CN110479348A - 一种金属单原子催化剂的制备方法及其应用 - Google Patents
一种金属单原子催化剂的制备方法及其应用 Download PDFInfo
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- CN110479348A CN110479348A CN201910833226.2A CN201910833226A CN110479348A CN 110479348 A CN110479348 A CN 110479348A CN 201910833226 A CN201910833226 A CN 201910833226A CN 110479348 A CN110479348 A CN 110479348A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 41
- 239000002184 metal Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000003197 catalytic effect Effects 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052737 gold Inorganic materials 0.000 claims abstract description 4
- 239000010931 gold Substances 0.000 claims abstract description 4
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 4
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 3
- 238000006479 redox reaction Methods 0.000 claims abstract description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 7
- 239000004327 boric acid Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 4
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 4
- 229910010277 boron hydride Inorganic materials 0.000 claims description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 4
- 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 description 3
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 3
- 229910001380 potassium hypophosphite Inorganic materials 0.000 claims description 3
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
- 229910000333 cerium(III) sulfate Inorganic materials 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- UCGZDNYYMDPSRK-UHFFFAOYSA-L trisodium;gold;hydroxy-oxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [Na+].[Na+].[Na+].[Au].OS([S-])(=O)=O.OS([S-])(=O)=O UCGZDNYYMDPSRK-UHFFFAOYSA-L 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 229910052796 boron Inorganic materials 0.000 claims 1
- -1 chlorauride Chemical compound 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052759 nickel Inorganic materials 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 2
- 229910017052 cobalt Inorganic materials 0.000 abstract description 2
- 239000010941 cobalt Substances 0.000 abstract description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 2
- 239000010949 copper Substances 0.000 abstract description 2
- 229910052697 platinum Inorganic materials 0.000 abstract description 2
- 229910052709 silver Inorganic materials 0.000 abstract description 2
- 239000004332 silver Substances 0.000 abstract description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 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 description 5
- 229940043267 rhodamine b Drugs 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000006392 deoxygenation reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000006197 hydroboration reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
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- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1064—Platinum group metal catalysts
- C01B2203/107—Platinum catalysts
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1076—Copper or zinc-based catalysts
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
本发明公开了一种金属单原子催化剂的制备方法。通过氧化还原反应,将溶液中的金属离子还原成单质,并且将氧化还原产物沉积于g‑C3N4载体表面,从而制得金属单原子催化剂。改变加入的无机金属盐的种类,可以制得不同金属种类的单原子催化剂,如镍、钯、钴、铜、金、银、铂单原子催化剂。通过调节工艺参数,可以调控沉积于载体表面的金属单原子的负载量,得到不同催化性能的催化剂,以满足不同使用环境的要求。与现有技术相比,本发明的催化剂制备方法能制备出多种不同种类的金属单原子催化剂,并且实现了金属单原子负载量的可调控性。本发明采用的金属单原子催化剂的制备方法具有工艺条件温和、设备要求低等优点,具有较好的应用前景。
Description
技术领域
本发明属于催化技术领域,涉及一种负载于石墨相氮化碳(g-C3N4)表面的一元金属单原子 催化剂的制备方法及其在催化析氢和光催化降解中的应用。
背景技术
(1)所谓单原子催化剂是指金属催化剂以单原子的形式均匀分散沉积于载体表面,催化活性 位点最大限度地暴露出来,提高了催化剂的利用效率,从而降低催化剂的成本。当粒子分散 度达到单原子尺寸时,会引起很多新的特性,如急剧增大的表面自由能、量子尺寸效应、不 饱和配位环境和金属-载体的相互作用等,正是这些与纳米或亚纳米级粒子显著不同的特性, 赋予单原子催化剂优越的活性和选择性,能进一步提高催化性能、降低制造成本。因此,单 原子催化剂在工业催化中具有巨大的应用潜能。本发明采用化学方法,在温和的条件下制备 出一元金属单原子催化剂,其工艺方法简单、设备要求低。
(2)g-C3N4具有独特的电子结构、高的化学稳定性和热稳定性、成本低廉、无毒无害等诸多 优势。但是,由于g-C3N4的层间具有较强的范德华力,导致其堆积紧密,故比表面积小,表 面活性位点少。加之,g-C3N4的可见光响应范围较窄、光生载流子易复合等严重降低了其催 化活性,故需对其进行改性以优化性能。改性方法种类很多,如微观结构调整、元素掺杂、 半导体复合、贵金属负载等。本发明以g-C3N4为载体,采用化学法在其表面负载一定量的金 属单原子,通过改变金属元素种类和调控单原子负载量,能提升催化剂活性和选择性。
(3)随着经济的发展和人口的增长,传统的化石燃料导致了一系列的污染问题,严重威胁着 人类社会的可持续发展。因此,人类面临着巨大的能源危机和环境问题。氢能具有燃烧热值 高、无污染、储量丰富等特点,被视为最理想的清洁能源。近年来,通过催化析氢技术的开 发越来越受到关注。本发明提供了一种新型催化剂的制备方法,得到一类催化析氢性能较好 的负载型一元金属单原子催化剂。
(4)随着工农业高速发展,各类有机污染物、重金属、放射性核素等污染物进入水体环境中。 其中可溶性污染物会随着水体流动在环境体系中迁移、转化,并在生物链中积累。面对水资 源的日益匮乏和日趋加剧的水污染,水体中污染物的治理迫在眉睫。在光催化剂作用下,能 降解水体中的有机污染物,且该方法具有成本低廉、无二次污染的优点。因此,开发性能优 异的光催化剂有利于高效分解污染物。本发明提供了一种金属单原子催化剂的制备方法,具 有较高的光催化活性,可以高效快速降解水体中的有机污染物。
发明内容
本发明的目的在于提供一种负载于g-C3N4载体表面的一元金属单原子催化剂的制备方法。通 过氧化还原反应,将溶液中的金属离子还原为金属单质,反应产物沉积于载体表面,从而制 得单原子催化剂。该制备方法不受金属元素种类的影响,可以通过改变金属离子前驱物和控 制负载量,得到不同金属种类和负载量的单原子催化剂,以满足不同催化体系的要求。
本发明所述的一元金属单原子光催化剂的制备方法包括以下步骤:
(1)在水浴锅中将10~500mL的去离子水加热至35~85℃后,加入0.2~20g硼酸、0.2~20g 柠檬酸、0.1~10g硝酸铵、0.1~20g无机金属盐,充分搅拌,待固体物质完全溶解后,停止加 热,自然冷却至室温,制得溶液A;
(2)通过氢氧化钠溶液调节溶液A的pH值为6.5~12范围,制得溶液B;
(3)将溶液B加热至35~85℃后,向溶液B中加入0.1~10g的g-C3N4粉末,在35~85℃下 搅拌10~60min后,制得溶液C;
(4)将0.2~20g次磷酸盐或硼氢化物加入到10~200mL去离水中,搅拌待固体物质完全溶 液后制得溶液D;
(5)将溶液D倒入溶液C中,在35~85℃下反应1min~12h,过滤后将固体物质放入60℃ 的烘箱中干燥0.5~12h后,制得g-C3N4负载的一元金属单原子催化剂。
步骤(1)中所述的无机金属盐为硫酸镍、氯化镍、硝酸镍、硫酸铜、氯化铜、硝酸铜、硫酸 钴、硝酸钴、氯化钴、氯化钯、硝酸钯、硫酸钯、硫酸铈、硝酸铈、氯化铈、硝酸银、氯化金、氯金酸钠、硫代硫酸金钠、氯化铂、硝酸铂中的一种。根据所选的金属盐制得对应金属的单原子催化剂。步骤(4)中所述的次磷酸盐可以为次磷酸钠、次磷酸钾中的一种;硼氢化物可以为硼氢化钠、硼氢化钾中的一种。
与现有方法相比,本发明具有以下有益效果:
(1)本发明提供的制备方法,可以通过选择不同的金属盐制得不同金属种类的单原子催化剂, 通过控制反应工艺参数调控金属单原子负载量在0.01~6wt%范围变化;
(2)本发明采用氧化还原法制备一元金属单原子催化剂,工艺条件温和、设备要求低、操作 简单。
附图说明
图1是三种不同催化剂的光催化析氢量曲线;图2是三种不同催化剂的光催化析氢速率曲线; 图3是三种不同催化剂的光催化降解罗丹明B溶液的降解率曲线。图1中曲线1、曲线2、 曲线3分别为g-C3N4、负载于g-C3N4的Ni单原子催化剂、负载于g-C3N4的Co单原子催化 剂的光催化析氢量曲线。图2中曲线1、曲线2、曲线3分别为g-C3N4、负载于g-C3N4的Ni 单原子催化剂、负载于g-C3N4的Co单原子催化剂的光催化析氢速率曲线。图3中曲线1、 曲线2、曲线3分别为g-C3N4、负载于g-C3N4的Ni单原子催化剂、负载于g-C3N4的Co单 原子催化剂的光催化降解罗丹明B溶液的降解率曲线。
在室温下进行光催化分解水制氢性能测试:向30%甲醇溶液中通入99.99%的高纯氮气除氧 30min,以此作为牺牲剂溶液。取已除氧的100mL 30%甲醇溶液,并加入10mg催化剂,超 声30min后移入石英玻璃反应器中。在25W,427nm波长的LED灯的照射下,采用排水法 收集所产生的氢气,得到析氢量和析氢速率随光照时间的关系曲线。
在室温下进行光催化降解罗丹明B性能测试:向100mL,10ppm的罗丹明B溶液中加入10 mg催化剂,在250W氙灯照射下进行光催化降解。通过分光光度法测试溶液中残留罗丹明B 的浓度,得到罗丹明B降解率随光照时间的关系曲线。
具体实施方式
下面通过实施例对本发明做进一步说明,其目的仅在于更好地理解本发明的内容而非限制本 发明的保护范围。
实施例1:
(1)在水浴锅中将200mL的去离子水加热至45℃后,加入0.25g硼酸、0.25g柠檬酸、0.2 g硝酸铵、0.1g硫酸铜,充分搅拌,待固体物质完全溶解后,停止加热,自然冷却至室温,制得溶液A;
(2)通过氢氧化钠溶液调节溶液A的pH值为11,制得溶液B;
(3)将溶液B加热至45℃后,向溶液B中加入0.1g的g-C3N4粉末,在45℃下搅拌30min后,制得溶液C;
(4)将0.2g次磷酸钠加入到100mL去离水中,搅拌待固体物质完全溶液后制得溶液D;
(5)将溶液D倒入溶液C中,在45℃下反应1min,过滤后将固体物质放入60℃的烘箱中 干燥4h后,制得g-C3N4负载的铜单原子催化剂。
实施例2:
(1)在水浴锅中将100mL的去离子水加热至60℃后,加入0.5g硼酸、0.5g柠檬酸、0.8g 硝酸铵、0.8g硝酸钴,充分搅拌,待固体物质完全溶解后,停止加热,自然冷却至室温,制 得溶液A;
(2)通过氢氧化钠溶液调节溶液A的pH值为10,制得溶液B;
(3)将溶液B加热至60℃后,向溶液B中加入0.2g的g-C3N4粉末,在60℃下搅拌45min后,制得溶液C;
(4)将0.5g硼氢化钠加入到200mL去离水中,搅拌待固体物质完全溶液后制得溶液D;
(5)将溶液D倒入溶液C中,在60℃下反应1h,过滤后将固体物质放入60℃的烘箱中干 燥6h后,制得g-C3N4负载的钴单原子催化剂。
实施例3:
(1)在水浴锅中将150mL的去离子水加热至50℃后,加入1g硼酸、1g柠檬酸、0.8g硝酸铵、1g硝酸铈,充分搅拌,待固体物质完全溶解后,停止加热,自然冷却至室温,制得溶 液A;
(2)通过氢氧化钠溶液调节溶液A的pH值为7,制得溶液B;
(3)将溶液B加热至50℃后,向溶液B中加入1g的g-C3N4粉末,在60℃下搅拌60min后,制得溶液C;
(4)将1g次磷酸钾加入到150mL去离水中,搅拌待固体物质完全溶液后制得溶液D;
(5)将溶液D倒入溶液C中,在50℃下反应0.5h,过滤后将固体物质放入60℃的烘箱中干 燥8h后,制得g-C3N4负载的铈单原子催化剂。
实施例4:
(1)在水浴锅中将300mL的去离子水加热至70℃后,加入1.5g硼酸、1.5g柠檬酸、1g硝 酸铵、2g硝酸银,充分搅拌,待固体物质完全溶解后,停止加热,自然冷却至室温,制得溶液A;
(2)通过氢氧化钠溶液调节溶液A的pH值为7,制得溶液B;
(3)将溶液B加热至70℃后,向溶液B中加入2g的g-C3N4粉末,在70℃下搅拌30min后,制得溶液C;
(4)将2g次磷酸钠加入到200mL去离水中,搅拌待固体物质完全溶液后制得溶液D;
(5)将溶液D倒入溶液C中,在70℃下反应45min,过滤后将固体物质放入60℃的烘箱中 干燥4h后,制得g-C3N4负载的银单原子催化剂。
实施例5:
(1)在水浴锅中将400mL的去离子水加热至80℃后,加入2g硼酸、2g柠檬酸、1.5g硝酸铵、2.5g氯化铂,充分搅拌,待固体物质完全溶解后,停止加热,自然冷却至室温,制得 溶液A;
(2)通过氢氧化钠溶液调节溶液A的pH值为7.5,制得溶液B;
(3)将溶液B加热至80℃后,向溶液B中加入1.5g的g-C3N4粉末,在80℃下搅拌10min后,制得溶液C;
(4)将2.5g硼氢化钠加入到100mL去离水中,搅拌待固体物质完全溶液后制得溶液D;
(5)将溶液D倒入溶液C中,在80℃下反应1.5h,过滤后将固体物质放入60℃的烘箱中干 燥6h后,制得g-C3N4负载的铂单原子催化剂。
Claims (7)
1.一种金属单原子催化剂,其特征在于:通过氧化还原反应,将溶液中的金属离子还原成单质,且还原产物沉积于分散在溶液中的g-C3N4载体表面,该催化剂具有较好的催化析氢性能以及较好的光催化降解性能。
2.如权利要求1所述的金属单原子催化剂的制备方法,其特征在于包括以下步骤:
(1)在水浴锅中将10~500mL的去离子水加热至35~85℃后,加入0.2~20g硼酸、0.2~20g柠檬酸、0.1~10g硝酸铵、0.1~20g无机金属盐,充分搅拌,待固体物质完全溶解后,停止加热,自然冷却至室温,制得溶液A;
(2)通过氢氧化钠溶液调节溶液A的pH值为6.5~12范围,制得溶液B;
(3)将溶液B加热至35~85℃后,向溶液B中加入0.1~10g的g-C3N4粉末,在35~85℃下搅拌10~60min后,制得溶液C;
(4)将0.2~20g次磷酸盐或硼氢化物加入到10~200mL去离水中,搅拌待固体物质完全溶液后制得溶液D;
(5)将溶液D倒入溶液C中,在35~85℃下反应1min~12h,过滤后将固体物质放入60℃的烘箱中干燥0.5~12h后,制得g-C3N4负载的一元金属单原子催化剂。
3.如权利要求2所述的一种金属单原子催化剂的制备方法,其特征在于步骤(1)中所述的无机金属盐是硫酸镍、氯化镍、硝酸镍、硫酸铜、氯化铜、硝酸铜、硫酸钴、硝酸钴、氯化钴、氯化钯、硝酸钯、硫酸钯、硫酸铈、硝酸铈、氯化铈、硝酸银、氯化金、氯金酸钠、硫代硫酸金钠、氯化铂、硝酸铂中的一种;将10~500mL的去离子水加热至35~85℃后,加入0.2~20g硼酸、0.2~20g柠檬酸、0.1~10g硝酸铵、0.1~20g无机金属盐,充分搅拌,待固体物质完全溶解后,停止加热,自然冷却至室温,制得溶液A。
4.如权利要求2所述的一种金属单原子催化剂的制备方法,其特征在于步骤(2)中所述的调节溶液A的pH值为6.5~12范围,制得溶液B。
5.如权利要求2所述的一种金属单原子催化剂的制备方法,其特征在于步骤(3)中所述的将溶液B加热至35~85℃后,向溶液B中加入0.1~10g的g-C3N4粉末,在35~85℃下搅拌10~60min后,制得溶液C。
6.如权利要求2所述的一种金属单原子催化剂的制备方法,其特征在于步骤(4)中所述的次磷酸盐为次磷酸钠、次磷酸钾中的一种,硼氢化物为硼氢化钠、硼氢化钾中的一种;将0.2~20g次磷酸盐或硼氢化物加入到10~200mL去离水中,搅拌待固体物质完全溶液后制得溶液D。
7.如权利要求2所述的一种金属单原子催化剂的制备方法,其特征在于步骤(5)中所述的将溶液D倒入溶液C中,在35~85℃下反应1min~12h,过滤后将固体物质放入60℃的烘箱中干燥0.5~12h后,制得g-C3N4负载的一元金属单原子催化剂。
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