CN105664944B - 一种基于金属有机框架的Cu催化剂、制备方法及用途 - Google Patents
一种基于金属有机框架的Cu催化剂、制备方法及用途 Download PDFInfo
- Publication number
- CN105664944B CN105664944B CN201610095270.4A CN201610095270A CN105664944B CN 105664944 B CN105664944 B CN 105664944B CN 201610095270 A CN201610095270 A CN 201610095270A CN 105664944 B CN105664944 B CN 105664944B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- organic
- copper
- metal organic
- organic frame
- 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.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 38
- 239000002184 metal Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000010949 copper Substances 0.000 claims abstract description 101
- 229910052802 copper Inorganic materials 0.000 claims abstract description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000003197 catalytic effect Effects 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 230000015556 catabolic process Effects 0.000 claims abstract description 11
- 238000006731 degradation reaction Methods 0.000 claims abstract description 11
- 239000011246 composite particle Substances 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims abstract description 7
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 7
- 230000003319 supportive effect Effects 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical group OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000013084 copper-based metal-organic framework Substances 0.000 claims description 18
- 239000013110 organic ligand Substances 0.000 claims description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 235000004515 gallic acid Nutrition 0.000 claims description 11
- 229940074391 gallic acid Drugs 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000003763 carbonization Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 5
- VBEGHXKAFSLLGE-UHFFFAOYSA-N n-phenylnitramide Chemical compound [O-][N+](=O)NC1=CC=CC=C1 VBEGHXKAFSLLGE-UHFFFAOYSA-N 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 4
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 239000001263 FEMA 3042 Substances 0.000 claims description 4
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 4
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 4
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000975 dye Substances 0.000 claims description 4
- 239000002957 persistent organic pollutant Substances 0.000 claims description 4
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 4
- 235000015523 tannic acid Nutrition 0.000 claims description 4
- 229940033123 tannic acid Drugs 0.000 claims description 4
- 229920002258 tannic acid Polymers 0.000 claims description 4
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical class OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 3
- 229940043267 rhodamine b Drugs 0.000 claims description 3
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical class NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 claims description 2
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 2
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 2
- 235000014220 Rhus chinensis Nutrition 0.000 claims description 2
- 240000003152 Rhus chinensis Species 0.000 claims description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000000463 material Substances 0.000 description 12
- RBXVOQPAMPBADW-UHFFFAOYSA-N nitrous acid;phenol Chemical compound ON=O.OC1=CC=CC=C1 RBXVOQPAMPBADW-UHFFFAOYSA-N 0.000 description 8
- 229910002651 NO3 Inorganic materials 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000009467 reduction Effects 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- -1 copper nitrate Chemical compound 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 4
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 3
- 229910002480 Cu-O Inorganic materials 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000013147 Cu3(BTC)2 Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 150000008319 1H-pyrimidin-2-ones Chemical class 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- JNRLEMMIVRBKJE-UHFFFAOYSA-N 4,4'-Methylenebis(N,N-dimethylaniline) Chemical compound C1=CC(N(C)C)=CC=C1CC1=CC=C(N(C)C)C=C1 JNRLEMMIVRBKJE-UHFFFAOYSA-N 0.000 description 1
- 229910002703 Al K Inorganic materials 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001922 gold oxide Inorganic materials 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 150000001261 hydroxy acids Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- ZFACJPAPCXRZMQ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O.OC(=O)C1=CC=CC=C1C(O)=O ZFACJPAPCXRZMQ-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000306 recurrent effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
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
- B01J31/20—Carbonyls
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
- B01J35/45—Nanoparticles
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
- C02F1/705—Reduction by metals
-
- 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
-
- 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]
-
- 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
- C02F2101/322—Volatile compounds, e.g. benzene
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Nanotechnology (AREA)
Abstract
本发明公开了一种基于金属有机框架的Cu催化剂、制备方法及用途。该基于金属有机框架的Cu催化剂,包括由不同氧化态铜组成的具有催化活性位点的复合颗粒和起支撑作用的多孔碳层。制备该催化剂的方法包括如下步骤:1)制备金属有机框架Cu‑MOF,2)将金属有机框架Cu‑MOF碳化。该Cu催化剂可用于水相催化,催化降解水中的有机污染物。
Description
技术领域
本发明涉及一种催化降解水中有机污染物的基于金属有机框架的Cu催化剂、以及基于金属有机框架的Cu催化剂的制备方法。
背景技术
金属有机框架(MOFs)是将有机配体和金属离子通过自组装形成的具有重复网络结构的一种类沸石材料。MOFs作为一种复合材料,具有多孔、结构有序和比表面积大等优点,在很多领域都有应用,传感、药物传输、气体吸附以及作为Lewis酸催化等,因此越来越得到关注。Cu-MOF作为应用比较广泛的金属有机框架,在催化“Click”等反应具有较好的表现。
K.Schlichte等人2004年发表的(Improved synthesis,thermal stability andcatalytic propertiesof the metal-organic framework compound Cu3(BTC)2,Microporous and Mesoporous Materials,2004,73,81-88.)即制备得到了一种金属有机框架材料Cu3(BTC)2,并对其催化性能进行了研究。另外,还有金属有机框架Cu-MOF(Cu(2-pymo)2、Cu(im)2、Cu(BDC)(pymo:2-羟基嘧啶,im:咪唑,BTC:苯三甲酸,BDC:苯二甲酸)均被报道用于催化“Click”反应。
但是由于金属有机框架(MOFs)在水中的稳定性比较差,使得其应用的广泛性和普遍性受到了一定的限制。
金属纳米颗粒作为催化剂具有催化选择性好、应用领域广、反应条件温和、催化效率高等优点而被广泛应用。K.C.Leung等人2012年发表的(Gold and iron oxide hybridnanocomposite materials,Chemical Society reviews,2012,41,1911-1928.)讨论了金和铁的氧化物组成的复合纳米颗粒的研究状况。该文章指出这类复合纳米材料可以用于药物传递、生物传感、细胞分选和催化反应等诸多领域,在用作催化剂时回收方便、快捷,能够循环使用。但这类材料由于表面能量大造成稳定性差和自我聚集,影响了其应用效率。很多催化反应采用贵金属如Au、Ag等作为催化剂,但是贵金属价格昂贵而且稀少,所以,我们有必要研究出非贵金属材料作为催化剂。
此外,制备出一种新型的基于多孔的金属有机框架的非贵金属催化剂,并将其用于催化降解水环境中的有机污染物,对于缓解水环境污染问题具有重要意义。
发明内容
为了解决金属有机框架由于水稳定性差不能用于水相催化,金属纳米颗粒催化剂易团聚且不稳定等技术问题,本发明的目的之一是提供一种催化效率高、制备过程简单的基于金属有机框架的Cu催化剂。
本发明的另一个目的是提供上述催化剂的制备方法。
本发明的再一个目的是将上述催化剂用于催化降解水中的有机污染物。
为了实现上述发明目的,本发明的一个技术方案提供了一种基于金属有机框架的Cu催化剂,该催化剂包括由不同氧化态铜组成的具有催化活性位点的复合颗粒和起支撑作用的多孔碳层。
所述复合颗粒中优选含有Cu2O、CuO和Cu。
本发明的另一个技术方案提供了一种制备上述Cu催化剂的方法,该方法包括如下步骤:1)采用铜源和有机配体制备金属有机框架Cu-MOF,2)金属有机框架Cu-MOF的碳化。
其中,1)采用铜源和有机配体制备金属有机框架Cu-MOF的步骤如下:
将铜源和作为碳源的有机配体按摩尔比称重后于溶剂中溶解,在100-140℃的密闭条件下反应8-24h,冷却后过滤,用有机溶剂清洗滤渣后离心,得下层固体沉淀,真空干燥;
2)金属有机框架Cu-MOF碳化是在200-800℃氮气保护条件下进行碳化。
本发明的再一个技术方案将基于金属有机框架的Cu催化剂用于催化降解水中的有机污染物。
与现有技术相比,本发明提供的基于金属有机框架的Cu催化剂及其制备方法具有以下优点:(1)成本低廉。制备过程中用到的主要原料铜源和作为碳源的有机配体,如Cu(NO3)2和没食子酸,价格低廉,与传统的贵金属(如Pt、Au、Ag等)催化剂相比,同等的催化效果,成本可以低几十倍。
(2)催化剂用量少,催化速率快,催化效率高。少量的催化剂能够在5min内将污染物催化还原降解,转化率高,催化还原的转化率达到99%以上,克服了一般催化剂费时费力的缺点。
(3)水稳定性好,可用于水相催化,可再生和重复利用。现有的Cu催化剂大都不能用于催化以水做溶剂的反应,而本发明提供的催化剂可以用于催化水中污染物的降解,而且,测试结果表明,本发明提供的催化剂重复使用5次后,催化剂的形态无明显变化,降解效率仍能达到99%。
(4)制备过程简单、对环境友好。催化剂制备过程无需复杂的处理过程,原料不涉及到重毒性物质,在催化过程中,不需消耗任何有毒物质,不会引入其他有毒有害的物质,对环境友好。
附图说明
图1为实施例1制得的Cu催化剂的TEM和SEM谱图;
图2为实施例1制得的Cu催化剂Cu-GA与没食子酸GA的红外对比谱图;
图3为实施例1制得的Cu催化剂的XRD谱图;
图4为实施例1制得的Cu催化剂的XPS谱图;
图5为实施例1制得的Cu催化剂的N2吸脱附测试结果。
具体实施方式
本发明涉及一种基于金属有机框架的Cu催化剂、制备方法及用途。根据本发明的基于金属有机框架的Cu催化剂,其水稳定性好,可用于水相催化。
对于本发明Cu催化剂中所述复合颗粒中含有Cu2O、CuO和Cu,优选为Cu2O的含量最高,CuO和Cu其次。
本发明所制备的基于金属有机框架的Cu催化剂为介孔、至少局部有结晶的结构。
对于本发明制备方法中铜源适合的化合物为铜的无机化合物,例如硝酸铜、卤化铜、硫酸铜和醋酸铜等,优选为Cu(NO3)2、CuCl2或CuSO4溶液中的一种或多种;更优选为Cu(NO3)2溶液。
所述作为碳源的有机配体优选为没食子酸和/或单宁酸,更优选为没食子酸。
所述溶解铜源和有机配体用的溶剂为乙醇、甲醇、DMF、DMSO和DMAC中的一种或多种,优选为DMF。
所述清洗用的有机溶剂为乙醇、甲醇、DMF、CH2Cl2和氯仿中的一种或多种,优选为DMF和乙醇。
在优选实施方案中,所述Cu催化剂的通过如下方法制备:
1)采用铜源和有机配体制备金属有机框架Cu-MOF的步骤如下:
将铜源和作为碳源的有机配体按摩尔比称重后于溶剂中溶解,在130-140℃更优选为130℃的密闭条件下反应时间为12-24h,更优选为24h,冷却后过滤,用有机溶剂清洗滤渣后离心,得下层固体沉淀,在40-65℃更优选为50℃下真空干燥;真空干燥时间为5-10h,更优选为8h;
2)金属有机框架Cu-MOF碳化是在200-800℃氮气保护条件下进行碳化,碳化的温度为500-800℃,更优选为500℃;碳化的时间为2-5h,更优选为4-5h。
对于本发明基于金属有机框架的Cu催化剂用于催化降解水中的有机污染物。有机污染物优选为苯酚、苯胺、硝基苯,以及它们的衍生物中的一种或组合和/或有机染料。更优选为苯酚的衍生物为硝基苯酚、氯苯酚、氨基苯酚或甲基苯酚;苯胺的衍生物为硝基苯胺、甲苯胺或联苯胺;硝基苯的衍生物为硝基甲苯或氯硝基苯;有机染料为罗丹明B和/或亚甲基蓝。最优选为硝基苯酚为4-硝基苯酚或邻硝基苯酚;硝基苯胺为对4-硝基苯胺。
通常地,基于金属有机框架的Cu催化剂粒径从50nm、优选从80nm最高至120nm。
通常地,所述Cu催化剂有利地具有100-180m2g-1的比表面积,0.2-0.75cm3/g的孔体积,2-40nm的孔径分布。优选具有100-154.6m2g-1的比表面积,0.5-0.75cm3/g的孔体积,2-30nm的孔径分布。
下面结合具体实施例对本发明做进一步详细的说明。
实施例1
一种基于金属有机框架的Cu催化剂,该催化剂包括由不同氧化态铜组成的具有催化活性位点的复合颗粒和起支撑作用的多孔碳层。
制备该催化剂的步骤如下:1)制备Cu-MOF:称取0.9664g Cu(NO3)2·6H2O和0.7526g没食子酸,分别溶解于20mL DMF中,将二者混合后置于100mL聚四氟乙烯不锈钢反应釜中,在130℃的密闭条件下反应24h,反应结束后冷却至室温,过滤,依次用DMF和乙醇清洗滤渣后离心,得下层固体沉淀,于50℃下真空干燥。
2)碳化:将制得的Cu-MOF置于管式炉中,在氮气保护下,于500℃碳化4h。
实施例2
一种基于金属有机框架的Cu催化剂,该催化剂包括由不同氧化态铜组成的具有催化活性位点的复合颗粒和起支撑作用的多孔碳层。
制备该催化剂的步骤如下:1)制备Cu-MOF:称取2.601g Cu(NO3)2·6H2O和0.7526g没食子酸,分别溶解于40mL DMSO中,将二者混合后置于150mL聚四氟乙烯不锈钢反应釜中,在150℃的密闭条件下反应12h,反应结束后冷却至室温,过滤,依次用二氯甲烷和乙醇清洗滤渣后离心,得下层固体沉淀,于50℃下真空干燥5h。
2)碳化:将制得的Cu-MOF置于管式炉中,在氮气保护下,于800℃碳化3h。
实施例3
一种基于金属有机框架的Cu催化剂,该催化剂包括由不同氧化态铜组成的具有催化活性位点的复合颗粒和起支撑作用的多孔碳层。
制备该催化剂的步骤如下:1)制备Cu-MOF:称取0.9664g Cu(NO3)2·6H2O和2.7815g单宁酸,分别溶解于80mL乙醇中,将二者混合后置于250mL聚四氟乙烯不锈钢反应釜中,在105℃的密闭条件下反应24h,反应结束后冷却至室温,过滤,依次用DMF和乙醇清洗滤渣后离心,得下层固体沉淀,于65℃下真空干燥8h。
2)碳化:将制得的Cu-MOF置于管式炉中,在氮气保护下,于220℃碳化4h。
结构表征:
对实施例1-3制得的催化剂进行结构表征,具体如下:
1、利用电子透射电子显微镜(TEM)(JEOL JEM-200CX型)加速电压160kV,和场发射扫描电镜(SEM)(Hitachi S-5500型)对催化剂的粒径与形貌进行分析,结果显示,所制备的由不同氧化态铜组成的具有催化活性位点的复合颗粒负载在碳层上,颗粒大小均匀,粒径为80-120nm,具体结果见表1.
表1实施例1-3制得的催化剂的比表面和孔径分布结果
2、利用傅立叶变换红外光谱仪(FTIR)(Nicolet 170SX型)对实施例1-3制得的Cu催化剂进行表征,使用KBr压片法,其中,实施例1的对比图如附图2所示。
比较实施例1和2中的没食子酸和制得的Cu催化剂的红外光谱图,没食子酸分子的O-H在3329cm-1处对应的宽峰变窄说明发生了伸缩振动。在1600cm-1和1366cm-1是没食子酸分子的COO-发生了伸缩振动。当没食子酸与Cu反应之后,O-H在3429cm-1处发生了伸缩振动,并且在493cm-1处出现了Cu-O的振动峰,在1029cm-1处的羧酸中的O-H峰消失,表明了没食子酸中的所有羧基和羟基基团均发生了反应,在Cu-GA中C=O向更低频率下发生了弯曲振动,羧酸基团中的COO-在1300和1600cm–1出现特征峰,在1500cm–1和1426cm–1发生了不对称的伸缩。这些结果表明所有的羧基和酚羟基均与Cu发生了反应。
实施例3中制得的Cu催化剂与单宁酸的红外谱图对比后表明,单宁酸分子上的O-H在3200-3420cm–1处对应的宽峰变窄,且在493cm–1出现了Cu-O的振动峰,这些结果表明酚羟基与Cu发生了反应。
3、XRD和XPS测试
利用X-射线衍射(XRD)(b/max-RB Diffractometer型),使用镍过滤Cu Kα射线,扫描范围从5°到90°,扫描的间隔为0.02°测试实施例1-3制得的催化剂的XRD谱图。
利用X-射线光电子(以Al Kα射线为光源XPS)分析了制得的Cu催化剂的XPS曲线。
测试结果表明,本发明实施例1-3制得的Cu催化剂XRD谱图均在2θ=29.5°,34.5°,42.2°,61.5°,67.9°,73.4°处出现了由(110),(111),(200),(220),(310)和(311)构成的Cu2O的特征峰;在10.26°,41.79°,43.27°,50.39°出现了Cu-O的特征峰;Cu的特征峰出现在32.5°(110),36.4°(111),38.6°(200),48.7°(20-2),53.4°(020),58.2°(202),66.1°(31-1),51.3°(200)和72.3°(220)。强且尖锐的峰代表着材料的结晶度高。从Cu的各种形式的峰的大小和数量能够判断各种形式的铜的含量,结果表明,该结构中Cu2O的含量最多,其次是CuO和Cu。其中,实施例1制得的Cu催化剂XRD谱图见附图3。
制得的Cu催化剂的Cu、O和C元素的XPS图谱进一步证明了Cu、Cu2O和CuO的存在。如附图4中所示的实施例1制得的Cu催化剂的XPS谱图。
Cu2p3/2在932.1and 933.8eV出现特征峰,在932.1eV出现的峰是Cu2O/Cu(Cu+/Cu0),由于Cu+和Cu0所在峰位置特别接近,所以很难具体区分,这与其他的文献报道很相似。在933.8eV出现的是CuO的特征峰,这与别的文献中提到的CuO特征峰出现在933.4~933.9eV一致。图中也展示了O1s的光谱,在530.2,531.6,533.6eV是O1s的特征峰,在930.2eV出现的是Cu2O中的O1s的特征峰,与文献中报道出现在530.0~530.7eV范围内一致。CuO中的O1s的特征峰出现在533.6eV,而出现在531.6eV中的峰是OH和H2O中的氧及吸附在材料表面的羧酸。
4、拉曼Raman谱图
应用拉曼光谱仪(RM2000,Renishaw,UK)获得实施例1-3制得的Cu催化剂的Raman光谱,其中激发波长为514或515nm,由Ar+激光激发产生。测试结果表明:拉曼光谱谱图上有2个峰,一个峰约在1588cm-1处,称为G峰,对应石墨结构的峰;另一个峰约在1375cm-1处,称为D峰,是对应缺陷的峰。这2个峰是石墨化碳材料的特征峰,可以说明所制备材料被成功石墨化。
实施例4
本发明提供的Cu催化剂的催化性能测试
本实验利用由实施例1制得的Cu催化剂催化还原降解4-硝基苯酚(4-NP)。
为了排除吸附作用的干扰,我们在未加入还原剂NaBH4,直接加入催化材料,经过24h,测定4-NP的浓度,我们发现其变化不大,说明该粒子的吸附效果不明显,从而证明4-NP的去除是由于粒子的催化还原造成的。
催化实验直接在比色皿中进行,反应时加入2mL去离子水,1mL 0.2M的NaBH4,0.1mL 5mM的4-NP及50uL(2mg/mL)催化剂溶液。在未加催化剂之前,加入NaBH4溶液之后溶液迅速变黄,随着催化剂的加入,溶液的黄色逐渐褪去,并且在3min之内完全没有了颜色,说明4-NP被还原降解,从催化效果可以看出,完全催化还原4-NP需要160s,比一般报道的材料的催化还原速度要快。
反应结束之后,将催化剂进行离心分离,得到的催化剂进行下一次催化实验,经过5次重复利用之后材料的催化效率仍能达到99%,从肉眼效果看,催化剂的形态并没有发生改变。
除此之外,我们还探索了该催化剂对其他的污染物如O-NP、亚甲基蓝、罗丹明B、硝基苯胺等在同样的条件下的催化性能,从催化结果看到,由本发明制得的催化剂对上述污染物的降解均具有较好的催化效果。对于硝基苯类物质,不管取代基位于哪里,均有较好的催化效果,而且催化还原的转化率达到99%以上,但是对于硝基甲苯和硝基氯苯的催化效果比硝基苯胺和硝基酚的效果稍微差些,可能的原因是硝基甲苯和硝基氯苯的降解机理和过程比硝基苯胺和硝基酚更复杂。
上述例子仅作为说明的目的,本发明的范围并不受此限制。对本领域的技术人员来说进行修改是显而易见的,本发明仅受所附权利要求范围的限制。
Claims (14)
1.一种催化降解水中有机污染物的基于金属有机框架的Cu催化剂,其中,该催化剂包括由不同氧化态铜组成的具有催化活性位点的复合颗粒和起支撑作用的多孔碳层;
其中,所述的复合颗粒中含有Cu2O、CuO和Cu,其中Cu2O 的含量最高;
所述的催化剂的粒径为50-120nm,比表面积为100-180m2g-1,孔体积为0.2-0.75cm3/g,孔径分布为2-40nm。
2.权利要求1的Cu催化剂,其中,所述的催化剂为介孔、局部结晶的结构。
3.权利要求2的Cu催化剂,其中,所述的催化剂的粒径为80-120nm,比表面积为100-154.6m2g-1,孔体积为0.5-0.75cm3/g,孔径分布为2-30nm。
4.制备权利要求1-3中任一项的Cu催化剂的方法,该方法包括如下步骤:1)采用铜前驱体和有机配体制备金属有机框架Cu-MOF,2)金属有机框架Cu-MOF的碳化。
5.权利要求4的方法,其中,1)采用铜前驱体和有机配体制备金属有机框架Cu-MOF:
将铜前驱体和作为碳源的有机配体按摩尔比称重后于溶剂中溶解,在100-140℃的密闭条件下反应8-24h,冷却后过滤,用有机溶剂清洗滤渣后离心,得下层固体沉淀,真空干燥;
2)将金属有机框架Cu-MOF在200-800℃氮气保护条件下进行碳化。
6.权利要求4或5的方法,其中,铜源为Cu(NO3)2、CuCl2或CuSO4溶液中的一种或多种;作为碳源的有机配体为没食子酸和/或单宁酸;铜前驱体和有机配体的摩尔比为1:0.5-2。
7.权利要求6所述的方法,其中,铜源为Cu(NO3)2溶液;作为碳源的有机配体为没食子酸;铜前驱体和有机配体的摩尔比为1:1。
8.权利要求5的方法,其中,溶解铜前驱体和有机配体用的溶剂为乙醇、甲醇、DMF、DMSO和DMAC中的一种或多种;反应时间为12-24h;反应温度为130-140℃。
9.权利要求8的方法,其中,溶解铜前驱体和有机配体用的溶剂为DMF;反应时间为24h;反应温度为130℃。
10.权利要求5的方法,其中,清洗用的有机溶剂为乙醇、甲醇、DMF、CH2Cl2和氯仿中的一种或多种;真空干燥的温度为40-65℃;真空干燥时间为5-10h;碳化的温度为500-800℃;碳化的时间为2-5h。
11.权利要求10的方法,其中,清洗用的有机溶剂为DMF和乙醇;真空干燥的温度为50℃;真空干燥时间为8h;碳化的温度为500℃;碳化的时间为4-5h。
12.权利要求1-3中任一项的Cu催化剂在催化降解水中有机污染物方面的用途。
13.权利要求12的用途,其中,所述的有机污染物为硝基苯酚、硝基苯胺、硝基甲苯及它们的衍生物中的一种或组合和/或有机染料。
14.权利要求12的用途,其中,所述的有机污染物为4-硝基苯酚、4-硝基苯胺、亚甲基蓝、罗丹明B中的一种或多种。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610095270.4A CN105664944B (zh) | 2016-02-19 | 2016-02-19 | 一种基于金属有机框架的Cu催化剂、制备方法及用途 |
PCT/CN2016/111427 WO2017140176A1 (zh) | 2016-02-19 | 2016-12-22 | 一种基于金属有机框架的Cu催化剂、制备方法及用途 |
US15/999,839 US10940469B2 (en) | 2016-02-19 | 2016-12-22 | Cu catalyst based on metal organic framework, preparation method and use thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610095270.4A CN105664944B (zh) | 2016-02-19 | 2016-02-19 | 一种基于金属有机框架的Cu催化剂、制备方法及用途 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN105664944A CN105664944A (zh) | 2016-06-15 |
CN105664944B true CN105664944B (zh) | 2018-03-27 |
Family
ID=56305732
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201610095270.4A Active CN105664944B (zh) | 2016-02-19 | 2016-02-19 | 一种基于金属有机框架的Cu催化剂、制备方法及用途 |
Country Status (3)
Country | Link |
---|---|
US (1) | US10940469B2 (zh) |
CN (1) | CN105664944B (zh) |
WO (1) | WO2017140176A1 (zh) |
Families Citing this family (48)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105664944B (zh) | 2016-02-19 | 2018-03-27 | 中国环境科学研究院 | 一种基于金属有机框架的Cu催化剂、制备方法及用途 |
CN106423164A (zh) * | 2016-09-30 | 2017-02-22 | 上海理工大学 | 一种CuOX催化剂、其制备方法和在防治环境污染中的应用 |
CN106540694A (zh) * | 2016-11-01 | 2017-03-29 | 辽宁石油化工大学 | 铜基MOF材料制备多孔碳负载的Cu2O/Cu复合材料的方法及其应用 |
CN106565964B (zh) * | 2016-11-04 | 2019-11-05 | 石家庄学院 | 一种微/纳米多层次复合结构金属多酚囊泡材料的制备方法 |
CN107321386B (zh) * | 2017-07-14 | 2019-09-27 | 东北大学 | 一种原位还原金属有机骨架薄膜的连续催化方法 |
CN107999079B (zh) * | 2017-12-29 | 2020-06-05 | 济南大学 | 一种基于Cu(II)-MOF/Ni复合材料的制备方法和应用 |
CN108440235B (zh) * | 2018-03-27 | 2021-01-29 | 浙江大学 | 一种从四碳烃混合气中分离1,3-丁二烯的方法 |
CN108888763B (zh) * | 2018-07-09 | 2021-07-27 | 中国科学院理化技术研究所 | 含铜基颗粒的多孔碳复合材料及其制备方法和应用 |
CN109097787B (zh) * | 2018-08-03 | 2020-04-28 | 首都师范大学 | 一种金属多酚配合物晶体电催化剂的制备方法与应用 |
CN109251536B (zh) * | 2018-08-08 | 2020-12-08 | 首都师范大学 | 有机金属骨架材料封装的铜/氧化亚铜复合材料的制备方法 |
CN109280936B (zh) * | 2018-10-22 | 2020-05-12 | 华东师范大学 | CuO电极制备方法及电催化合成醇类化合物的应用 |
CN109759134B (zh) * | 2019-01-24 | 2021-11-23 | 湖北大学 | MOF衍生的Cu@C催化剂及其制备方法与应用 |
CN109701535B (zh) * | 2019-01-28 | 2021-06-29 | 中北大学 | 氧化亚铜-碳点-铜三元复合光催化剂的制备方法 |
CN110078931B (zh) * | 2019-04-12 | 2020-08-28 | 浙江大学 | 一种有机框架材料与用途 |
CN110227456B (zh) * | 2019-06-05 | 2021-08-06 | 华南理工大学 | MOFs衍生二维多级孔Cu/C复合材料及其制备方法 |
CN110898836B (zh) * | 2019-12-06 | 2023-05-12 | 怀化学院 | 掺铜mof基衍生催化剂及其制备方法与应用 |
CN110975868A (zh) * | 2019-12-16 | 2020-04-10 | 生态环境部环境规划院 | 一种基于有机金属框架的磁性纳米铜催化剂的制备方法及应用 |
CN111151251A (zh) * | 2020-01-15 | 2020-05-15 | 清创人和生态工程技术有限公司 | 一种Fe-Ni-Co复合类芬顿催化剂及制备方法 |
CN111330577B (zh) * | 2020-04-15 | 2023-03-10 | 广州大学 | 一种碳化有机骨架包覆零价铜的芬顿催化剂及其制备方法与应用 |
CN111569875A (zh) * | 2020-04-15 | 2020-08-25 | 江苏大学 | 一种铜/多孔碳纳米棒材料、制备方法和应用 |
CN113332996B (zh) * | 2020-08-31 | 2022-10-28 | 中国科学技术大学 | 一种超薄碳层稳定的金属纳米颗粒催化剂及其制备方法 |
CN112108119B (zh) * | 2020-09-21 | 2023-01-31 | 广东石油化工学院 | 一种改性mof吸附材料及其制备方法 |
CN112604506B (zh) * | 2020-10-22 | 2022-11-25 | 山东东岳高分子材料有限公司 | 用于染料催化脱色的聚四氟乙烯膜的制备方法及聚四氟乙烯膜的应用方法 |
CN112657464B (zh) * | 2020-11-26 | 2022-03-29 | 中国农业科学院油料作物研究所 | 一种Cu-BTC MOF碳化多孔材料及其制备方法和应用 |
CN112522738B (zh) * | 2020-12-17 | 2021-09-03 | 哈尔滨工业大学 | 一种MOF衍生的CuAl/N-C催化剂的制备方法和应用 |
CN112844479B (zh) * | 2020-12-31 | 2022-02-11 | 中南大学 | 一种zif-8负载银纳米颗粒催化剂及其制备方法和应用 |
CN112619608B (zh) * | 2021-01-11 | 2022-04-01 | 福州大学 | 一种葡萄糖基多孔碳材料的制备及应用 |
CN113233539B (zh) * | 2021-04-09 | 2022-08-19 | 厦门大学 | 电子束协同催化下高分子有机化合物的降解方法及其在污水处理中的应用 |
CN115490868B (zh) * | 2021-06-17 | 2023-12-01 | 上海科技大学 | 一种hkust-1晶体的制备方法 |
CN113697791A (zh) * | 2021-07-29 | 2021-11-26 | 中南大学 | 一种富缺陷碳材料及其制备方法和应用 |
CN113413921B (zh) * | 2021-07-30 | 2022-11-18 | 陕西科技大学 | 一种zif-8型复合光催化剂及其制备方法 |
CN113564632B (zh) * | 2021-08-10 | 2023-01-24 | 广东电网有限责任公司 | 一种燃料电池性能优化异质结材料及其制备方法、电催化二氧化碳还原 |
EP4170808A4 (en) | 2021-08-25 | 2023-06-28 | Contemporary Amperex Technology Co., Limited | Organic-inorganic hybrid porous material and preparation method therefor, membrane, electrochemical device, and electrical device |
CN114522686B (zh) * | 2021-09-07 | 2023-11-21 | 盐城工学院 | 玉米芯负载金属-有机框架制备的Cu/Cu2O/C复合材料及其应用 |
CN115140757B (zh) * | 2021-11-04 | 2023-06-27 | 燕山大学 | 一种中空多孔结构氧化铜及其制备方法和应用 |
CN113893882B (zh) * | 2021-11-10 | 2023-08-08 | 武汉纺织大学 | 一种基于金属有机配体的铜氧化物催化剂及其制备方法和应用 |
CN114164446B (zh) * | 2021-11-19 | 2023-12-22 | 常州大学 | 一种金属有机框架衍生的Cu掺杂CeO2负载PdCu合金催化剂及其制备方法 |
CN114345337B (zh) * | 2021-12-17 | 2024-03-22 | 广东省科学院化工研究所 | 一种乳酸的制备方法 |
CN114288869B (zh) * | 2021-12-28 | 2023-01-20 | 广州大学 | 一种CuO@Cu-PDA/PEI改性膜的制备方法 |
CN114477434A (zh) * | 2022-01-24 | 2022-05-13 | 重庆大学 | 厌氧反应系统 |
CN114471728B (zh) * | 2022-02-16 | 2024-02-09 | 天津工业大学 | 铜系纳米粒子和铁卟啉纳米片复合的纳米酶及制备与应用 |
CN114632533B (zh) * | 2022-03-09 | 2024-02-13 | 深圳信息职业技术学院 | 一种亚纳米金属催化剂及其制备方法、应用方法 |
CN114875674B (zh) * | 2022-05-06 | 2023-01-24 | 南通大学 | 一种负载PVP/Cu-MOFs的抗菌羊毛织物的制备方法 |
CN115090289B (zh) * | 2022-07-20 | 2024-02-02 | 上海理工大学 | 一种新型钙钛矿原位生长FeCo-MOFs衍生纳米碳微波催化剂及其制备方法和应用 |
CN116004184B (zh) * | 2023-02-07 | 2024-04-16 | 西南石油大学 | 一种纳米金属氧化物/碳复合吸波材料及其制备方法 |
CN115947337B (zh) * | 2023-03-01 | 2024-07-23 | 昆明理工大学 | 一种固废型生物炭的制备方法及其应用 |
CN116422329B (zh) * | 2023-05-05 | 2024-06-28 | 浙江工业大学 | 一种有序Cu-CuxO多孔碳催化材料、制备方法及其应用 |
CN117430819B (zh) * | 2023-10-16 | 2024-07-12 | 东北师范大学 | 用于电还原co2至乙醇的金属有机框架材料制备方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101269317A (zh) * | 2007-03-23 | 2008-09-24 | 中国科学院大连化学物理研究所 | 一种负载型多孔金属有机化合物储氢材料 |
CN103111262A (zh) * | 2013-01-31 | 2013-05-22 | 北京大学 | 一种金属有机骨架多孔材料及其制备方法 |
CN103601756A (zh) * | 2013-11-06 | 2014-02-26 | 江苏华富储能新技术股份有限公司 | 铋金属有机框架材料、制备方法及其铅蓄电池正极添加剂 |
CN105214726A (zh) * | 2015-09-29 | 2016-01-06 | 齐鲁工业大学 | 一种用于催化还原的纳米铜复合材料的制备 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10326145B2 (en) * | 2012-04-11 | 2019-06-18 | Uchicago Argonne, Llc | Synthesis of electrocatalysts using metal-organic framework materials |
DE202013102315U1 (de) * | 2013-04-06 | 2014-04-09 | BLüCHER GMBH | Aktivkohle mit spezieller Ausrüstung |
US9795948B2 (en) * | 2015-01-16 | 2017-10-24 | King Abdulaziz University | Sunlight active composite photocatalyst for water purification |
CN104868109B (zh) | 2015-05-04 | 2017-04-19 | 南开大学 | 一种二氧化锡/多孔碳复合的锂离子电池负极材料 |
CN105664944B (zh) * | 2016-02-19 | 2018-03-27 | 中国环境科学研究院 | 一种基于金属有机框架的Cu催化剂、制备方法及用途 |
-
2016
- 2016-02-19 CN CN201610095270.4A patent/CN105664944B/zh active Active
- 2016-12-22 US US15/999,839 patent/US10940469B2/en active Active
- 2016-12-22 WO PCT/CN2016/111427 patent/WO2017140176A1/zh active Application Filing
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101269317A (zh) * | 2007-03-23 | 2008-09-24 | 中国科学院大连化学物理研究所 | 一种负载型多孔金属有机化合物储氢材料 |
CN103111262A (zh) * | 2013-01-31 | 2013-05-22 | 北京大学 | 一种金属有机骨架多孔材料及其制备方法 |
CN103601756A (zh) * | 2013-11-06 | 2014-02-26 | 江苏华富储能新技术股份有限公司 | 铋金属有机框架材料、制备方法及其铅蓄电池正极添加剂 |
CN105214726A (zh) * | 2015-09-29 | 2016-01-06 | 齐鲁工业大学 | 一种用于催化还原的纳米铜复合材料的制备 |
Non-Patent Citations (3)
Title |
---|
"MOF derived porous Carbon supported Cu/Cu2O composite as high performance non-noble catalysy";Hongyun Niu et al.;《Microporous and Mesoporous Materials》;20150731;第279卷;第48-53页 * |
"MOF-derived Cu/nanoporous carbon composite and its application for electro-catalysis of hydrogen evolution reaction";Jahan-Bakhsh Raoof et al.;《Energy》;20150828;第90卷;第1075-1081 * |
"One-pot achieving well-dispersed copper nanoparticles on N-doped carbon films";Lin Chen et al.;《Journal of Alloys and Compounds》;20151103;第656卷;第622-627页 * |
Also Published As
Publication number | Publication date |
---|---|
CN105664944A (zh) | 2016-06-15 |
WO2017140176A1 (zh) | 2017-08-24 |
US20200129971A1 (en) | 2020-04-30 |
US10940469B2 (en) | 2021-03-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN105664944B (zh) | 一种基于金属有机框架的Cu催化剂、制备方法及用途 | |
CN109305917B (zh) | 一种卤代苯胺的合成方法 | |
Chen et al. | Synergy effect between adsorption and heterogeneous photo-Fenton-like catalysis on LaFeO3/lignin-biochar composites for high efficiency degradation of ofloxacin under visible light | |
Yu et al. | Temperature‐Controlled Selectivity of Hydrogenation and Hydrodeoxygenation of Biomass by Superhydrophilic Nitrogen/Oxygen Co‐Doped Porous Carbon Nanosphere Supported Pd Nanoparticles | |
Li et al. | Novel Ag3PO4 modified tubular carbon nitride with visible-light-driven peroxymonosulfate activation: A wide pH tolerance and reaction mechanism | |
Liu et al. | Efficient selective oxidation of aromatic alkanes by double cobalt active sites over oxygen vacancy‐rich mesoporous Co3O4 | |
CN111151285B (zh) | 一种氮掺杂多孔碳负载ZnS纳米复合材料及其制备方法和应用 | |
Elfiad et al. | Low-cost synthesis of Cu/α-Fe2O3 from natural HFeO2: application in 4-nitrophenol reduction | |
Dou et al. | Metal–Organic Framework (MOF)‐Derived Electron‐Transfer Enhanced Homogeneous PdO‐Rich Co3O4 as a Highly Efficient Bifunctional Catalyst for Sodium Borohydride Hydrolysis and 4‐Nitrophenol Reduction | |
CN108212217A (zh) | 一种降解氯酚类污染物的催化剂、制备方法和应用 | |
CN106984324A (zh) | 可见光响应型笼型结构钒酸铜水合物光催化剂的制备方法 | |
Yu et al. | Visible-light-assisted activation of peroxymonosulfate (PMS) over CoOx@ C/g-C3N4 composite for efficient organic pollutant degradation | |
Xu et al. | Impact of Pore Structure on Two‐Electron Oxygen Reduction Reaction in Nitrogen‐Doped Carbon Materials: Rotating Ring‐Disk Electrode vs. Flow Cell | |
Peng et al. | Green synthesis of Pd truncated octahedrons using of firmiana simplex leaf extract and their catalytic study for electro‐oxidation of methanol and reduction of p‐nitrophenol | |
Zhou et al. | Comparison of the catalytic properties of Au nanoparticles supported on different two-dimensional carriers | |
Bagheri et al. | Enhanced Catalytic Performance of Quasi‐HKUST‐1 for the Tandem Imine Formation | |
Hu et al. | Core‐Shell ZIF‐67@ CeO2 Nanosphere as Efficient Acid‐Base Catalyst for the Cycloaddition of CO2 and Epoxides | |
Lu et al. | Synergistic degradation of fluorene in soil by dielectric barrier discharge plasma combined with P25/NH2-MIL-125 (Ti) | |
Wang et al. | Fe Doped MIL-101/Graphene Nanohybrid for Photocatalytic Oxidation of Alcohols Under Visible-Light Irradiation | |
He et al. | Photo‐activated direct catalytic oxidation of gaseous benzene with a Cu‐connected serial heterojunction array of Co3O4/CuxO/foam Cu assembled via layer upon layer oxidation | |
Xu et al. | An Efficient, Multi‐element AC/TiO2/WO3 Photocatalyst for the Degradation of Tetracycline Hydrochloride | |
Lin et al. | Hollow N‐ZIFs@ NiCo‐LDH as highly efficient catalysts for 4‐nitrophenol and dyes | |
CN113751006B (zh) | 碳包覆氧化镍的纳米复合材料及其制备方法和应用 | |
Sun et al. | Bimetallic Mn-Ce oxides modified α-Fe2O3 nanorods for low temperature catalytic thermal desorption of naphthalene in soil | |
Xu et al. | Preparation of organic porous materials-TiO 2/cu composite with excellent photocatalytic degradation performances toward degradation of organic pollutants in wastewater |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |