CN110180523A - 一种非金属多孔碳纳米催化剂及其制备方法 - Google Patents
一种非金属多孔碳纳米催化剂及其制备方法 Download PDFInfo
- Publication number
- CN110180523A CN110180523A CN201910402045.4A CN201910402045A CN110180523A CN 110180523 A CN110180523 A CN 110180523A CN 201910402045 A CN201910402045 A CN 201910402045A CN 110180523 A CN110180523 A CN 110180523A
- Authority
- CN
- China
- Prior art keywords
- porous carbon
- metal porous
- nanocatalyst
- catalyst
- zinc
- 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.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 62
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 46
- 229910052755 nonmetal Inorganic materials 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 229960001860 salicylate Drugs 0.000 claims abstract description 14
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 claims abstract description 14
- 230000002687 intercalation Effects 0.000 claims abstract description 13
- 238000009830 intercalation Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 239000007791 liquid phase Substances 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 6
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims abstract description 6
- 229940007718 zinc hydroxide Drugs 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 8
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 4
- 150000003751 zinc Chemical class 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 150000002843 nonmetals Chemical class 0.000 claims description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 229960004889 salicylic acid Drugs 0.000 claims description 3
- 238000000975 co-precipitation Methods 0.000 claims description 2
- FRMWBRPWYBNAFB-UHFFFAOYSA-M potassium salicylate Chemical compound [K+].OC1=CC=CC=C1C([O-])=O FRMWBRPWYBNAFB-UHFFFAOYSA-M 0.000 claims description 2
- 229960003629 potassium salicylate Drugs 0.000 claims description 2
- 238000000197 pyrolysis Methods 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 241000219000 Populus Species 0.000 claims 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 abstract description 14
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 239000003863 metallic catalyst Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 210000003850 cellular structure Anatomy 0.000 abstract description 3
- 238000005087 graphitization Methods 0.000 abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 230000001681 protective effect Effects 0.000 abstract description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000009938 salting Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000002041 carbon nanotube Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ABBQHOQBGMUPJH-UHFFFAOYSA-M Sodium salicylate Chemical compound [Na+].OC1=CC=CC=C1C([O-])=O ABBQHOQBGMUPJH-UHFFFAOYSA-M 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 229960004025 sodium salicylate Drugs 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 229960001296 zinc oxide Drugs 0.000 description 2
- OEHNVKBOQOXOJN-UHFFFAOYSA-N 2-(4-nitrophenyl)phenol Chemical compound OC1=CC=CC=C1C1=CC=C([N+]([O-])=O)C=C1 OEHNVKBOQOXOJN-UHFFFAOYSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 240000000203 Salix gracilistyla Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- -1 graphite Alkene Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride 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
- 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
- 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
- B01J35/618—Surface area more than 1000 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
- B01J35/638—Pore volume more than 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
- B01J37/03—Precipitation; Co-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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/205—Preparation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Thermal Sciences (AREA)
- Physics & Mathematics (AREA)
- Nanotechnology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种非金属多孔碳纳米催化剂及其制备方法。本发明首次以水杨酸根插层的层状氢氧化锌为单一前驱体，在无模板和额外碳源的情况下，在惰性气氛中通过一步固相合成方法制备得到了非金属多孔碳纳米催化剂。本发明制备得到的催化剂石墨化程度高，有很大的比表面积和丰富的孔道结构，表面含有大量的还原态氧功能基团。将该催化剂应用于对硝基苯酚(4‑NP)液相加氢反应，其在4min就能将4‑NP降解完全，优于商业化Pb/C和Pt/C催化剂。另外，本发明得到碳纳米催化剂为非金属催化剂，较金属催化剂相比，具有有价格便宜，稳定性高，绿色环保等优点，是非常有前景的催化材料。
Description
技术领域
本发明属于纳米催化剂制备技术领域，具体涉及一种非金属多孔碳纳米催化剂及其制备方法。
背景技术
在化工、石化、生化、环保等领域，有90％以上的工业过程都使用催化剂。实现环境友好的绿色化工主要依托于新型高效绿色催化剂的研制与开发，因此研究与开发新型的催化剂成为了当前学术界和工业界普遍关注的热点问题。在现代催化技术中，相比于均相催化剂，非均相催化剂由于其易于回收再利用的独特优势而更具有经济实用性。目前基于Au、Pd、Pt、Rh、Ag等贵金属纳米粒子的催化剂已经被广泛应用在很多重要的化工反应中。虽然贵金属纳米催化剂可以有效地提高反应速率，但其具有稳定性差、成本高昂、稀缺等缺点，阻碍了其在化工、环保等领域大规模的应用。
碳纳米材料是一类重要的新型材料，可分为零维的富勒烯、一维的碳纳米管、二维石墨烯等，由于其具有高稳定性、大比表面积、特殊的光电性能等特点，一般作为催化剂载体。目前，有少数研究表明，单独碳材料经过某些特殊的处理能够表现出催化性能，如热氧化、杂原子掺杂以及有机试剂修饰等。Lu等通过将碳纳米管(CNTs)在强氧化剂(HCl、HNO3、H2SO4)下进行处理得到了氧化碳纳米管(o-CNTs)，在经过水热和电化学活化处理之后，应用于电解水析氧(OER)反应中。Yang等用水热法180℃处理尿素和氧化石墨烯制备得到了氮掺杂的石墨烯，将其用于多种硝基污染物物处理，表现出了催化活性。Gu等通过液相方法将菲醌引入到多壁碳纳米管表面，得到了菲醌修饰的多壁碳纳米管，在硝基苯的还原反应表现出了催化活性。目前，报道碳纳米催化剂的制备过程往往需要使用强氧化剂，制备方法复杂，原料昂贵，且产物的组成、结晶度和孔结构难以控制，不利于实际应用。
层状金属氢氧化物是一类新型的阴离子型层状材料，其组成可以表示为M(OH)2-x(An-)x/n·mH2O。其中M为层板二价金属阳离子，包括Zn2+，Co2+，Cu2+，Ni2+等，An-代表层间阴离子，如Cl-，CO3 2-，NO3 -，SO4 2-,CH3COO-等无机或有机阴离子。层状金属氢氧化物组成多样，可以将其作为模板，应用于金属、金属氧化物、金属硫化物、纳米碳(碳纳米管、碳量子点和石墨烯等)及其复合材料的制备，展现了广阔的应用前景。
发明内容
本发明的目的是提供一种非金属多孔碳纳米催化剂的制备方法，并将所制备的催化剂应用于对硝基苯酚液相催化加氢反应中。
本发明所述的非金属多孔碳纳米催化剂为二维片状结构的多孔碳纳米片，纳米片直径为50-300nm之间，纳米片的厚度为10-50nm之间；多孔碳是石墨化的，比表面积在1000-3000m2g-1之间，孔径在2-25nm之间，孔体积在1.5-4.0cm3g-1之间。多孔碳表面含有5-20％的还原态氧官能团。
本发明所述的非金属多孔碳纳米催化剂的制备方法为：以水杨酸根插层的层状氢氧化锌纳米超分子材料为前驱体，在惰性气氛中一步固态热解蒸发掉氧化锌得到非金属多孔碳纳米催化剂。
本发明所述的非金属多孔碳纳米催化剂的制备方法的具体步骤如下：
(1)配制无机锌盐和水杨酸盐的混合盐溶液，配制NaOH碱溶液，将混合盐溶液和碱溶液混合，通过共沉淀法制备得到二维片状水杨酸插层层状氢氧化锌前驱体；
(2)将层状氢氧化锌前驱体置于管式炉中，在惰性气氛下700-1100℃焙烧1-8h得到非金属多孔碳纳米催化剂。
步骤(1)中所述的无机锌盐是硝酸锌、氯化锌、硫酸锌中的一种或几种，在水溶液中的浓度为0.05-0.4mol/L。
步骤(1)中所述的水杨酸盐为水杨酸钾，水杨酸钠中的一种或两种，在水溶液的浓度为0.1-0.8mol/L。
将上述制备得到的非金属多孔碳纳米催化剂应用于对硝基苯酚的液相催化加氢反应。
本发明首次以水杨酸根插层的层状氢氧化锌为单一前驱体，在无模板和额外碳源的情况下，在惰性气氛中通过一步固相合成方法制备得到了非金属多孔碳纳米催化剂。本发明制备技术简单、经济、绿色、高效，无需昂贵的设备，适用于工业化大规模生产。制备得到的催化剂石墨化程度高，有很大的比表面积和丰富的孔道结构，表面含有大量的还原态氧功能基团。将该催化剂应用于对硝基苯酚(4-NP)液相加氢反应，其在4min就能将4-NP降解完全，优于商业化Pb/C和Pt/C催化剂。另外，本发明得到碳纳米催化剂为非金属催化剂，较金属催化剂相比，具有有价格便宜，稳定性高，绿色环保等优点，是非常有前景的催化材料。
附图说明
图1是实施例1制备的二维水杨酸根插层层状氢氧化锌纳米片前驱体的SEM照片。
图2是实施例1制备的二维水杨酸根插层层状氢氧化锌纳米片前驱体的XRD谱图。
图3是实施例1制备的非金属多孔碳纳米催化剂的SEM图。
图4是实施例1制备的非金属多孔碳纳米催化剂的XRD图谱。
图5是实施例1制备的非金属多孔碳纳米催化剂的FTIR图。
图6是实施例1制备的非金属多孔碳纳米催化剂的Raman图。
图7是实施例1制备的非金属多孔碳纳米催化剂的能谱图。
图8是实施例1制备的非金属多孔碳纳米催化剂的氮气吸附脱附曲线及孔径分布图(内图)。
图9是实施例1制备的非金属多孔碳纳米催化剂的电镜图。
图10是实施例1制备的非金属多孔碳纳米催化剂催化对硝基苯酚加氢制备对氨基苯酚的紫外吸收谱图。
图11是实施例1制备的非金属多孔碳纳米催化剂的循环利用柱状图。
具体实施方式
下面结合具体的实施实例来对本发明所述的制备方法做进一步说明，但是本发明的保护范围并不限于此。
实施例1
(1)称取5.9498g Zn(NO3)2·6H2O和6.4044g的水杨酸钠，室温下分别溶于100mL去离子水配置成盐溶液，将配制好的两种盐溶液倒入四口烧瓶中，并开始用电动搅拌器匀速转动，使盐溶液混合均匀；
(2)称取8gNaOH溶于200mL去离子水中配制成碱液，向混合盐溶液中缓慢滴加碱液后，溶液中开始有白色沉淀析出，调节pH＝7，升高温度至95℃，在此温度下反应24h，反应结束后，待温度降到室温，用去离子水洗涤，离心3次，在60℃下干燥12h，得到二维片状水杨酸根插层层状氢氧化锌前驱体。
(3)将步骤2)制得的二维片状水杨酸根插层层状氢氧化锌前驱体在氮气气氛中900℃焙烧4h，得到非金属多孔碳纳米催化剂。
验证本发明所述的非金属多孔碳纳米催化剂的结构和性能，对实施例1制备的样品结构及其对硝基苯酚催化加氢反应进行了评价。
催化反应：常温条件下，首先将50mg NaBH4溶解到50mL去离子水中配制成NaBH4溶液，然后用移液枪分别抽取6mL去离子水、0.5mL对硝基苯酚溶液(1mmol/L)和2mL NaBH4溶液混合均匀配制成反应物溶液(对硝基苯酚和NaBH4的摩尔比为1:100)。准确称量1mg的多孔碳催化剂于2mL离心管中，并向其中加入2mL去离子水超声1h得到黑色催化剂浆液。用移液枪吸取0.2mL催化剂浆液加入到3mL反应物溶液中，然后用紫外分光光度计实时监测对硝基苯酚浓度的变化。
从图1可以看出制得的层状氢氧化锌为二维纳米片状结构。
从图2可以看出，制得的层状氢氧化锌前驱体的XRD谱图的主要衍射峰的位置为(5.36°，10.99°，16.48°)，分别对应d值为1.65nm,0.81nm,0.54nm，均呈现良好的倍数关系，说明合成的前驱体为层状结构。
从图3可以看出，焙烧后的制得的非金属多孔碳纳米催化剂的XRD图谱中并没有ZnO的衍射峰，只有碳的002晶面衍射峰，说明样品中不含ZnO，证明了其非金属性。
从图4可以看出，所得到非金属多孔碳纳米催化剂为二维片状结构，与前驱体相比，片状结构没有发生明显改变，二维碳纳米片的直径为50-300nm，厚度为10-50nm，由石墨化碳组成。
从图5可以看出，所得到非金属多孔碳纳米催化剂中含有大量的羟基。
从图6可以看出，所得到的非金属多孔碳纳米催化剂在1350cm-1和1589cm-1出现了石墨碳的D峰和G峰，且ID/IG的比值为0.99，表明该催化剂具有较高的石墨化程度。
从图7可以看出，所得到的非金属多孔碳纳米催化剂不含有锌元素，证明了其为非金属材料。氧原子含量为8.68％，表明催化剂含有大量的还原态氧功能基团。
从图8可以看出，所得到的非金属多孔碳纳米催化剂的比表面积高达2480m2/g。
从图9可以看出，所得到的非金属多孔碳纳米催化剂含有丰富的孔道结构。
从图10可以看出，所得到的非金属多孔碳纳米催化剂在对硝基苯酚加氢还原反应中表现出了优异的催化性能，其在4min就能将4-NP降解完全，优于商业化Pb/C和Pt/C催化剂。
从图11可以看出，所得到的非金属多孔碳纳米催化剂具有良好的稳定性，在第5次循环使用时对4-NP的降解率仍能到达90％以上。
实施例2
(1)称取5.9498g Zn(NO3)2·6H2O和6.4044g的水杨酸钠，室温下分别溶于100mL去离子水配置成盐溶液，将配制好的两种盐溶液倒入四口烧瓶中，并开始用电动搅拌器匀速转动，使盐溶液混合均匀；
(2)称取8g NaOH溶于200mL去离子水中配制成碱液，向混合盐溶液中缓慢滴加碱液后溶液中开始有白色沉淀析出，调节pH＝7，将所得混合盐溶液转移到高压反应釜当中，调节温度为100℃，在此温度下反应24h，反应结束后，待温度降到室温，用去离子水洗涤，离心3次，在60℃下干燥12h，得到二维片状水杨酸根插层层状氢氧化锌前驱体。
(3)将步骤2)制得的二维片状水杨酸根插层层状氢氧化锌前驱体在氮气气氛中900℃焙烧2h，得到非金属多孔碳纳米催化剂。
实施例3
(1)称取2.9749g Zn(NO3)2·6H2O和12.8088g的水杨酸钠，室温下分别溶于100mL去离子水配置成盐溶液，将配制好的两种盐溶液倒入四口烧瓶中，并开始用电动搅拌器匀速转动，使盐溶液混合均匀；
(2)称取4gNaOH溶于200mL去离子水中配制成碱液，向混合盐溶液中缓慢滴加碱液后溶液中开始有白色沉淀析出，调节pH＝6.5，升高温度至70℃，在此温度下反应24h，反应结束后，待温度降到室温，用去离子水洗涤，离心3次，在60℃下干燥12h，得到二维片状水杨酸根插层层状氢氧化锌前驱体。
(3)将步骤2)制得的二维片状水杨酸根插层层状氢氧化锌前驱体在氮气气氛中900℃焙烧2h，得到非金属多孔碳纳米催化剂。
Claims (6)
1.一种非金属多孔碳纳米催化剂，其特征在于，该催化剂为二维片状结构的多孔碳纳米片，纳米片直径为50-300nm之间，纳米片的厚度为10-50nm之间；多孔碳是石墨化的，比表面积在1000-3000m2g-1之间，孔径在2-25nm之间，孔体积在1.5-4.0cm3g-1之间；多孔碳表面含有5-20％的还原态氧官能团。
2.一种非金属多孔碳纳米催化剂的制备方法，其特征在于，该方法为：以水杨酸根插层的层状氢氧化锌纳米超分子材料为前驱体，在惰性气氛中一步固态热解蒸发掉氧化锌得到非金属多孔碳纳米催化剂。
3.一种非金属多孔碳纳米催化剂的制备方法，其特征在于，该方法的具体步骤如下：
(1)配制无机锌盐和水杨酸盐的混合盐溶液，配制NaOH碱溶液，将混合盐溶液和碱溶液混合，通过共沉淀法制备得到二维片状水杨酸插层层状氢氧化锌前驱体；
(2)将层状氢氧化锌前驱体置于管式炉中，在惰性气氛下700-1100℃焙烧1-8h得到非金属多孔碳纳米催化剂。
4.根据权利要求3所述的方法，其特征在于，步骤(1)中所述的无机锌盐是硝酸锌、氯化锌、硫酸锌中的一种或几种，在水溶液中的浓度为0.05-0.4mol/L。
5.根据权利要求3所述的方法，其特征在于，步骤(1)中所述的水杨酸盐为水杨酸钾，水杨酸钠中的一种或两种，在水溶液的浓度为0.1-0.8mol/L。
6.根据权利要求3-5任一所述的方法制备得到的非金属多孔碳纳米催化剂在对硝基苯酚的液相催化加氢反应中的应用。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910402045.4A CN110180523A (zh) | 2019-05-15 | 2019-05-15 | 一种非金属多孔碳纳米催化剂及其制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910402045.4A CN110180523A (zh) | 2019-05-15 | 2019-05-15 | 一种非金属多孔碳纳米催化剂及其制备方法 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110180523A true CN110180523A (zh) | 2019-08-30 |
Family
ID=67716334
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910402045.4A Pending CN110180523A (zh) | 2019-05-15 | 2019-05-15 | 一种非金属多孔碳纳米催化剂及其制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110180523A (zh) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111266114A (zh) * | 2020-03-17 | 2020-06-12 | 北京化工大学 | 一种金属铁/氧化锌/碳三元纳米复合可见光催化剂及其制备方法和应用 |
| CN113546617A (zh) * | 2021-08-10 | 2021-10-26 | 四川轻化工大学 | 一种分解n-甲基氧化吗啉产品中残余双氧水的中间相沥青基介孔碳催化剂及其制备方法 |
| CN115318318A (zh) * | 2021-09-30 | 2022-11-11 | 湘潭大学 | 一种用于硝基芳烃加氢的氮掺杂石墨烯催化剂的制备方法和应用 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437453A (zh) * | 2014-11-28 | 2015-03-25 | 浙江大学 | 一种碳气凝胶催化剂及其制备方法和用途 |
| CN105776181A (zh) * | 2016-04-29 | 2016-07-20 | 大连理工大学 | 一种片状纳米多孔碳与碳纳米管复合材料的制备方法 |
| CN108383104A (zh) * | 2018-03-27 | 2018-08-10 | 清华大学 | 一种原位生成的碳纳米管及其制备方法与应用 |
-
2019
- 2019-05-15 CN CN201910402045.4A patent/CN110180523A/zh active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104437453A (zh) * | 2014-11-28 | 2015-03-25 | 浙江大学 | 一种碳气凝胶催化剂及其制备方法和用途 |
| CN105776181A (zh) * | 2016-04-29 | 2016-07-20 | 大连理工大学 | 一种片状纳米多孔碳与碳纳米管复合材料的制备方法 |
| CN108383104A (zh) * | 2018-03-27 | 2018-08-10 | 清华大学 | 一种原位生成的碳纳米管及其制备方法与应用 |
Non-Patent Citations (2)
| Title |
|---|
| XIAODI GUO ET AL.: "Hydroxyl-rich nanoporous carbon nanosheets synthesized by a one-pot method and their application in the in situ preparation of well-dispersed Ag nanoparticles", 《RSC ADVANCES》 * |
| 周宏跃等: "酸处理活性炭催化水合肼还原硝基苯", 《催化学报》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111266114A (zh) * | 2020-03-17 | 2020-06-12 | 北京化工大学 | 一种金属铁/氧化锌/碳三元纳米复合可见光催化剂及其制备方法和应用 |
| CN113546617A (zh) * | 2021-08-10 | 2021-10-26 | 四川轻化工大学 | 一种分解n-甲基氧化吗啉产品中残余双氧水的中间相沥青基介孔碳催化剂及其制备方法 |
| CN113546617B (zh) * | 2021-08-10 | 2023-04-21 | 四川轻化工大学 | 一种分解n-甲基氧化吗啉产品中残余双氧水的中间相沥青基介孔碳催化剂及其制备方法 |
| CN115318318A (zh) * | 2021-09-30 | 2022-11-11 | 湘潭大学 | 一种用于硝基芳烃加氢的氮掺杂石墨烯催化剂的制备方法和应用 |
| CN115318318B (zh) * | 2021-09-30 | 2024-06-11 | 湘潭大学 | 一种用于硝基芳烃加氢的氮掺杂石墨烯催化剂的制备方法和应用 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Han et al. | Metallic ruthenium-based nanomaterials for electrocatalytic and photocatalytic hydrogen evolution | |
| Yao et al. | Facile synthesis of graphene-supported Ni-CeO x nanocomposites as highly efficient catalysts for hydrolytic dehydrogenation of ammonia borane | |
| Deng et al. | Improving the electrocatalytic N 2 reduction activity of Pd nanoparticles through surface modification | |
| Wu et al. | Synthesis of g-C3N4 with heating acetic acid treated melamine and its photocatalytic activity for hydrogen evolution | |
| Wan et al. | Facile synthesis of mesoporous NiCo2O4 fibers with enhanced photocatalytic performance for the degradation of methyl red under visible light irradiation | |
| Huang et al. | 3D nanospherical CdxZn1− xS/reduced graphene oxide composites with superior photocatalytic activity and photocorrosion resistance | |
| Wang et al. | Facile solid-state synthesis of highly dispersed Cu nanospheres anchored on coal-based activated carbons as an efficient heterogeneous catalyst for the reduction of 4-nitrophenol | |
| CN110433816B (zh) | 一种负载型钴掺杂的二氧化铈纳米片的制备方法 | |
| Liu et al. | A facile fabrication of nanoflower-like Co3O4 catalysts derived from ZIF-67 and their catalytic performance for CO oxidation | |
| Liu et al. | Two-dimensional porous γ-AlOOH and γ-Al 2 O 3 nanosheets: hydrothermal synthesis, formation mechanism and catalytic performance | |
| CN110152664B (zh) | 一种一维氧化亚铜/碳纳米复合催化剂的制备方法及应用 | |
| CN110180523A (zh) | 一种非金属多孔碳纳米催化剂及其制备方法 | |
| Yang et al. | TePbPt alloy nanotube as electrocatalyst with enhanced performance towards methanol oxidation reaction | |
| CN111036247B (zh) | 一种钴铁氧化物-磷酸钴电催化析氧复合材料及其制备方法和应用 | |
| CN109665525B (zh) | 一种“哑铃型”铁氮双掺杂多孔碳的制备方法 | |
| CN109926054A (zh) | 一种高分散NiCo合金-石墨烯纳米复合催化剂的制备方法 | |
| Yang et al. | Cu-anchored CNTs for effectively catalytic reduction of 4-nitrophenol | |
| CN104538648B (zh) | 一种石墨烯负载铂钴合金纳米粒子复合催化剂及其制备方法 | |
| CN111330620A (zh) | 插层型类石墨氮化碳复合材料、其制备方法及其应用 | |
| Yin et al. | Two-dimensional materials for high-performance oxygen evolution reaction: Fundamentals, recent progress, and improving strategies | |
| Gu et al. | Enhancement of the hydrogen evolution performance by finely tuning the morphology of Co-based catalyst without changing chemical composition | |
| Tang et al. | Positive regulation of active sites for oxygen evolution reactions by encapsulating NiFe 2 O 4 nanoparticles in N-doped carbon nanotubes in situ to construct efficient bifunctional oxygen catalysts for rechargeable Zn–air batteries | |
| CN114377691B (zh) | 一种甜甜圈状空心多孔Pt-Ni纳米粒子负载氧化钛材料及其制备方法 | |
| CN112495412A (zh) | 一种多孔薄层石墨相氮化碳及制备方法和应用 | |
| Chen et al. | Fabrication of CNTs encapsulated nickel-nickel phosphide nanoparticles on graphene for remarkable hydrogen evolution reaction performance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190830 |
|
| WD01 | Invention patent application deemed withdrawn after publication |