CN109305922A - 一种氨基苯酚类化合物的合成方法 - Google Patents
一种氨基苯酚类化合物的合成方法 Download PDFInfo
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- CN109305922A CN109305922A CN201810842134.6A CN201810842134A CN109305922A CN 109305922 A CN109305922 A CN 109305922A CN 201810842134 A CN201810842134 A CN 201810842134A CN 109305922 A CN109305922 A CN 109305922A
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- nanocomposite
- synthetic method
- carbon
- nickel
- nitrogen
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- -1 amino phenols compound Chemical class 0.000 title claims abstract description 66
- 238000010189 synthetic method Methods 0.000 title claims abstract description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 195
- 239000002114 nanocomposite Substances 0.000 claims abstract description 135
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 90
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 87
- 238000000576 coating method Methods 0.000 claims abstract description 77
- 239000011248 coating agent Substances 0.000 claims abstract description 76
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 45
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 40
- 239000001301 oxygen Substances 0.000 claims abstract description 38
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000009826 distribution Methods 0.000 claims abstract description 36
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 239000001257 hydrogen Substances 0.000 claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 25
- 230000009467 reduction Effects 0.000 claims abstract description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011258 core-shell material Substances 0.000 claims abstract description 19
- 239000012298 atmosphere Substances 0.000 claims abstract description 17
- 239000013335 mesoporous material Substances 0.000 claims abstract description 13
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 8
- 239000011148 porous material Substances 0.000 claims description 47
- 239000002253 acid Substances 0.000 claims description 38
- 229910052799 carbon Inorganic materials 0.000 claims description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 35
- 238000005406 washing Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 229910001868 water Inorganic materials 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- 125000001424 substituent group Chemical group 0.000 claims description 8
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- RTZZCYNQPHTPPL-UHFFFAOYSA-N 3-nitrophenol Chemical compound OC1=CC=CC([N+]([O-])=O)=C1 RTZZCYNQPHTPPL-UHFFFAOYSA-N 0.000 claims description 5
- KGDIYDUZVHFMHQ-UHFFFAOYSA-N 4,5-dimethyl-2-nitrophenol Chemical compound CC1=CC(O)=C([N+]([O-])=O)C=C1C KGDIYDUZVHFMHQ-UHFFFAOYSA-N 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 3
- 238000006722 reduction reaction Methods 0.000 claims 3
- 239000004575 stone Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 65
- 238000000034 method Methods 0.000 abstract description 40
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- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 20
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 18
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 17
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 16
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 7
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 7
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- 239000002184 metal Substances 0.000 description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
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- 239000000126 substance Substances 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 230000002269 spontaneous effect Effects 0.000 description 3
- 230000002459 sustained effect Effects 0.000 description 3
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
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- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
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- 238000005260 corrosion Methods 0.000 description 2
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- 239000003814 drug Substances 0.000 description 2
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- 235000013399 edible fruits Nutrition 0.000 description 2
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical compound O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 description 2
- ZHUXMBYIONRQQX-UHFFFAOYSA-N hydroxidodioxidocarbon(.) Chemical compound [O]C(O)=O ZHUXMBYIONRQQX-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 230000032258 transport Effects 0.000 description 2
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- DOLQYFPDPKPQSS-UHFFFAOYSA-N 3,4-dimethylaniline Chemical class CC1=CC=C(N)C=C1C DOLQYFPDPKPQSS-UHFFFAOYSA-N 0.000 description 1
- 229940018563 3-aminophenol Drugs 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
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- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
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- 208000012839 conversion disease Diseases 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- FFXSKLNKKMNFDZ-UHFFFAOYSA-N iron 4-nitrophenol Chemical compound [Fe].[N+](=O)([O-])C1=CC=C(C=C1)O FFXSKLNKKMNFDZ-UHFFFAOYSA-N 0.000 description 1
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- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/11—Making porous workpieces or articles
- B22F3/1143—Making porous workpieces or articles involving an oxidation, reduction or reaction step
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/38—Removing components of undefined structure
- B01D53/44—Organic components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
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- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- 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
- 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
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Abstract
本发明提供一种氨基苯酚类化合物的合成方法,包括:以碳包覆镍的纳米复合材料为催化剂,在氢气气氛下催化硝基苯酚类化合物进行加氢还原反应;其中,所述纳米复合材料含具有壳层和内核的核壳结构,所述壳层为掺杂氮和氧的石墨化碳层,所述内核为镍纳米颗粒,其中所述纳米复合材料为具有至少一个介孔分布峰的介孔材料。该方法采用含核壳结构的碳包覆镍的纳米复合材料为催化剂,其丰富的介孔结构,有利于催化反应的传质,用于硝基苯酚类化合物加氢还原合成氨基苯酚类化合物,具有优异的活性、选择性及安全性。
Description
技术领域
本发明涉及催化领域,具体涉及一种氨基苯酚类化合物的合成方法。
背景技术
氨基苯酚类化合物可广泛应用于染料工业、医药工业和香料中间体。例如,对氨基苯酚是一种用途广泛的有机化工中间体,主要用于生产药物、染料、抗氧剂、显影剂等,它也是分散染料、酸性染料、直接染料、硫化染料和皮毛染料的中间体醇类化合物是非常重要的化工中间体,在有机溶剂、精细化工、医药,农药,家用化妆品等行业有十分广泛的用途。
目前,工业上生产对氨基苯酚主要有三种方法:硝基苯加氢还原法,对硝基苯酚铁粉还原法,对硝基苯酚加氢还原法。其中,对硝基苯酚加氢还原法是应用较广泛的工艺。用于催化加氢反应的催化剂以铂(Pt)、钯(Pd)和铑(Rh)等贵金属催化剂及铜(Cu)、镍(Ni)、铅(Zn)、钼(Mo)等非贵金属催化剂为主。但实际应用中,贵金属催化剂价格成本过高,且贵金属流失对环境危害大,在工业化生产中的应用有限;非贵金属负载型催化剂也存在一系列问题,例如,在制备过程中易发生团聚、催化加氢过程中易被洗脱,稳定性差、具有较大安全隐患等。
因此,开发在空气中稳定并具有优异催化性能的加氢还原催化剂用于硝基苯酚类化合物的加氢还原以合成氨基苯酚类化合物,是本领域亟待解决的问题。
需注意的是,前述背景技术部分公开的信息仅用于加强对本发明的背景理解,因此它可以包括不构成对本领域普通技术人员已知的现有技术的信息。
发明内容
本发明提供一种氨基苯酚类化合物的合成方法,该方法采用含核壳结构的碳包覆镍的纳米复合材料为催化剂,碳材料与镍纳米颗粒协同发挥作用,产生了良好的催化效果,其包覆严密的金属纳米粒子,有利于在更苛刻的条件下发挥作用,用于硝基苯酚类化合物加氢还原合成氨基苯酚类化合物,具有优异的活性、选择性及安全性。
为了实现上述目的,本发明采用如下技术方案:
本发明提供一种氨基苯酚类化合物的合成方法,包括:
以碳包覆镍的纳米复合材料为催化剂,在氢气气氛下催化硝基苯酚类化合物进行加氢还原反应;
其中,所述纳米复合材料含具有壳层和内核的核壳结构,所述壳层为掺杂氮和氧的石墨化碳层,所述内核为镍纳米颗粒,所述纳米复合材料的酸洗损失率≤60%。
根据本发明的一个实施方式,其中所述硝基苯酚类化合物的苯环上还含有取代基,所述取代基选自C1-20的烷基、环烷基和芳基中的一种或多种。
根据本发明的一个实施方式,其中所述硝基苯酚类化合物选自邻硝基苯酚、对硝基苯酚、间硝基苯酚和4,5-二甲基-2-硝基苯酚中的一种或多种。
根据本发明的一个实施方式,其中所述催化剂占所述硝基苯酚类化合物质量的1%~50%,优选5%~30%。
根据本发明的一个实施方式,其中所述加氢还原反应温度一般为50℃~120℃。
根据本发明的一个实施方式,其中所述氢气的压力一般为0.5MPa~2MPa。
根据本发明的一个实施方式,所述加氢还原反应的反应时间优选为1~3h。
根据本发明的一个实施方式,其中所述硝基苯酚类化合物与所述催化剂在溶剂中混合后进行加氢还原反应,所述溶剂选自醇类、醚类、烷烃类和水中的一种或多种。
根据本发明的一个实施方式,其中所述纳米复合材料为具有至少一个介孔分布峰的介孔材料。任选地,所述纳米复合材料为具有两个或两个以上介孔分布峰的介孔材料。任选地,所述纳米复合材料在2nm~7nm的孔径范围和8nm~20nm的孔径范围分别具有一个介孔分布峰。任选地,所述介孔材料中介孔体积占总孔体积的比例大于50%,优选大于80%,更优选大于95%。任选地,所述石墨化碳层的厚度为0.3nm~6.0nm,优选为0.3nm~3nm。任选地,其中所述核壳结构的粒径为1nm~200nm,优选为3nm~100nm,更优选为4nm~50nm。任选地,以质量百分比计,所述纳米复合材料的碳含量为10.0%~60.0%,镍含量为30.0%~85.0%;优选地,碳含量为30.0%~50.0%,镍含量为30.0%~60.0%。任选地,以质量百分比计,该纳米复合材料中,氮和氧的总含量小于15.0%,优选为0.2%~12.0%,更优选为0.5%~10.0%。任选地,以质量百分比计,该纳米复合材料中,氮含量小于15%,优选为0.1%~10%,更优选为1%~5%。上述纳米复合材料中各组分的含量之和为100%。
根据本发明的一个实施方式,其中所述纳米复合材料的酸洗损失率≤10%。任选地,所述纳米复合材料为具有至少一个介孔分布峰的介孔材料。任选地,所述纳米复合材料为具有两个或两个以上介孔分布峰的介孔材料。任选地,所述纳米复合材料在2nm~7nm的孔径范围和8nm~20nm的孔径范围分别具有一个介孔分布峰。任选地,所述介孔材料中介孔体积占总孔体积的比例大于50%,优选大于80%,更优选大于95%。任选地,所述石墨化碳层的厚度为0.3nm~6.0nm,优选为0.3nm~3nm。任选地,所述核壳结构的粒径为1nm~200nm,优选为3nm~100nm,更优选为4nm~50nm。任选地,以质量百分比计,所述纳米复合材料的碳含量为碳含量为15%~60%,镍含量为30%~80%,优选地,碳含量为30%~60%,镍含量为30%~60%。任选地,以质量百分比计,该纳米复合材料中,氮和氧的总含量小于15.0%。任选地,以质量百分比计,氮的含量为2%~8%,氧的含量为3%~9%。
本发明的有益效果在于:
本发明提供的氨基苯酚类化合物的合成方法,以碳包覆镍的纳米复合材料作为催化剂对硝基苯酚类化合物进行加氢还原,由于催化剂材料含石墨化碳层/金属核壳结构,没有可使反应物接近镍金属中心的孔道或缺陷,使内核的镍十分稳定,不自燃,耐酸腐蚀,危险性低,适合保存与运输,从而保证了复合材料使用的安全性。本发明的催化剂材料非常稳定,不自燃,抗氧化,耐酸腐蚀,危险性低,适合保存与运输,从而保证了硝基苯酚类化合物合成过程的安全性。
本发明的碳包覆镍的纳米复合材料在催化还原硝基苯酚类化合物为氨基苯酚类化合物的反应中表现了良好的重复性、高活性及高选择性,此外,由于该纳米复合材料具有较强的磁性,还可方便利用其磁性分离催化剂或用于磁稳定床等工艺。
附图说明
图1为制备例1所制备的氮氧掺杂碳包覆镍纳米复合材料的TEM图;
图2为制备例1所制备的氮氧掺杂碳包覆镍纳米复合材料的XRD图;
图3a为制备例1所制备的氮氧掺杂碳包覆镍纳米复合材料的N2吸附-脱附等温线;
图3b为制备例1所制备的氮氧掺杂碳包覆镍纳米复合材料的BJH孔径分布曲线。
图4a是制备例1所制备的氮氧掺杂碳包覆镍纳米复合材料的XPS图;
图4b是制备例1所制备的氮氧掺杂碳包覆镍纳米复合材料的XPS中的Ni 2p谱图;
图4c是制备例1所制备的氮氧掺杂碳包覆镍纳米复合材料的XPS中的O 1s分峰结果;
图5是制备例2所制备的氮氧掺杂碳包覆镍纳米复合材料的TEM图;
图6是制备例2所制备的氮氧掺杂碳包覆镍纳米复合材料的XRD图;
图7是制备例2所制备的氮氧掺杂碳包覆镍纳米复合材料的BJH孔径分布曲线;
图8为制备例3所制备的氮氧掺杂碳包覆镍纳米复合材料的TEM图;
图9为制备例3所制备的氮氧掺杂碳包覆镍纳米复合材料的XRD图;
图10a是制备例3所制备的氮氧掺杂碳包覆镍纳米复合材料的N2吸附-脱附等温线;
图10b是制备例3所制备的氮氧掺杂碳包覆镍纳米复合材料的BJH孔径分布曲线。
图11a是制备例3所制备的氮氧掺杂碳包覆镍纳米复合材料的XPS图;
图11b是制备例3所制备的氮氧掺杂碳包覆镍纳米复合材料的XPS中的Ni 2p谱图;
图11c是制备例3所制备的氮氧掺杂碳包覆镍纳米复合材料的XPS中的O 1s分峰结果;
图12是制备例4所制备的氮氧掺杂碳包覆镍纳米复合材料的TEM图;
图13是制备例4所制备的氮氧掺杂碳包覆镍纳米复合材料的XRD图;
图14是制备例4所制备的氮氧掺杂碳包覆镍纳米复合材料的BJH孔径分布曲线;
图15是对比例1所制备的材料的XRD图。
具体实施方式
以下结合附图通过具体的实施例对本发明作出进一步的详细描述,应当理解的是,此处所描述的具体实施方式仅用于说明和解释本发明,但不以任何方式限制本发明。
本发明中,除了明确说明的内容之外,未提到的任何事宜或事项均直接适用本领域已知的那些而无需进行任何改变。而且,本文描述的任何实施方式均可以与本文描述的一种或多种其他实施方式自由结合,由此形成的技术方案或技术思想均视为本发明原始公开或原始记载的一部分,而不应被视为是本文未曾披露或预期过的新内容,除非本领域技术人员认为该结合明显不合理。
本发明所公开的所有特征可以任意组合,这些组合应被理解为本发明所公开或记载的内容,除非本领域技术人员认为该组合明显不合理。本说明书所公开的数值点,不仅包括实施例中具体公开的数值点,还包括说明书中各数值范围的端点,这些数值点所任意组合的范围都应被视为本发明已公开或记载的范围。
在此未直接定义的任何术语应当被理解为具有与它们在本发明技术领域中通常所理解的相关联的含义。如贯穿本说明书使用的下面术语除非另外说明,应当理解为具有下面含义。
术语
术语“烷基”在本文中定义为直链或支链的烷基,例如甲基、乙基、丙基、异丙基、丁基、叔丁基、戊基、己基等。
术语“环烷基”在本文中定义为由单键连接并构成环状的烷基基团,例如环己基。
术语“芳基”在本文中定义为从简单苯环衍生出的官能团或取代基,例如苯甲基。
术语“硝基苯酚类化合物”是指苯环上至少一个氢原子被硝基取代,至少另一个氢原子被羟基取代而生成的一类化合物,包括苯环上未有羟基和硝基以外的其它取代基的硝基苯酚和苯环上其它氢原子至少一个被羟基和硝基以外的基团取代的硝基苯酚。
术语“氨基苯酚类化合物”是指苯环上至少一个氢原子被氨基取代,至少另一个氢原子被羟基取代而生成的一类化合物,包括苯环上未有羟基和氨基以外的其它取代基的氨基苯酚和苯环上其它氢原子至少一个被羟基和氨基以外的基团取代的氨基苯酚。
术语“石墨化碳层”是指在高分辨透射电镜下可明显观察到层状结构的碳结构,而非无定型结构,且层间距为0.34nm。该石墨化碳层包覆镍纳米粒子后形成的纳米复合材料呈球形或类球形。
术语“介孔”定义为孔径在2~50nm范围的孔。孔径小于2nm的孔定义为微孔,大于50nm的孔定义为大孔。
术语“介孔材料”定义为包含介孔孔道结构的多孔材料。
术语“碳包覆率”反映镍被石墨化碳层有效包覆的比例,可通过高分辨透射电镜(HRTEM)的分析结果和催化氧化反应的实验结果表征。
术语“碳包覆严密程度”反映镍被石墨化碳层与外部环境隔绝的比例,可通过高分辨透射电镜(HRTEM)的分析结果、镍含量分析结果和酸洗实验结果表征。
术语“掺杂氮和氧的石墨化碳层”中的“氮”是指氮元素,“氧”是指氧元素,其中“氧含量”是指氧元素的含量,具体是指,在碳包覆纳米复合材料制备过程中,形成石墨化碳层中含有以各种形式存在的氧元素,所述“氧含量”为所有形式的氧元素的总含量,同理,“氮含量”是指氮元素的含量,即所有形式的氮元素的总含量。
术语“介孔分布峰”是指根据Barrett-Joyner-Halenda(BJH)方法对脱附曲线进行计算得到的孔分布曲线上的介孔分布峰。
术语“酸处理”是指在制备碳包覆镍的纳米复合材料时对高温热解步骤后生成的产物所进行的处理方式,是制备复合材料中的步骤。
术语“酸洗损失率”是指制备完成的碳包覆镍的纳米复合材料产品经酸洗后镍的损失比例。其反映了石墨化碳层对镍包覆的严密程度。如果石墨化碳层对镍包覆不严密,则在酸处理后,内核的镍会被酸溶解从而流失。酸洗损失率越大,表明石墨化碳层对镍包覆的严密程度越低,反之,酸洗损失率越小,表明石墨化碳层对镍包覆的严密程度越高。本发明中定义酸洗损失率≤10%为“严密包覆”的核壳结构的纳米复合材料。
所述的“酸洗损失率”按以下方式测量并计算:
按20mL硫酸水溶液(1mol/L)投加1g样品的比例,在90℃下对样品处理8h,然后用去离子水洗涤至中性,干燥后称重、分析,按下式计算酸洗损失率。
酸洗损失率=[1-(酸洗后复合材料中镍的质量分数×酸洗后复合材料的质量)÷(待酸洗复合材料中镍的质量分数×待酸洗复合材料的质量)]×100%。
试剂、仪器与测试
如无特殊说明,本发明所采用试剂均为分析纯,所用试剂均为市售可得,例如购自西格玛奥德里奇(Sigma-Aldrich)。
本发明所采用XRD衍射仪的型号为XRD-6000型X射线粉末衍射仪(日本岛津),XRD测试条件为:Cu靶,Kα射线(波长λ=0.154nm),管电压为40kV,管电流为200mA,扫描速度为10°(2θ)/min。
本发明所采用高分辨透射电镜(HRTEM)的型号为JEM-2100(HRTEM)(日本电子株式会社),高分辨透射电镜测试条件为:加速电压为200kV。
本发明所采用X射线光电子能谱分析仪(XPS)为VG Scientifc公司生产配备有Avantage V5.926软件的ESCALab220i-XL型射线电子能谱仪,X射线光电子能谱分析测试条件为:激发源为单色化A1KαX射线,功率为330W,分析测试时基础真空为3×10-9mbar。另外。电子结合能用C1s峰(284.6eV)校正,后期分峰处理软件为XPSPEAK。
碳(C)、氢(H)、氧(O)、氮(N)四种元素的分析在Elementar Micro Cube元素分析仪上进行,具体操作方法和条件如下:样品在锡杯中称量1mg~2mg,放入自动进样盘,通过球阀进入燃烧管燃烧,燃烧温度为1000℃(为了去除进样时大气干扰,采用氦气吹扫),然后用还原铜对燃烧后的气体进行还原,形成氮气、二氧化碳和水。混合气体通过三根解吸柱进行分离,依次进TCD检测器检测。氧元素的分析是利用高温分解,在碳催化剂的作用下,将样品中的氧转化为CO,然后采用TCD检测CO。由于本发明的复合材料中仅含有碳、氢、氧、氮和金属元素,因此由碳、氢、氧、氮四种元素的总含量即可知金属元素的总含量。
不同金属元素之间的比例由X射线荧光光谱分析仪(XRF)测定,由已知的碳、氢、氧、氮四种元素总含量,算出不同金属元素在复合材料中的含量。本发明所采用X射线荧光光谱分析仪(XRF)的型号为Rigaku 3013X射线荧光光谱仪,X射线荧光光谱分析测试条件为:扫描时间为100s,气氛为空气。
BET测试方法:本发明中,样品的孔结构性质由Quantachrome AS-6B型分析仪测定,催化剂的比表面积和孔体积由Brunauer-Emmett-Taller(BET)方法得到,孔分布曲线根据Barrett-Joyner-Halenda(BJH)方法对脱附曲线进行计算得到。
本发明中,碳包覆镍纳米粒子的平均粒径由XRD图分峰后,由谢乐公式:D=kγ/(Bcosθ)计算得到。其中k为Scherrer常数,k=0.89;B为半高宽;θ为衍射角,单位弧度;γ为x射线波长,0.154054nm。
本发明提供一种氨基苯酚类化合物的合成方法,包括:以碳包覆镍的纳米复合材料为催化剂,在氢气气氛下催化硝基苯酚类化合物进行加氢还原反应;化学反应方程式例示如下,其中R代表苯环上的一个或多个取代基:
其中,所述纳米复合材料含具有壳层和内核的核壳结构,所述壳层为掺杂氮和氧的石墨化碳层,所述内核为镍纳米颗粒,所述纳米复合材料的酸洗损失率≤60%。
在一些实施例中,所述硝基苯酚类化合物的苯环上还含有取代基,所述取代基R选自C1-20的烷基、环烷基和芳基中的一种或多种,上述取代可以为单取代,也可以为多取代,例如邻硝基苯酚、对硝基苯酚、间硝基苯酚、4,5-二甲基-2-硝基苯酚。
在一些实施例中,其中所述催化剂占所述硝基苯酚类化合物质量的1%~50%,优选5%~30%。
在一些实施例中,其中所述加氢还原反应温度一般为50℃~120℃。
在一些实施例中,其中所述氢气的压力一般为0.5MPa~2MPa。
在一些实施例中,其中所述硝基苯酚类化合物与所述催化剂在溶剂中混合后进行加氢还原反应,所述溶剂选自醇类、醚类、烷烃类和水中的一种或多种,例如乙醇、四氢呋喃、环己烷等。
根据本发明的一个实施方式,在上述合成方法中采用的纳米复合材料为具有至少一个介孔分布峰的介孔材料。即指,该纳米复合材料在根据Barrett-Joyner-Halenda(BJH)方法对脱附曲线进行计算得到的孔分布曲线上,至少具有一个介孔分布峰。
上述纳米复合材料,其掺杂氮和氧的石墨化碳层表面具有丰富的缺陷位,碳材料本身就具有催化活性,与镍纳米颗粒协同发挥作用,可使本发明的纳米复合材料具有较佳的催化性能;此外,该纳米复合材料还具有丰富的介孔结构,使其传质效率更高,从而具有更优异的催化性能。
在一些实施例中,单批次制造的复合材料,在介孔范围内有两个分布峰;如将多批次制造的复合材料混合,则在介孔范围内可以有更多的分布峰。当纳米复合材料具有不同孔径范围的多级介孔结构时,可以使其表现出更独特的性能,且多级介孔结构可适用的应用范围更广。
在一些实施例中,所述纳米复合材料的介孔结构在2~7nm的孔径范围和8~20nm的孔径范围分别具有一个介孔分布峰。
在一些实施例中,所述纳米复合材料的介孔体积占总孔体积的比例大于50%,优选大于80%。在一些实施例中,介孔体积占总孔体积的比例为100%。
在一些实施例中,所述纳米复合材料的比表面积一般大于140m2/g,可以大于200m2/g。
本发明的纳米复合材料在空气中不自燃,可以在空气中储存。
所述纳米复合材料的酸洗损失率一般为≤40%,可以为≤10%、10%~20%、20%~30%或30%~40%。如上文所述,酸洗损失率反映了石墨化碳层对镍包覆的严密程度。
在一些实施例中,以质量百分比计,该纳米复合材料中,碳含量为10.0%-60.0%,镍含量为30.0%-85.0%;优选地,碳含量为30.0%-50.0%,镍含量为30.0%-60.0%。
根据本发明的纳米复合材料,在碳层中掺杂有氮和氧。氮、氧含量可以通过在制造过程中额外引入含氧化合物、含氮化合物,比如六亚甲基四胺、多元醇来调节。通过调节所述纳米复合材料中的氮、氧含量,可以调节碳层的催化性能,使其适用与催化不同的反应。在一些实施例中,以质量百分比计,所述纳米复合材料中,氮、氧的总含量小于15.0%,优选为0.2%-12.0%,更优选为0.5%-10.0%,其中氮含量小于15.0%,优选0.1%-10%,更优选为1%-5%。
根据本发明,所述纳米复合材料中,各组分的含量之和为100%。
在一些实施例中,所述石墨化碳层的厚度为0.3nm~6.0nm,优选为0.3nm~3nm。
在一些实施例中,所述核壳结构的粒径为1nm~200nm,优选为3nm~100nm,更优选为4nm~50nm。
在一些实施例中,镍纳米粒子的晶格结构为面心立方晶格结构(fcc)。
在一些实施例中,镍纳米粒子的晶格结构为面心立方晶格结构(fcc)和密排六方晶格结构(hcp)。
在一些实施例中,上述碳包覆镍的纳米复合材料通过如下方法制备:
将镍盐、“多元有机羧酸和含氮化合物,或者含氮的有机多元羧酸”以及可选的其他有机化合物在溶剂中混合形成含镍的水溶性混合物;
将水溶性混合物在惰性气氛或还原性气氛下高温热解。
具体地,制备方法中所提及的水溶性混合物是指将“多元有机羧酸和含氮化合物,或者含氮的有机多元羧酸”及可选的除前者外的其它有机化合物在水、乙醇等溶剂中溶解成均相溶液,然后直接蒸发除去溶剂得到含镍的水溶性混合物。蒸发溶剂的温度和工艺可以采用任意可行的现有技术,例如,在80℃-120℃下喷雾干燥,或在烘箱中干燥。蒸发除去溶剂的过程一般在2小时内完成,优选在1小时内完成。
在一些实施例中,制备中所用到的有机多元羧酸包括但不限于柠檬酸,含氮的有机多元羧酸包括但不限于乙二胺四乙酸(EDTA),镍盐包括但不限于醋酸镍,含氮化合物包括但不限于六亚甲基四胺,所述的其它有机化合物包括但不限于有机多元醇。
在一些实施例中,高温热解步骤中的惰性气氛采用氮气或氩气保护,所述还原性气氛可以为在惰性气氛中掺有少量氢气的气氛其中热解过程包括升温段和恒温段,升温段的升温速率为0.5℃/min~10℃/min,优选2.5℃/min~10℃/min;恒温段的温度为400℃~800℃,优选500℃~700℃;恒温时间为20min~600min,优选30min~300min。
在一些实施例中,镍盐、多元有机羧酸、含氮化合物和其它有机化合物的质量比为1:0.5~10:0.5~10:0~10,优选1:1~3:1~3:0~3,即可以完全不加入其它有机化合物。
又根据本发明的另一个实施方式,在上述合成方法中采用的纳米复合材料的酸洗损失率≤10%。上述严密包覆的纳米复合材料较非严密包覆的复合材料而言,可以更好的保证内核镍在制备和应用中损失率降低,从而更好的发挥复合材料的作用。此外,本领域通常认为催化加氢反应的活性中心是内核镍,不管催化剂的具体结构如何,必须能使反应物与金属中心接触。而本发明的被石墨化碳层严密包覆的镍纳米复合材料,仍具有极佳的催化加氢还原有机化合物的能力,进一步证明了石墨化碳层包裹镍内核的严密性对其催化性能十分重要,金属镍在此起到了不可或缺的修饰作用。
在该实施方式中,该“严密包覆”的碳包覆镍的纳米复合材料,可以具有介孔结构,也可以不具有介孔结构。丰富的介孔结构,更有利于催化反应的传质。在一些实施例中,该纳米复合材料具有至少一个介孔分布峰。在一些实施中,单批次制造的复合材料,在介孔范围内有两个分布峰;如将多批次制造的复合材料混合,则在介孔范围内可以有更多的分布峰。当纳米复合材料具有不同孔径范围的多级介孔结构时,可以使其表现出更独特的性能,且多级介孔结构可适用的应用范围更广。
在一些实施例中,严密包覆的所述纳米复合材料的介孔结构在2~7nm的孔径范围和8~20nm的孔径范围分别具有一个介孔分布峰。
在一些实施例中,孔径在2~5nm范围内的介孔体积占总孔体积的比例大于5%,通过控制介孔体积占总孔体积的比例,使该纳米复合材料具有丰富的介孔孔结构,可以保证传质效率更高。
在一些实施例中,以质量百分比计,所述纳米复合材料中的碳含量为15~60wt%,镍含量为30~80wt%,。
在一些实施例中,纳米复合材料在石墨化碳层中掺杂有氧和氮。氧含量可以通过在制造过程中额外引入含氧化合物,比如多元醇来调节。氮含量可以通过在制造过程中额外引入含氮化合物来调节。通过调节纳米复合材料中的氧含量和氮含量,可以调节石墨化碳层的催化性能,使其适用于催化不同的反应。
在一些实施例中,以质量百分比计,该纳米复合材料中,氮和氧的总含量小于15%。
本发明的纳米复合材料中,各组分的含量之和为100%。
在一些实施例中,所述石墨化碳层的厚度为0.3nm~6.0nm,优选为0.3~3nm。所述核壳结构的粒径为1~200nm,优选为3~100nm,更优选为4~50nm。
在一些实施例中,镍纳米粒子的晶格结构为面心立方晶格结构(fcc)。
在一些实施例中,镍纳米粒子的晶格结构为面心立方晶格结构(fcc)和密排六方晶格结构(hcp)。
在一些实施例中,上述碳包覆镍的纳米复合材料通过如下方法制备:
将镍盐、“多元有机羧酸和含氮化合物,或者含氮的有机多元羧酸”以及其他有机化合物在溶剂中混合形成均相溶液,然后除去溶剂,从而形成含镍的水溶性混合物;
将水溶性混合物在惰性气氛保护下高温热解;
将经过高温热解的产物用酸处理,得到碳包覆镍的纳米复合材料。
具体地,制备方法中所提及的水溶性混合物是指将镍盐、“多元有机羧酸和含氮化合物,或者含氮的有机多元羧酸”及除前者外的其它有机化合物在水、乙醇等中溶解成均相溶液,然后直接蒸发除去水分得到含镍的水溶性混合物。蒸发水分的温度和工艺可以采用任意可行的现有技术,例如,在80℃-120℃下喷雾干燥,或在烘箱中干燥。蒸发除去溶剂的过程一般在2小时内完成,优选在1小时内完成。
在一些实施例中,制备中所用到的有机多元羧酸包括但不限于柠檬酸。镍盐为可溶性盐,包括但不限于醋酸镍。含氮化合物包括但不限于六亚甲基四胺等。其它有机化合物包括但不限于有机多元醇。
在一些实施例中,高温热解步骤中的惰性气氛采用氮气或氩气保护,其中热解过程包括升温段和恒温段,升温段的升温速率为0.5℃/min~10℃/min,优选2.5℃/min~10℃/min;恒温段的温度为400℃~1300℃,优选500℃~800℃;恒温时间为20min~600min,优选30min~300min。
在一些实施例中,镍盐、多元有机羧酸、含氮化合物和其它有机化合物的质量比为1:0.5~10:0.5~10:0~10,优选1:1~3:1~3:0~3,即可以完全不加入其它有机化合物。
一些实施例中,所述酸处理中优选用非氧化性强酸处理,所述非氧化性强酸包括但不限于氢氟酸、盐酸、硝酸和硫酸中的一种或其任意的组合,优选盐酸和/或硫酸。
在一些实施例中,酸处理的条件为:在30℃~100℃之间处理1h以上,优选在60℃~100℃之间处理1h~20h,更优选在70℃~90℃之间处理1h~10h。
本发明通过上述方法制备碳包覆镍纳米复合材料,而没有采用以金属-有机骨架化合物(MOF)为前驱体热解的方法,该方法需要在高温、高压下于溶剂中制得具有周期性结构的晶态固体材料(即MOF),通常制备MOFs的条件比较严格,所需配体价格昂贵,并且很难进行大量生产;此外,该方法制备的复合材料中对金属粒子的包覆不严密,与本发明的纳米复合材料结构上有显著不同。本发明制备碳包覆镍复合材料的方法,方便在制备过程中调节石墨化碳层中的氮含量和氧含量,从而方便调节纳米复合材料的电子特性,以适用于催化不同反应。
下面通过实施例进一步说明:
制备例1
(1)称取10g醋酸镍、10g柠檬酸、20g六亚甲基四胺,将它们加入到装有30mL去离子水的烧杯中,在70℃下搅拌得到均相溶液,并继续加热蒸干得到固体前驱体。试验证明,本步骤所得固体前驱体溶于水。
(2)将步骤(1)得到的前驱体置于瓷舟内,然后将瓷舟置于管式炉的恒温区,通入流量为100mL/min的氮气,并以5℃/min的速率升温至650℃,恒温2h后停止加热,在氮气气氛下冷却至室温,得到碳包覆镍的纳米复合材料。经元素分析仪和X射线荧光光谱分析仪(XRF)测定,该纳米复合材料中所含元素的质量百分含量列于表1中。
材料的表征:该材料的TEM图如图1。可看出,该材料为含有碳包覆金属的纳米复合材料,在镍纳米颗粒的外层包裹着具有一定石墨化程度的碳层,形成完整的核壳结构。碳包覆镍的纳米复合材料的X射线衍射谱图如图2所示,可看出,在该纳米复合材料的衍射图中存在对应于石墨碳的衍射峰(2θ角为25.96°)和fcc Ni的衍射峰(2θ角为44.38°、51.83°和76.42°),由谢乐公式计算出该碳包覆镍纳米粒子的平均粒径为6.3nm。
BET测试表明,该纳米复合材料的比表面积为114m2/g,孔体积为0.181cm3/g,其中介孔体积为0.173cm3/g,占总孔体积的95.6%。图3a和图3b为该纳米复合材料的N2吸附-脱附等温线及BJH孔径分布曲线,可以看出,纳米复合材料在3.75nm和10.03nm处存在两个介孔分布峰。
该纳米复合材料的X射线光电子能谱(XPS)如图4a-图4c所示,从图4a可以看到明显存在C、O、N和Ni的XPS峰,证明了N、O元素的有效掺杂。从图4b可以看出,其中Ni价态为0价。从图4c可以看出,该复合纳米材料中的O不存在金属-氧(M-O)键,只存在羧基氧、羰基氧和羟基氧,充分证明了这种核壳结构有效的将高活性的Ni纳米粒子与空气隔绝,核壳结构完整。
按术语部分所述方法测量、计算,本制备例制得的复合材料的酸洗损失率为14%。在术语部分所述方法的基础上,继续增加酸洗时间,酸洗损失率基本保持不变。
制备例2
(1)称取10g醋酸镍、20g柠檬酸、20g六亚甲基四胺,将它们加入到含有100mL去离子水的烧杯中,在80℃下搅拌得到均相溶液,并继续加热蒸干得到固体前驱体。
(2)将步骤(1)得到的前驱体置于瓷舟内,然后将瓷舟置于管式炉的恒温区,通入流量为150mL/min的氮气,并以5℃/min的速率升温至600℃,恒温2h后停止加热,在氮气气氛下冷却至室温,得到碳包覆纳米材料。经元素分析仪和X射线荧光光谱分析仪(XRF)测定后,该纳米复合材料中所含元素的质量百分含量列于表1中。
材料的表征:该纳米复合材料含有以纳米金属镍为核,具有一定石墨化的碳为壳的核壳结构,TEM图如图5所示;碳包覆镍的纳米复合材料的X射线衍射谱图如图6所示,可看出,在该纳米复合材料的XRD衍射图中存在对应于fcc Ni的衍射峰(2θ角为44.4°、51.9°和76.5°)和hcp Ni的衍射峰(2θ角为41.9°、44.4°和47.5°,由谢乐公式计算出该碳包覆镍纳米粒子的平均粒径为31.4nm。BET测试结果如图7所示,表明该纳米复合材料的比表面积为126m2/g,孔体积为0.213cm3/g,其中介孔体积为0.207cm3/g,占总孔体积的97.1%。通过测定该纳米复合材料的N2吸附-脱附等温线及BJH孔径分布曲线,该纳米复合材料在3.83nm和11.16nm处存在两个介孔分布峰。
按术语部分所述方法测量、计算,本制备例制得的复合材料的酸洗损失率为9.3%。在术语部分所述方法的基础上,继续增加酸洗时间,酸洗损失率基本保持不变。
制备例3
(1)称取10g醋酸镍、10g柠檬酸、20g六亚甲基四胺,将它们加入到含有30mL去离子水的烧杯中,在70℃下搅拌得到均相溶液,并继续加热蒸干得到固体。
(2)将步骤(1)得到的前驱体置于瓷舟内,然后将瓷舟置于管式炉的恒温区,通入流量为100mL/min的氮气,并以5℃/min的速率升温至650℃,恒温2h后停止加热,在氮气气氛下冷却至室温,得到碳包覆镍纳米材料
(3)将步骤(2)得到的材料加入100mL10%的盐酸中,在回流温度下处理12h,然后用去离子水将样品洗涤至中性,干燥。该材料中所含元素的质量百分含量列于表1中。
材料的表征:该材料的TEM图如图8所示,可看出,该材料为含有碳包覆金属核壳结构的纳米复合材料,在镍纳米颗粒的外层包裹着具有一定石墨化程度的碳层,形成完整的核壳结构。碳包覆镍的纳米材料的X射线衍射谱图如图9所示,可看出,在该材料的衍射图中存在对应于石墨碳的衍射峰(2θ角为25.97°)和fcc Ni的衍射峰(2θ角为44.47°、51.34°和76.26°),由谢乐公式计算出该碳包覆镍纳米粒子的平均粒径为8.1nm。
BET测试表明,该材料的比表面积为200m2/g,孔体积为0.204cm3/g,其中介孔体积为0.201cm3/g,占总孔体积的98.6%;其中2-5nm的孔体积为0.0245cm3/g,占总孔体积的12.0%。图10a和图10b为该材料的N2吸附-脱附等温线及BJH孔径分布曲线,可以看出,所述复合材料在3.79nm和10.01nm处存在两个介孔分布峰。
该纳米复合材料的X射线光电子能谱(XPS)如图11a-图11c所示,从图11a可以看到明显存在C、O、N和Ni的XPS峰,证明了N、O元素的有效掺杂。从图11b可以看出,其中Ni价态为0价。从图11c可以看出,该复合纳米材料中的O不存在金属-氧(M-O)键,只存在羧基氧、羰基氧和羟基氧,充分证明了这种核壳结构有效的将高活性的Ni纳米粒子与空气隔绝,核壳结构完整。
按术语部分所述方法测量、计算,本制备例制得的复合材料的酸洗损失率为0。在术语部分所述方法的基础上,继续增加酸洗时间,酸洗损失率基本保持不变。
制备例4
(1)称取10g醋酸镍、20g柠檬酸、20g六亚甲基四胺,将它们加入到含有100mL去离子水的烧杯中,在80℃下搅拌得到均相溶液,并继续加热蒸干得到固体。
(2)将步骤(1)得到的前驱体置于瓷舟内,然后将瓷舟置于管式炉的恒温区,通入流量为150mL/min的氮气,并以5℃/min的速率升温至600℃,恒温2h后停止加热,在氮气气氛下冷却至室温,得到碳包覆纳米材料。
(3)将步骤(2)得到的材料加入80mL 10%的盐酸中,在回流温度下处理10h,然后用去离子水将样品洗涤至中性,干燥。经元素分析仪和X射线荧光光谱分析仪(XRF)测定后,该材料中所含元素的质量百分含量列于表1中。
材料的特征:该纳米复合材料的TEM图如图12所示,该纳米复合材料含有以纳米金属镍为核,具有一定石墨化的碳为壳的纳米粒子;该材料的X射线衍射谱图如图13所示,在该材料的XRD衍射图中存在对应于碳的衍射峰(2θ角为26.1°)、fcc Ni的衍射峰(44.6°、51.8°和76.4°)和hcp Ni的衍射峰(2θ角为41.7°、44.6°、47.6°和62.4°),由谢乐公式计算出该碳包覆镍纳米粒子的平均粒径为34.5nm;BET测试表明,该材料的比表面积为183m2/g,孔体积为0.278cm3/g,其中介孔体积为0.276cm3/g,占总孔体积的99.3%;其中2-5nm的孔体积为0.0646cm3/g,占总孔体积的23.2%。图14为该材料的BJH孔径分布曲线,可以看出,该复合材料在3.83nm和9.97nm处存在两个介孔分布峰。
按术语部分所述方法测量、计算,本制备例制得的复合材料的酸洗损失率为0。在术语部分所述方法的基础上,继续增加酸洗时间,酸洗损失率基本保持不变。
表1 制备例1-4中测得元素的质量百分含量
制备例 | 碳,wt% | 氢,wt% | 氮,wt% | 氧,wt% | 镍,wt% |
制备例1 | 43.30 | 1.08 | 3.88 | 3.99 | 47.75 |
制备例2 | 46.86 | 1.20 | 4.26 | 5.22 | 42.46 |
制备例3 | 47.55 | 1.33 | 4.27 | 4.84 | 42.01 |
制备例4 | 48.57 | 1.35 | 4.61 | 5.79 | 39.68 |
对比例1
将10g醋酸镍固体置于瓷舟内,然后将瓷舟置于管式炉的恒温区,通入流量为150mL/min的氮气,并以5℃/min的速率升温至600℃,恒温2h后停止加热,并在氮气气氛下冷却至室温,得到样品材料。经元素分析仪和X射线荧光光谱分析仪(XRF)测定,该复合材料中所含元素的质量百分含量为:碳1.34%,氢0.32%,氧0.18%,镍98.16%。该纳米复合材料的X射线衍射谱图如图15所示,可看出,在该材料的衍射图中存在对应于fcc Ni的衍射峰(44.2°、51.6°和76.2°)。
按术语部分所述方法测量、计算,本对比例制得的复合材料的酸洗损失率为100%。
实施例1
将制备例1所得纳米复合材料作为催化剂用于硝基苯酚类化合物反应物加氢制备目的产物氨基苯酚类化合物的反应,具体的实验步骤为:
将0.1g纳米复合材料、1.95g对硝基苯酚,100mL乙醇加入反应釜中,通入H2置换反应釜3次后,再次通入H2使反应釜内压力为2MPa,搅拌升温,升温至预定反应温度50℃,持续反应3小时后停止加热,降至室温后排压,打开反应釜取出产物进行色谱分析。通过以下公式计算反应物转化率及目的产物选择性:
转化率=已反应的反应物质量/反应物加入量×100%
选择性=目的产物质量/反应生成物质量×100%
经分析后,得到对硝基苯酚的转化率为100%,对氨基苯酚的选择性为99.1%。
实施例2
将制备例1所得纳米复合材料作为催化剂用于硝基苯酚类化合物反应物加氢制备目的产物氨基苯酚类化合物的反应,具体的实验步骤为:
将0.1g纳米复合材料、0.33g对硝基苯酚、30mL乙醇加入反应釜中,通入H2置换反应釜3次后,再次通入H2使反应釜内压力为1MPa,搅拌升温,升温至预定反应温度60℃,持续反应2小时后停止加热,降至室温后排压,打开反应釜取出产物进行色谱分析。通过实施例1所列公式计算反应物转化率及目的产物选择性。
经分析后,得到对硝基苯酚的转化率为100%,对氨基苯酚的选择性为99.9%。
实施例3
将制备例1所得纳米复合材料作为催化剂用于硝基苯酚类化合物反应物加氢制备目的产物氨基苯酚类化合物的反应,具体的实验步骤为:
将0.1g纳米复合材料、0.49g对硝基苯酚、50mL乙醇加入反应釜中,通入H2置换反应釜3次后,再次通入H2使反应釜内压力为0.5MPa,搅拌升温,升温至预定反应温度120℃,持续反应1小时后停止加热,降至室温后排压,打开反应釜取出产物进行色谱分析。通过实施例1所列公式计算反应物转化率及目的产物选择性。
经分析后,得到对硝基苯酚的转化率为100%,对氨基苯酚的选择性为98.8%。
实施例4
将制备例1所得纳米复合材料作为催化剂用于硝基苯酚类化合物反应物加氢制备目的产物氨基苯酚类化合物的反应,具体的实验步骤为:
将0.1g纳米复合材料、0.49g对硝基苯酚、30mL环己烷加入反应釜中,通入H2置换反应釜3次后,再次通入H2使反应釜内压力为2MPa,搅拌升温,升温至预定反应温度100℃,持续反应1小时后停止加热,降至室温后排压,打开反应釜取出产物进行色谱分析。通过实施例1所列公式计算反应物转化率及目的产物选择性。
经分析后,得到对硝基苯酚的转化率为100%,对氨基苯酚的选择性为99.4%。
实施例5
将制备例1所得纳米复合材料作为催化剂用于硝基苯酚类化合物反应物加氢制备目的产物氨基苯酚类化合物的反应,具体的实验步骤为:
将0.1g纳米复合材料、0.33g邻硝基苯酚、30mL乙醇加入反应釜中,通入H2置换反应釜3次后,再次通入H2使反应釜内压力为1MPa,搅拌升温,升温至预定反应温度60℃,持续反应2小时后停止加热,降至室温后排压,打开反应釜取出产物进行色谱分析。通过实施例1所列公式计算反应物转化率及目的产物选择性。
经分析后,得到邻硝基苯酚的转化率为100%,邻氨基苯酚的选择性为99.5%。
实施例6
将制备例1所得纳米复合材料作为催化剂用于硝基苯酚类化合物反应物加氢制备目的产物氨基苯酚类化合物的反应,具体的实验步骤为:
将0.1g纳米复合材料、0.33g间硝基苯酚、30mL乙醇加入反应釜中,通入H2置换反应釜3次后,再次通入H2使反应釜内压力为1MPa,搅拌升温,升温至预定反应温度60℃,持续反应2小时后停止加热,降至室温后排压,打开反应釜取出产物进行色谱分析。通过实施例1所列公式计算反应物转化率及目的产物选择性。
经分析后,得到间硝基苯酚的转化率为100%,间氨基苯酚的选择性为99.6%。
实施例7
将制备例1所得纳米复合材料作为催化剂用于硝基苯酚类化合物反应物加氢制备目的产物氨基苯酚类化合物的反应,具体的实验步骤为:
将0.1g纳米复合材料、0.33g 4,5-二甲基-2-硝基苯酚、30mL乙醇加入反应釜中,通入H2置换反应釜3次后,再次通入H2使反应釜内压力为1MPa,搅拌升温,升温至预定反应温度60℃,持续反应2小时后停止加热,降至室温后排压,打开反应釜取出产物进行色谱分析。通过实施例1所列公式计算反应物转化率及目的产物选择性。
经分析后,得到4,5-二甲基-2-硝基苯酚的转化率为100%,4,5-二甲基-2-氨基苯酚的选择性为98.8%。
实施例8
将制备例2所得纳米复合材料作为催化剂用于硝基苯酚类化合物反应物加氢制备目的产物氨基苯酚类化合物的反应,具体的实验步骤为:
将0.2g纳米复合材料、0.67g对硝基苯酚、50mL乙醇加入反应釜中,通入H2置换反应釜3次后,再次通入H2使反应釜内压力为1MPa,搅拌升温,升温至预定反应温度60℃,持续反应2小时后停止加热,降至室温后排压,打开反应釜取出产物进行色谱分析。通过实施例1所列公式计算反应物转化率及目的产物选择性。
经分析后,得到对硝基苯酚的转化率为100%,对氨基苯酚的选择性为99.2%。
实施例9
将制备例3所得纳米复合材料作为催化剂用于硝基苯酚类化合物反应物加氢制备目的产物氨基苯酚类化合物的反应,具体的实验步骤为:
将0.2g纳米复合材料、0.67g对硝基苯酚、50mL乙醇加入反应釜中,通入H2置换反应釜3次后,再次通入H2使反应釜内压力为1MPa,搅拌升温,升温至预定反应温度60℃,持续反应2小时后停止加热,降至室温后排压,打开反应釜取出产物进行色谱分析。通过实施例1所列公式计算反应物转化率及目的产物选择性。
经分析后,得到对硝基苯酚的转化率为100%,对氨基苯酚的选择性为99.8%。
实施例10
将制备例4所得纳米复合材料作为催化剂用于硝基苯酚类化合物反应物加氢制备目的产物氨基苯酚类化合物的反应,具体的实验步骤为:
将0.2g纳米复合材料、0.67g对硝基苯酚、50mL乙醇加入反应釜中,通入H2置换反应釜3次后,再次通入H2使反应釜内压力为1MPa,搅拌升温,升温至预定反应温度60℃,持续反应2小时后停止加热,降至室温后排压,打开反应釜取出产物进行色谱分析。通过实施例1所列公式计算反应物转化率及目的产物选择性。
经分析后,得到对硝基苯酚的转化率为100%,对氨基苯酚的选择性为99.9%。
可见,采用本发明的碳包覆镍纳米复合材料催化硝基苯酚类化合物合成氨基苯酚类化合物,在宽的温度范围和压力范围内,均可实现反应转化率100%,且氨基苯酚类化合物的选择性均可达到98%以上,材料的催化性能稳定,表现了良好的重复性、高活性及高选择性。
本领域技术人员应当注意的是,本发明所描述的实施方式仅仅是示范性的,可在本发明的范围内作出各种其他替换、改变和改进。因而,本发明不限于上述实施方式,而仅由权利要求限定。
Claims (20)
1.一种氨基苯酚类化合物的合成方法,包括:
以碳包覆镍的纳米复合材料为催化剂,在氢气气氛下催化硝基苯酚类化合物进行加氢还原反应;
其中,所述纳米复合材料含具有壳层和内核的核壳结构,所述壳层为掺杂氮和氧的石墨化碳层,所述内核为镍纳米颗粒,所述纳米复合材料的酸洗损失率≤60%。
2.根据权利要求1所述的合成方法,其中所述硝基苯酚类化合物的苯环上还含有取代基,所述取代基选自C1-20的烷基、环烷基和芳基中的一种或多种。
3.根据权利要求1所述的合成方法,其中所述硝基苯酚类化合物选自邻硝基苯酚、对硝基苯酚、间硝基苯酚和4,5-二甲基-2-硝基苯酚中的一种或多种。
4.根据权利要求1所述的合成方法,其中所述催化剂占所述硝基苯酚类化合物质量的1%~50%,优选5%~30%。
5.根据权利要求1所述的合成方法,其中所述加氢还原反应的温度为50℃~120℃。
6.根据权利要求1所述的合成方法,其中所述氢气的压力为0.5MPa~2MPa。
7.根据权利要求1所述的合成方法,其中所述硝基苯酚类化合物与所述催化剂在溶剂中混合后进行加氢还原反应,所述溶剂选自醇类、醚类、烷烃类和水中的一种或多种。
8.根据权利要求1至7中任一项所述的合成方法,其中所述纳米复合材料为具有至少一个介孔分布峰的介孔材料。
9.根据权利要求1至7中任一项所述的合成方法,其中所述纳米复合材料的酸洗损失率≤10%。
10.根据权利要求9所述的合成方法,其中所述纳米复合材料为具有至少一个介孔分布峰的介孔材料。
11.根据权利要求8或10所述的合成方法,其中所述纳米复合材料为具有两个或两个以上介孔分布峰的介孔材料。
12.根据权利要求8或10所述的合成方法,其中所述介孔材料中介孔体积占总孔体积的比例大于50%,优选大于80%,更优选大于95%。
13.根据权利要求8或9所述的合成方法,其中所述石墨化碳层的厚度为0.3nm~6.0nm,优选为0.3nm~3nm。
14.根据权利要求8或9所述的合成方法,其中所述核壳结构的粒径为1nm~200nm,优选为3nm~100nm,更优选为4nm~50nm。
15.根据权利要求8所述的合成方法,其中以质量百分比计,所述纳米复合材料的碳含量为10.0%~60.0%,镍含量为30.0%~85.0%;优选地,碳含量为30.0%~50.0%,镍含量为30.0%~60.0%。
16.根据权利要求8所述的合成方法,其中以质量百分比计,该纳米复合材料中,氮和氧的总含量小于15.0%,优选为0.2%~12.0%,更优选为0.5%~10.0%。
17.根据权利要求8所述的合成方法,其中以质量百分比计,该纳米复合材料中,氮含量小于15%,优选为0.1%~10%,更优选为1%~5%。
18.根据权利要求9所述的合成方法,其中以质量百分比计,所述纳米复合材料的碳含量为碳含量为15%~60%,镍含量为30%~80%,优选地,碳含量为30%~60%,镍含量为30%~60%。
19.根据权利要求9所述的合成方法,其中以质量百分比计,该纳米复合材料中,氮和氧的总含量小于15.0%。
20.根据权利要求9所述的合成方法,其中以质量百分比计,氮的含量为2%~8%,氧的含量为3%~9%。
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