and involved zirconium polymerization of olefin using catalyst polymer is UIO-66 and its analog;
Described zirconium polymerization of olefin using catalyst polymer is any one of UIO-66 and analog, and dehydration general formula is ZrOL, and when L is terephthalic acid (TPA), ZrOL is UIO-66; When L is following part: fumaric acid, 4,4 '-biphenyl dicarboxylic acid, 2,6-naphthalene diacid, 4,4 '-Lian three phthalic acids, anti-, trans-1,6-muconic acid, and with-CH 3,-CHO ,-COOH ,-COOCH 3or the Isosorbide-5-Nitrae-terephthalic acid (TPA) of-OH functional group, 4,4 '-biphenyl dicarboxylic acid, 4,4 '-Lian three phthalic acids, 2,6-naphthalene diacid, instead, the derivative of trans-1,6-muconic acid, ZrOL is the analog of UIO-66.UIO-66 and the analog of all method synthesis all may be used for ZrO 2synthesis.
The invention provides a kind of preparation method of solid super acid catalyst, step and condition as follows:
(1) ZrO 2preparation
By zirconium polymerization of olefin using catalyst polymer in air atmosphere, ZrO is obtained by roasting 2, roasting time is 4 ~ 36 hours, and sintering temperature is 450 ~ 650 ° of C, obtains ZrO 2;
(2) SO 4 2-/ ZrO 2the preparation of solid super acid catalyst
ZrO 2quality g: be 1:8 ~ 24 with the volume mL of sulfuric acid solution, the concentration of sulfuric acid solution is 0.5 ~ 2 mol/L, ZrO roasting obtained by proportioning 2be immersed in sulfuric acid solution, dip time is 1 ~ 8 hour, filters, obtains SO 4 2-/ ZrO 2solids;
The SO obtained 4 2-/ ZrO 2solids carries out drying, calcines in air atmosphere, and calcining heat is 450 ~ 650 ° of C, and calcination time is 2-8 hour, obtains solid super acid catalyst SO 4 2-/ ZrO 2.
The SO obtained 4 2-/ ZrO 2the mass content of middle sulphur, between 3 ~ 20%, has super acids acidity, can be used for esterification and isomerization reaction.
beneficial effect:the invention provides a kind of solid super acid catalyst and preparation method.The carrier ZrO used 2have the UIO-66 of highly crystalline and analog through preparing through calcining.The feature of UIO-66 and analog is because they have same topological structure, and is all by a cluster ZrO 4(OH) 4(CO 2) 12formed.Results for calcination shows, the ZrO obtained 2content of tetragonal phase higher.SO prepared by additive method of therefore comparing 4 2-/ ZrO 2catalyst, SO prepared by the present invention 4 2-/ ZrO 2catalyst there is obvious advantage: 1) in this catalyst, sulfur content, between 3% ~ 20%, has super acids acidity; 2) do not need to introduce other metal ions as Tetragonal ZrO 2stabilizing agent; 3) technological process is short, and equipment investment is few, easy and simple to handle, suitable for mass production.
Detailed description of the invention
embodiment 1
(1) ZrO 2preparation
UIO-66-FA (part is the UIO-66 analog of fumaric acid) ,under air, 450 ° of C calcine the ZrO obtained for 36 hours 2;
(2) SO 4 2-/ ZrO 2the preparation of solid super acid catalyst
ZrO 2quality g: be 1:8 with the volume mL of sulfuric acid solution, the concentration of sulfuric acid solution is 0.5 mol/L, ZrO roasting obtained by proportioning 2be immersed in sulfuric acid solution, dip time is 1 hour, filters, obtains SO 4 2-/ ZrO 2solids;
The SO obtained 4 2-/ ZrO 2solids carries out drying, calcines in air atmosphere, and calcining heat is 450 ° of C, and calcination time is 2 hours, obtains solid super acid catalyst SO 4 2-/ ZrO 2.
Product carries out elementary analysis through ICP-AES, and result shows that sulphur mass content is 3%.
embodiment 2
(1) ZrO 2preparation
Under air, UIO-67 calcines 4 hours in 650 ° of C, obtains ZrO 2;
(2) SO 4 2-/ ZrO 2the preparation of solid super acid catalyst
ZrO 2quality g: be 1:24 with the volume mL of sulfuric acid solution, the concentration of sulfuric acid solution is 2 mol/L, ZrO roasting obtained by proportioning 2be immersed in sulfuric acid solution, dip time is 8 hours, filters, obtains SO 4 2-/ ZrO 2solids;
The SO obtained 4 2-/ ZrO 2solids carries out drying, calcines under the atmosphere of air, and calcining heat is 650 ° of C, and calcination time is 8 hours, obtains solid super acid catalyst SO 4 2-/ ZrO 2.Product carries out elementary analysis through ICP-AES, and result shows that sulphur mass content is 18%.Described UIO-67 is the analog of UIO-66, and L is 4,4 '-biphenyl dicarboxylic acid.
embodiment 3
(1) ZrO 2preparation
Under air, 500 ° of C calcine the ZrO obtained for 24 hours to UIO-66 2;
(2) SO 4 2-/ ZrO 2the preparation of solid super acid catalyst
ZrO 2quality g: be 1:16 with the volume mL of sulfuric acid solution, the concentration of sulfuric acid solution is 2 mol/L, ZrO roasting obtained by proportioning 2be immersed in sulfuric acid solution, dip time is 4 hours, filters, obtains SO 4 2-/ ZrO 2solids;
The SO obtained 4 2-/ ZrO 2solids carries out drying, calcines in air atmosphere, and calcining heat is 550 ° of C, and calcination time is 4 hours, obtains solid super acid catalyst SO 4 2-/ ZrO 2.
Product carries out elementary analysis through ICP-AES, and result shows that sulphur mass content is 20%.
embodiment 4
(1) ZrO 2preparation
Under air, 500 ° of C calcine and obtain ZrO in 24 hours UIO-66 2;
ZrO 2quality g: be 1:16 with the volume mL of sulfuric acid solution, the concentration of sulfuric acid solution is 1 mol/L, ZrO roasting obtained by proportioning 2be immersed in sulfuric acid solution, dip time is 3 hours, filters, obtains SO 4 2-/ ZrO 2solids;
The SO obtained 4 2-/ ZrO 2solids carries out drying, calcines in air atmosphere, and calcining heat is 500 ° of C, and calcination time is 3 hours, obtains solid super acid catalyst SO 4 2-/ ZrO 2.
Product carries out elementary analysis through ICP-AES, and result shows that sulphur mass content is 15%.
embodiment 5
(1) ZrO 2preparation
NH 2under air, 500 ° of C calcine and obtain ZrO in 24 hours-UIO-66 2;
(2) SO 4 2-/ ZrO 2the preparation of solid super acid catalyst
ZrO 2quality g: be 1:16 with the volume mL of sulfuric acid solution, the concentration of sulfuric acid solution is 1 mol/L, ZrO roasting obtained by proportioning 2be immersed in sulfuric acid solution, dip time is 3 hours, filters, obtains SO 4 2-/ ZrO 2solids;
The SO obtained 4 2-/ ZrO 2solids carries out drying, calcines in air atmosphere, and calcining heat is 550 ° of C, and calcination time is 3 hours, obtains solid super acid catalyst SO 4 2-/ ZrO 2.
Product carries out elementary analysis through ICP-AES, and result shows that sulphur mass content is 17%.
embodiment 6
(1) ZrO 2preparation
CH 3under air, 500 ° of C calcine and obtain ZrO in 24 hours-UIO-66 2;
(2) SO 4 2-/ ZrO 2the preparation of solid super acid catalyst
ZrO 2quality g: be 1:16 with the volume mL of sulfuric acid solution, the concentration of sulfuric acid solution is 1 mol/L, ZrO roasting obtained by proportioning 2be immersed in sulfuric acid solution, dip time is 3 hours, filters, obtains SO 4 2-/ ZrO 2solids;
The SO obtained 4 2-/ ZrO 2solids carries out drying, calcines in air atmosphere, and calcining heat is 500 ° of C, and calcination time is 3 hours, obtains solid super acid catalyst SO 4 2-/ ZrO 2.
Product carries out elementary analysis through ICP-AES, and result shows that sulphur mass content is 14%.

Claims (8)

1. solid super acid catalyst and a preparation method, is characterized in that, described solid super acid catalyst is the zirconium dioxide of load sulfuric acid, referred to as SO 4 2-/ ZrO 2;
Described ZrO 2zirconium polymerization of olefin using catalyst polymer is prepared through calcining, and involved zirconium polymerization of olefin using catalyst polymer is UIO-66 and its analog;
Described zirconium polymerization of olefin using catalyst polymer is any one of UIO-66 and analog, and dehydration general formula is ZrOL, and when L is terephthalic acid (TPA), ZrOL is UIO-66; When L is following part: fumaric acid, 4,4 '-biphenyl dicarboxylic acid, 2,6-naphthalene diacid, 4,4 '-Lian three phthalic acids, anti-, trans-1,6-muconic acid, and with-CH 3,-CHO ,-COOH ,-COOCH 3or the Isosorbide-5-Nitrae-terephthalic acid (TPA) of-OH functional group, 4,4 '-biphenyl dicarboxylic acid, 4,4 '-Lian three phthalic acids, 2,6-naphthalene diacid, instead, the derivative of trans-1,6-muconic acid, ZrOL is the analog of UIO-66.
2. the invention provides a kind of preparation method of solid super acid catalyst as claimed in claim 1, step and condition as follows:
(1) ZrO 2preparation
By zirconium polymerization of olefin using catalyst polymer in air atmosphere, ZrO is obtained by roasting 2, roasting time is 4 ~ 36 hours, and sintering temperature is 450 ~ 650 ° of C, obtains ZrO 2;
(2) SO 4 2-/ ZrO 2the preparation of solid super acid catalyst
ZrO 2quality g: be 1:8 ~ 24 with the volume mL of sulfuric acid solution, the concentration of sulfuric acid solution is 0.5 ~ 2 mol/L, ZrO roasting obtained by proportioning 2be immersed in sulfuric acid solution, dip time is 1 ~ 8 hour, filters, obtains SO 4 2-/ ZrO 2solids;
The SO obtained 4 2-/ ZrO 2solids carries out drying, calcines in air atmosphere, and calcining heat is 450 ~ 650 ° of C, and calcination time is 2-8 hour, obtains solid super acid catalyst SO 4 2-/ ZrO 2.
3. the invention provides a kind of preparation method of solid super acid catalyst as claimed in claim 2, step and condition as follows:
(1) ZrO 2preparation
UIO-66-FA (part is the UIO-66 analog of fumaric acid) ,under air, 450 ° of C calcine the ZrO obtained for 36 hours 2;
(2) SO 4 2-/ ZrO 2the preparation of solid super acid catalyst
ZrO 2quality g: be 1:8 with the volume mL of sulfuric acid solution, the concentration of sulfuric acid solution is 0.5 mol/L, ZrO roasting obtained by proportioning 2be immersed in sulfuric acid solution, dip time is 1 hour, filters, obtains SO 4 2-/ ZrO 2solids;
The SO obtained 4 2-/ ZrO 2solids carries out drying, calcines in air atmosphere, and calcining heat is 450 ° of C, and calcination time is 2 hours, obtains solid super acid catalyst SO 4 2-/ ZrO 2.
4. the invention provides a kind of preparation method of solid super acid catalyst as claimed in claim 2, step and condition as follows:
(1) ZrO 2preparation
Under air, UIO-67 calcines 4 hours in 650 ° of C, obtains ZrO 2;
(2) SO 4 2-/ ZrO 2the preparation of solid super acid catalyst
ZrO 2quality g: be 1:24 with the volume mL of sulfuric acid solution, the concentration of sulfuric acid solution is 2 mol/L, ZrO roasting obtained by proportioning 2be immersed in sulfuric acid solution, dip time is 8 hours, filters, obtains SO 4 2-/ ZrO 2solids;
The SO obtained 4 2-/ ZrO 2solids carries out drying, calcines under the atmosphere of air, and calcining heat is 650 ° of C, and calcination time is 8 hours, obtains solid super acid catalyst SO 4 2-/ ZrO 2; Described UIO-67 is the analog of UIO-66, and L is 4,4 '-biphenyl dicarboxylic acid.
5. the invention provides a kind of preparation method of solid super acid catalyst as claimed in claim 2, step and condition as follows:
(1) ZrO 2preparation
Under air, 500 ° of C calcine the ZrO obtained for 24 hours to UIO-66 2;
(2) SO 4 2-/ ZrO 2the preparation of solid super acid catalyst
ZrO 2quality g: be 1:16 with the volume mL of sulfuric acid solution, the concentration of sulfuric acid solution is 2 mol/L, ZrO roasting obtained by proportioning 2be immersed in sulfuric acid solution, dip time is 4 hours, filters, obtains SO 4 2-/ ZrO 2solids;
The SO obtained 4 2-/ ZrO 2solids carries out drying, calcines in air atmosphere, and calcining heat is 550 ° of C, and calcination time is 4 hours, obtains solid super acid catalyst SO 4 2-/ ZrO 2.
6. the invention provides a kind of preparation method of solid super acid catalyst as claimed in claim 2, step and condition as follows:
(1) ZrO 2preparation
Under air, 500 ° of C calcine and obtain ZrO in 24 hours UIO-66 2;
ZrO 2quality g: be 1:16 with the volume mL of sulfuric acid solution, the concentration of sulfuric acid solution is 1 mol/L, ZrO roasting obtained by proportioning 2be immersed in sulfuric acid solution, dip time is 3 hours, filters, obtains SO 4 2-/ ZrO 2solids;
The SO obtained 4 2-/ ZrO 2solids carries out drying, calcines in air atmosphere, and calcining heat is 500 ° of C, and calcination time is 3 hours, obtains solid super acid catalyst SO 4 2-/ ZrO 2.
7. the invention provides a kind of preparation method of solid super acid catalyst as claimed in claim 2, step and condition as follows:
(1) ZrO 2preparation
NH 2under air, 500 ° of C calcine and obtain ZrO in 24 hours-UIO-66 2;
(2) SO 4 2-/ ZrO 2the preparation of solid super acid catalyst
ZrO 2quality g: be 1:16 with the volume mL of sulfuric acid solution, the concentration of sulfuric acid solution is 1 mol/L, ZrO roasting obtained by proportioning 2be immersed in sulfuric acid solution, dip time is 3 hours, filters, obtains SO 4 2-/ ZrO 2solids;
The SO obtained 4 2-/ ZrO 2solids carries out drying, calcines in air atmosphere, and calcining heat is 550 ° of C, and calcination time is 3 hours, obtains solid super acid catalyst SO 4 2-/ ZrO 2.
8. the invention provides a kind of preparation method of solid super acid catalyst as claimed in claim 2, step and condition as follows:
(1) ZrO 2preparation
CH 3under air, 500 ° of C calcine and obtain ZrO in 24 hours-UIO-66 2;
(2) SO 4 2-/ ZrO 2the preparation of solid super acid catalyst
ZrO 2quality g: be 1:16 with the volume mL of sulfuric acid solution, the concentration of sulfuric acid solution is 1 mol/L, ZrO roasting obtained by proportioning 2be immersed in sulfuric acid solution, dip time is 3 hours, filters, obtains SO 4 2-/ ZrO 2solids;
The SO obtained 4 2-/ ZrO 2solids carries out drying, calcines in air atmosphere, and calcining heat is 500 ° of C, and calcination time is 3 hours, obtains solid super acid catalyst SO 4 2-/ ZrO 2.
CN201510771286.8A 2015-11-12 2015-11-12 Solid superacid catalyst and preparation method thereof Pending CN105195179A (en)

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CN109294341A (en) * 2018-09-25 2019-02-01 南昌蓝珀笔业画材有限公司 A kind of preparation method of drawing pigment low discoloration dextrin glue
CN109364967A (en) * 2018-10-17 2019-02-22 中国科学院山西煤炭化学研究所 A kind of multi-functional catalysis material of superionic conductors type and preparation method and application
CN109513449A (en) * 2018-11-22 2019-03-26 南京林业大学 A kind of method that solid super-strong acid is prepared by metal-organic framework materials UiO-66 and products thereof and application
CN111777584A (en) * 2020-03-27 2020-10-16 东北林业大学 Method for degrading larch bark poly-procyanidine
CN115869932A (en) * 2022-10-31 2023-03-31 浙江工业大学 UIO-66 derived carbon material catalyst, preparation method thereof and application thereof in catalyzing carbon dioxide desorption
CN116081686A (en) * 2023-02-13 2023-05-09 中国人民解放军国防科技大学 Nano ZrO 2 C heat-resistant wave-absorbing material and preparation method thereof

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Cited By (9)

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CN106684355A (en) * 2016-12-29 2017-05-17 中国电子科技集团公司第十八研究所 Metal organic framework Uio-66@ S lithium sulfur positive electrode material and preparation method thereof
CN109294341A (en) * 2018-09-25 2019-02-01 南昌蓝珀笔业画材有限公司 A kind of preparation method of drawing pigment low discoloration dextrin glue
CN109364967A (en) * 2018-10-17 2019-02-22 中国科学院山西煤炭化学研究所 A kind of multi-functional catalysis material of superionic conductors type and preparation method and application
CN109364967B (en) * 2018-10-17 2021-03-26 中国科学院山西煤炭化学研究所 Super-ionic conductor type multifunctional catalytic material, preparation method and application
CN109513449A (en) * 2018-11-22 2019-03-26 南京林业大学 A kind of method that solid super-strong acid is prepared by metal-organic framework materials UiO-66 and products thereof and application
CN109513449B (en) * 2018-11-22 2024-05-07 南京林业大学 Method for preparing solid super acid from metal organic framework material UiO-66, product and application thereof
CN111777584A (en) * 2020-03-27 2020-10-16 东北林业大学 Method for degrading larch bark poly-procyanidine
CN115869932A (en) * 2022-10-31 2023-03-31 浙江工业大学 UIO-66 derived carbon material catalyst, preparation method thereof and application thereof in catalyzing carbon dioxide desorption
CN116081686A (en) * 2023-02-13 2023-05-09 中国人民解放军国防科技大学 Nano ZrO 2 C heat-resistant wave-absorbing material and preparation method thereof

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Application publication date: 20151230