JP2019166483A - Method for manufacturing composite metal nanoparticle carrier - Google Patents
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- 239000002082 metal nanoparticle Substances 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title abstract description 19
- 239000002105 nanoparticle Substances 0.000 claims abstract description 112
- 229910052751 metal Inorganic materials 0.000 claims abstract description 78
- 239000002184 metal Substances 0.000 claims abstract description 78
- 239000002245 particle Substances 0.000 claims abstract description 41
- 238000000151 deposition Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 5
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 35
- 239000007864 aqueous solution Substances 0.000 description 19
- 238000010304 firing Methods 0.000 description 15
- 239000010931 gold Substances 0.000 description 11
- 229910002696 Ag-Au Inorganic materials 0.000 description 9
- 150000002736 metal compounds Chemical class 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 8
- 239000002243 precursor Substances 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 230000001376 precipitating effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- -1 perovskite Chemical compound 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 3
- 229910000929 Ru alloy Inorganic materials 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- OYJSZRRJQJAOFK-UHFFFAOYSA-N palladium ruthenium Chemical compound [Ru].[Pd] OYJSZRRJQJAOFK-UHFFFAOYSA-N 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 241000003832 Lantana Species 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 2
- 229910002094 inorganic tetrachloropalladate Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 239000010944 silver (metal) Substances 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- FXCWJOMEAGKNSP-UHFFFAOYSA-K [Cl-].[Cl-].[Cl-].Cl.[K+].[Pt+2] Chemical compound [Cl-].[Cl-].[Cl-].Cl.[K+].[Pt+2] FXCWJOMEAGKNSP-UHFFFAOYSA-K 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-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
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002116 nanohorn Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000009736 wetting 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
Abstract
Description
本発明は、複合金属ナノ粒子担持体の製造方法に関する。 The present invention relates to a method for producing a composite metal nanoparticle carrier.
銀（Ａｇ）、金（Ａｕ）、白金（Ｐｔ）、パラジウム（Ｐｄ）、ロジウム（Ｒｈ）などの貴金属は、高い触媒活性をもつことが知られており、排ガス処理用触媒や燃料電池の電極用触媒として利用されている。しかしながら、これらの貴金属は、いずれも高価であることから、できるだけ少ない使用量で触媒活性が得られることが望ましい。 Noble metals such as silver (Ag), gold (Au), platinum (Pt), palladium (Pd), and rhodium (Rh) are known to have high catalytic activity. It is used as a catalyst. However, since these noble metals are all expensive, it is desirable that catalytic activity be obtained with as little use amount as possible.
また、平均粒子径が１μｍ未満、特に１〜１００ｎｍである粒子は、ナノ粒子と呼ばれ、特に、貴金属のナノ粒子は、例えば１０μｍ以上の大きな平均粒子径をもつ一般的な貴金属粒子に比べて、比表面積が大きく、触媒活性が優れていることが知られている。また、２種類以上の金属からなる複合金属ナノ粒子は、それぞれの元素の性質を併せ持つだけではなく、新規な特性を発現することが期待されている。 In addition, particles having an average particle diameter of less than 1 μm, particularly 1 to 100 nm are called nanoparticles, and in particular, noble metal nanoparticles are larger than general noble metal particles having a large average particle diameter of, for example, 10 μm or more. It is known that the specific surface area is large and the catalytic activity is excellent. In addition, composite metal nanoparticles composed of two or more types of metals are expected not only to have the properties of each element but also to develop new characteristics.
例えば、特許文献１および非特許文献１には、粒径を制御するため、保護剤として機能するＰＶＰ（ポリ（Ｎ−ビニル−２−ピロリドン））を、還元剤および溶媒として機能するトリエチレングリコールに溶解させることによって溶液（１）を調製するとともに、テトラクロロパラジウム酸カリウム（[Ｋ２第１金属Ｃｌ４]）と塩化ルテニウム（［ＲｕＣｌ３・ｎＨ２Ｏ］）を水に溶解させて調整した水溶液（２）を調製した上で、２００℃に加熱した溶液（１）に水溶液（２）を噴霧することによって混合液を作製し、この混合液を、室温まで放冷させた後に遠心分離によって、平均粒径が１０ｎｍ程度の合金微粒子を、混合溶液から分離して得る方法が開示されている。 For example, Patent Document 1 and Non-Patent Document 1 disclose that PVP (poly (N-vinyl-2-pyrrolidone)) that functions as a protective agent is used to control the particle size, and triethylene glycol that functions as a reducing agent and a solvent. Solution (1) is prepared by dissolving in water, and potassium tetrachloropalladate ([K 2 first metal Cl 4 ]) and ruthenium chloride ([RuCl 3 · nH 2 O]) are dissolved in water and adjusted. The prepared aqueous solution (2) is prepared, and then the aqueous solution (2) is sprayed onto the solution (1) heated to 200 ° C., and then the mixture is allowed to cool to room temperature and then centrifuged. Discloses a method of obtaining alloy fine particles having an average particle diameter of about 10 nm from a mixed solution.
しかしながら、特許文献１および非特許文献１の製造方法は、Ｐｄ−Ｒｕ合金粒子を合成する際に、溶液(１)の加熱や、溶液（１）に対する水溶液（２）の噴霧が必要であり、加えて、粒径を制御するための保護剤（ＰＶＰ）も必要であるなど、合成プロセスが複雑であるという問題がある。 However, the production methods of Patent Document 1 and Non-Patent Document 1 require heating the solution (1) and spraying the aqueous solution (2) on the solution (1) when synthesizing the Pd—Ru alloy particles. In addition, there is a problem that the synthesis process is complicated such that a protective agent (PVP) for controlling the particle size is also required.
加えて、上記Ｐｄ−Ｒｕ合金粒子を触媒として使用する場合には、上記Ｐｄ−Ｒｕ合金粒子を水に投入した分散液に、アルミナ担体を加え、撹拌し、液をロータリーエバポレータに移し、減圧下で６０℃に加熱、乾燥して粉体とし、粉砕した後に円盤状に成形し、破砕し、篩にかけることにより、アルミナ担体に担持された触媒として調製されるものであって、触媒製造プロセスも非常に複雑である。 In addition, when the Pd-Ru alloy particles are used as a catalyst, an alumina carrier is added to the dispersion in which the Pd-Ru alloy particles are added to water, and the mixture is stirred and transferred to a rotary evaporator. The catalyst is produced as a catalyst supported on an alumina carrier by heating to 60 ° C., drying to form a powder, pulverizing, forming into a disk shape, crushing, and passing through a sieve. Is also very complex.
また、担体上に金属微粒子を担持させる他の方法としては、例えば、含浸法が挙げられる。この方法は、金属塩の水溶液中に担体を含浸させ、その後、乾燥や焼成工程を経ることによって、担体上の金属塩を分解して金属微粒子担持体を作製する方法である。 Further, as another method for supporting the metal fine particles on the carrier, for example, an impregnation method can be mentioned. This method is a method in which an aqueous metal salt solution is impregnated with a carrier, and thereafter a metal salt on the carrier is decomposed by a drying or firing step to produce a metal fine particle carrier.
含浸法は、Ａｇ、Ａｕ、Ｐｔ、Ｐｄ、Ｒｈなどの単一金属を微粒子（ナノ粒子）として担体上に析出させて単一金属ナノ粒子を作製する場合には適した方法であるが、ＡｇとＡｕなどの２種以上の金属を担体上に析出させて、複合金属ナノ粒子を作製する場合には、粒子径が大きくなる傾向があり、触媒活性を発現するために必要な比表面積を効果的に増加させることができないことから、例えば、粒子径が１０ｎｍ以下の複合金属ナノ粒子の作製には適さない。 The impregnation method is a method suitable for producing single metal nanoparticles by depositing single metals such as Ag, Au, Pt, Pd, and Rh as fine particles (nanoparticles) on a support. When composite metal nanoparticles are produced by precipitating two or more metals such as Au and Au on the support, the particle diameter tends to increase, and the specific surface area necessary to develop catalytic activity is effective. For example, it is not suitable for the production of composite metal nanoparticles having a particle diameter of 10 nm or less.
本発明の目的は、異なる金属成分をそれぞれ含有する第１および第２ナノ粒子を、別工程で順次適正に析出させることにより、担体上に、適正な微細析出形態で複合金属ナノ粒子を析出（担持）させることが可能な複合金属ナノ粒子担持体の製造方法を提供する。 An object of the present invention is to deposit composite metal nanoparticles in an appropriate fine precipitation form on a support by sequentially and appropriately depositing first and second nanoparticles each containing different metal components in separate steps ( A method for producing a composite metal nanoparticle carrier capable of being carried) is provided.
上記課題を解決するため、本発明の要旨構成は以下の通りである。
（１）担体上に、第１金属成分を含有する第１ナノ粒子を析出させる第１工程と、該第１ナノ粒子よりも小さな粒子径をもち、第２金属成分を含有する第２ナノ粒子を、前記第１ナノ粒子の表面上に析出させる第２工程とを含むことを特徴とする複合金属ナノ粒子担持体の製造方法。
（２）前記第１ナノ粒子の平均粒子径が、１００ｎｍ以下であり、前記第２ナノ粒子の平均粒子径が、１０ｎｍ未満である上記（１）に記載の複合金属ナノ粒子担持体の製造方法。
（３）前記担体が、アルミナ、シリカ、ジルコニアおよびゼオライトの中から選択される少なくとも１種からなる上記（１）または（２）に記載の複合金属ナノ粒子担持体の製造方法。
（４）前記第１工程は、前記担体を、前記第１金属成分を含有する溶液で濡らした後に、乾燥および焼成の少なくとも一方を行なうことを含む、上記（１）〜（３）のいずれか１項に記載の複合金属ナノ粒子担持体の製造方法。
（５）前記第２工程は、前記担体上に担持される前記第１ナノ粒子の表面を、前記第２金属成分を含有する溶液で濡らした状態で光を照射した後に、乾燥および焼成の少なくとも一方を行なうことを含む、上記（１）〜（４）のいずれか１項に記載の複合金属ナノ粒子担持体の製造方法。
In order to solve the above problems, the gist of the present invention is as follows.
(1) A first step of precipitating first nanoparticles containing a first metal component on a carrier, and a second nanoparticle having a smaller particle diameter than the first nanoparticles and containing a second metal component Including a second step of precipitating a metal nanoparticle on the surface of the first nanoparticle.
(2) The method for producing a composite metal nanoparticle carrier according to (1), wherein the average particle diameter of the first nanoparticles is 100 nm or less, and the average particle diameter of the second nanoparticles is less than 10 nm. .
(3) The method for producing a composite metal nanoparticle support according to (1) or (2), wherein the carrier is at least one selected from alumina, silica, zirconia, and zeolite.
(4) Any of the above (1) to (3), wherein the first step includes performing at least one of drying and baking after the support is wetted with the solution containing the first metal component. 2. A method for producing a composite metal nanoparticle carrier according to item 1.
(5) In the second step, the surface of the first nanoparticles supported on the carrier is irradiated with light in a state of being wetted with a solution containing the second metal component, and then at least drying and baking are performed. The manufacturing method of the composite metal nanoparticle support | carrier of any one of said (1)-(4) including performing one.
本発明によれば、担体上に、第１金属成分を含有する第１ナノ粒子を析出させる第１工程と、第１ナノ粒子よりも小さな粒子径をもち、第２金属成分を含有する第２ナノ粒子を、第１ナノ粒子の表面上に析出させる第２工程とを別個に分けて順次行なうことによって、複雑な製造プロセスを採用することなく、簡単な工程だけで、例えば、粒子径が１０ｎｍ以下の複合金属ナノ粒子担持体の製造方法の提供が可能になった。 According to the present invention, the first step of precipitating the first nanoparticles containing the first metal component on the carrier, the second step having a smaller particle diameter than the first nanoparticles and containing the second metal component. By separately performing the second step of depositing the nanoparticles on the surface of the first nanoparticles separately and sequentially, it is possible to perform, for example, a particle size of 10 nm without using a complicated manufacturing process and only by simple steps. The following method for producing a composite metal nanoparticle carrier can be provided.
＜複合金属ナノ粒子担持体＞
次に、本発明に従う複合金属ナノ粒子担持体の実施形態について図面を参照しながら以下で説明する。図１は、本実施形態の複合金属ナノ粒子担持体の表面の一部だけを拡大して模式的に示したものである。
<Composite metal nanoparticle carrier>
Next, an embodiment of a composite metal nanoparticle carrier according to the present invention will be described below with reference to the drawings. FIG. 1 schematically shows only a part of the surface of the composite metal nanoparticle carrier of the present embodiment in an enlarged manner.
図示した本実施形態の複合金属ナノ粒子担持体１は、担体２と、担体２上に、微細析出物として担持された、第１金属成分を含有する複数の第１ナノ粒子３と、これら複数の第１ナノ粒子３の各々の表面上に、第１ナノ粒子３よりも小さな粒子径をもつ超微細析出物として形成された、第２金属成分を含有する複数の第２ナノ粒子４とを有する。すなわち、複合金属ナノ粒子担持体１は、１個の第１ナノ粒子３と複数個の第２ナノ粒子４とで構成された複合金属ナノ粒子７の複数個が担体２上に担持された構造を有している。 The composite metal nanoparticle carrier 1 of the present embodiment shown in the figure includes a carrier 2, a plurality of first nanoparticles 3 containing a first metal component supported on the carrier 2 as fine precipitates, and a plurality of these nanoparticles. A plurality of second nanoparticles 4 containing a second metal component formed on each surface of the first nanoparticles 3 as ultrafine precipitates having a particle diameter smaller than that of the first nanoparticles 3; Have. That is, the composite metal nanoparticle carrier 1 has a structure in which a plurality of composite metal nanoparticles 7 composed of one first nanoparticle 3 and a plurality of second nanoparticles 4 are supported on the carrier 2. have.
複合金属ナノ粒子７は、第１ナノ粒子３を、担体２上に析出させるが、第２ナノ粒子４は、担体２上にはほとんど析出させずに、第１ナノ粒子３の表面上に優先析出させた、いわゆるタンデム型の析出形態（粒子上に粒子が析出する析出形態）を有している。このようなタンデム型の析出形態を有する複合金属ナノ粒子７は、これまでには存在しなかった新規な構造を有するものである。 The composite metal nanoparticles 7 precipitate the first nanoparticles 3 on the carrier 2, but the second nanoparticles 4 do not substantially deposit on the carrier 2, but preferentially on the surface of the first nanoparticles 3. It has a so-called tandem precipitation form (a precipitation form in which particles are deposited on the particles). The composite metal nanoparticles 7 having such a tandem-type precipitation form have a novel structure that has not existed so far.
そして、本実施形態の複合金属ナノ粒子担持体１は、新規なタンデム型の析出形態の複合金属ナノ粒子７を有することによって、第１ナノ粒子３の表面上に多数存在する、第１ナノ粒子３と第２ナノ粒子４との界面が活性点となる結果、高い活性を発現することができる。 And the composite metal nanoparticle carrier 1 of the present embodiment has a plurality of first nanoparticles that are present on the surface of the first nanoparticle 3 by having the composite metal nanoparticles 7 in a novel tandem-type precipitation form. As a result of the interface between 3 and the second nanoparticle 4 being an active point, high activity can be expressed.
第１ナノ粒子３を構成する第１金属成分としては、含浸法などで用いる溶液中での分散安定性の高い金属成分（金属塩）を用いるのが好ましく、例えば、Ａｇ、Ｐｄ、Ｐｔ、Ｍｎなどの金属成分（金属塩）が挙げられる。 As the first metal component constituting the first nanoparticle 3, it is preferable to use a metal component (metal salt) having high dispersion stability in a solution used in the impregnation method, for example, Ag, Pd, Pt, Mn And metal components (metal salts).
第２ナノ粒子４を構成する第２金属成分としては、（水）溶液中での酸化還元電位が比較的貴な金属成分（金属塩）を用いるのが好ましく、例えば、Ａｕ、Ｃｕ、Ｎｉ、Ｆｅ、Ｒｕなどの金属成分（金属塩）が挙げられる。 As the second metal component constituting the second nanoparticle 4, it is preferable to use a metal component (metal salt) having a relatively noble oxidation-reduction potential in (water) solution. For example, Au, Cu, Ni, Examples thereof include metal components (metal salts) such as Fe and Ru.
第１ナノ粒子３の平均粒子径は、できるだけ小さくすること、好ましくは、１００ｎｍ以下とすることが好ましく、より好ましくは２０ｎｍ以下、さらに好ましくは１０ｎｍ以下とする。第１ナノ粒子３の粒子径は、小さくするほど、担体２上に、より多くの第１ナノ粒子３を析出（担持）させることが可能になり、それに伴って、第２ナノ粒子４を析出させることができる第１ナノ粒子３の総表面積も増加する結果、活性点となる第１ナノ粒子３と第２ナノ粒子４との界面の存在個数（または延在長さの合計）も増加するからである。なお、第１ナノ粒子３の平均粒子径の下限値は、第１ナノ粒子３が小さすぎると、第１ナノ粒子３の表面上に第２ナノ粒子４が析出し難くなって、活性点となる、第１ナノ粒子３と第２ナノ粒子４とで形成される界面の存在個数（または延在長さの合計）が不足する傾向があることから、３ｎｍ以上とすることが好ましい。 The average particle diameter of the first nanoparticles 3 should be as small as possible, preferably 100 nm or less, more preferably 20 nm or less, and even more preferably 10 nm or less. The smaller the particle diameter of the first nanoparticles 3, the more first nanoparticles 3 can be deposited (supported) on the carrier 2, and accordingly the second nanoparticles 4 are deposited. As a result, the total surface area of the first nanoparticles 3 that can be generated also increases, and as a result, the number of existing interfaces (or the total length of extension) of the interfaces between the first nanoparticles 3 and the second nanoparticles 4 that become active points also increases. Because. In addition, the lower limit of the average particle diameter of the first nanoparticles 3 is such that if the first nanoparticles 3 are too small, the second nanoparticles 4 are difficult to precipitate on the surface of the first nanoparticles 3, and the active points and Since there is a tendency that the number of the interfaces formed by the first nanoparticles 3 and the second nanoparticles 4 (or the total extension length) tends to be insufficient, the thickness is preferably 3 nm or more.
第２ナノ粒子４の平均粒子径は、第１ナノ粒子３の表面上に、多くの第２ナノ粒子４を析出させることが、第１ナノ粒子３と第２ナノ粒子４とで形成される界面の存在個数を増加させることになるため、できるだけ小さくすること、具体的には１０ｎｍ以下とすることが好ましく、より好ましくは５ｎｍ以下、さらに好ましくは１ｎｍ以下とする。
なお、ここでいう「ナノ粒子の平均粒子径」は、透過型電子顕微鏡（ＴＥＭ）によって得られた複合金属ナノ粒子担持体１を撮像した写真から、複合金属ナノ粒子７を構成する各ナノ粒子３、４ごとに、少なくとも１００個以上の粒子径を測定し、測定した粒子径から算出した平均値である。ＴＥＭの観察倍率は、特に限定はしないが、例えば、１０００００倍〜５０００００倍の範囲とすることが好ましい。
The average particle diameter of the second nanoparticles 4 is formed by the first nanoparticles 3 and the second nanoparticles 4 such that a large number of the second nanoparticles 4 are deposited on the surface of the first nanoparticles 3. In order to increase the number of existing interfaces, it is preferable to make it as small as possible, specifically 10 nm or less, more preferably 5 nm or less, and even more preferably 1 nm or less.
The “average particle diameter of the nanoparticles” referred to here is each nanoparticle constituting the composite metal nanoparticle 7 from a photograph of the composite metal nanoparticle carrier 1 obtained by a transmission electron microscope (TEM). It is an average value calculated from the measured particle diameter by measuring at least 100 particle diameters every 3 or 4. Although the observation magnification of TEM is not specifically limited, For example, it is preferable to set it as the range of 100,000 times-500,000 times.
加えて、本発明でいう「微細析出物」とは、例えば、平均粒径が１００ｎｍ以下の析出物をいい、また、「超微細析出物」とは、微細析出物よりも小さな粒子径をもち、かつ例えば、平均粒径が１０ｎｍ以下の析出物をいうこととする。
複合金属ナノ粒子担持体１は、第１ナノ粒子３の質量割合が０．１〜１０．００質量％であることが好ましく、第２ナノ粒子４の質量割合が０．０１〜５．００質量％であることが好ましい。また、第１ナノ粒子３と第２ナノ粒子４の存在割合は、質量比で５：１〜１：２の範囲であることが好ましい。
In addition, the “fine precipitate” in the present invention means, for example, a precipitate having an average particle size of 100 nm or less, and the “ultra fine precipitate” has a particle size smaller than that of the fine precipitate. And, for example, a precipitate having an average particle size of 10 nm or less is used.
In the composite metal nanoparticle carrier 1, the mass ratio of the first nanoparticles 3 is preferably 0.1 to 10.00 mass%, and the mass ratio of the second nanoparticles 4 is 0.01 to 5.00 mass. % Is preferred. Moreover, it is preferable that the presence ratio of the 1st nanoparticle 3 and the 2nd nanoparticle 4 is the range of 5: 1 to 1: 2 by mass ratio.
担体２は、第１ナノ粒子３を担持（析出）できる表面性状を有していればよく、特に限定はないが、例えば、より多くの第１ナノ粒子３を担持できるようにする点で、比表面積が大きくなる多孔質体を用いることが好ましい。また、担体２の形状は、複合金属ナノ粒子７を担持できる形状であればよく、粒状、板状、ハニカム状など種々の形状が挙げられる。さらに、担体２は、使用用途や製造条件にもよるが、２００℃以上の耐熱性を有していることがより好ましい。 The support 2 only needs to have a surface property capable of supporting (depositing) the first nanoparticles 3 and is not particularly limited. For example, in order to support more first nanoparticles 3, It is preferable to use a porous body having a large specific surface area. Moreover, the shape of the support | carrier 2 should just be a shape which can carry | support the composite metal nanoparticle 7, and various shapes, such as a granular form, plate shape, and honeycomb shape, are mentioned. Furthermore, it is more preferable that the carrier 2 has a heat resistance of 200 ° C. or higher, depending on the intended use and production conditions.
担体２の材質としては、例えば、セラミックス材料、高分子材料、炭素材料などが挙げられる。 Examples of the material of the carrier 2 include ceramic materials, polymer materials, and carbon materials.
セラミックス材料としては、例えば，アルミナ、シリカ、シリカアルミナ、カルシア、マグネシア、チタニア、セリア、ジルコニア、セリアジルコニア、ランタナ、ランタナアルミナ、酸化スズ、酸化タングステン、アルミノシリケート（ゼオライト）、アルミノホスフェート、ボロシリケート、リンタングステン酸、ヒドロキシアパタイト、ハイドロタルサイト、ペロブスカイト、コージェライト、ムライト，シリコンカーバイドが挙げられる。 Examples of the ceramic material include alumina, silica, silica alumina, calcia, magnesia, titania, ceria, zirconia, ceria zirconia, lantana, lantana alumina, tin oxide, tungsten oxide, aluminosilicate (zeolite), aluminophosphate, borosilicate, Examples thereof include phosphotungstic acid, hydroxyapatite, hydrotalcite, perovskite, cordierite, mullite, and silicon carbide.
高分子材料としては、ポリエチレン(ＰＥ)、ポリプロピレン、プラスチック、ゴム、化学繊維が挙げられる。 Examples of the polymer material include polyethylene (PE), polypropylene, plastic, rubber, and chemical fiber.
炭素材料としては、例えば、活性炭、カーボンブラック、アセチレンブラック、カーボンナノチューブ又はカーボンナノホーンが挙げられる。本実施形態では、これらの担体２の中から１種だけを使用するか、又は２種以上を併用してもよい。 Examples of the carbon material include activated carbon, carbon black, acetylene black, carbon nanotube, and carbon nanohorn. In the present embodiment, only one type of these carriers 2 may be used, or two or more types may be used in combination.
＜複合金属ナノ粒子担持体の製造方法＞
次に、本発明に従う複合金属ナノ粒子担持体１の代表的な製造方法の例を説明する。
本発明の複合金属ナノ粒子担持体の製造方法は、担体上に、第１金属または第１金属の化合物の形で第１金属成分を含有する複数の第１ナノ粒子を析出させる第１工程と、第１ナノ粒子よりも小さな粒子径をもち、第２金属または第２金属の化合物の形で第２金属成分を含有する複数の第２ナノ粒子を、第１ナノ粒子の表面上に析出させる第２工程とで主に構成されている。
<Method for producing composite metal nanoparticle carrier>
Next, the example of the typical manufacturing method of the composite metal nanoparticle support 1 according to this invention is demonstrated.
The method for producing a composite metal nanoparticle carrier of the present invention includes a first step of depositing a plurality of first nanoparticles containing a first metal component in the form of a first metal or a compound of a first metal on a support, A plurality of second nanoparticles having a particle size smaller than that of the first nanoparticles and containing a second metal component in the form of a second metal or a compound of the second metal are deposited on the surface of the first nanoparticles. This is mainly composed of the second step.
第１工程は、担体上に複数の第１ナノ粒子を析出させる工程であって、担体の表面を、第１金属化合物または第１金属イオンを含有する溶液（以下、単に「第１金属含有溶液」という。）で濡らした後に、乾燥および焼成の少なくとも一方を行なう工程を含んでいる。 The first step is a step of precipitating a plurality of first nanoparticles on a carrier, and the surface of the carrier is coated with a solution containing a first metal compound or a first metal ion (hereinafter simply referred to as “first metal-containing solution”). And the step of performing at least one of drying and baking after wetting.
図２は、本実施形態の複合金属ナノ粒子担持体１の製造方法を示したフロー図である。図２に示す第１工程は、担体２を第１金属含有溶液中に浸漬または担体２の表面に第１金属含有溶液を塗布して、担体２に第１金属含有溶液を含浸させる工程（第１金属含浸工程Ｓ１）と、担体２に含浸させた第１金属含有溶液中の第１金属成分を含有する第１ナノ粒子３を担体２上に析出させるために、乾燥や焼成を行なう工程（乾燥・焼成工程Ｓ２）とで構成されている。 FIG. 2 is a flowchart showing a method for manufacturing the composite metal nanoparticle carrier 1 of the present embodiment. The first step shown in FIG. 2 is a step of immersing the carrier 2 in the first metal-containing solution or applying the first metal-containing solution to the surface of the carrier 2 and impregnating the carrier 2 with the first metal-containing solution (first step). 1 metal impregnation step S1) and a step of drying and firing in order to deposit the first nanoparticles 3 containing the first metal component in the first metal-containing solution impregnated in the carrier 2 on the carrier 2 ( And drying / firing step S2).
第１金属含有溶液としては、第１金属化合物または第１金属イオンを含有する溶液であればよく、特に限定はしないが、第１金属が、例えば、Ａｇの場合には、硝酸銀水溶液が挙げられ、Ｐｄの場合には、例えばテトラクロロパラジウム酸アンモニウム水溶液、硝酸パラジウム水溶液等が挙げられ、Ｐｔの場合には、テトラクロリド白金(II)酸カリウム水溶液、ヘキサクロリド白金(IV)酸水溶液が挙げられ、Ｍｎの場合には、硝酸マンガン水溶液が挙げられる。また、第１金属含有溶液の溶媒は、水だけには限定されず、有機溶媒を用いることもできる。また、第１工程は、第１金属含浸工程Ｓ１に代えて、共沈法を用いた第１金属共沈工程に変更することもできる。 The first metal-containing solution is not particularly limited as long as it is a solution containing the first metal compound or the first metal ion, but when the first metal is, for example, Ag, an aqueous silver nitrate solution is used. In the case of Pd, for example, an aqueous solution of ammonium tetrachloropalladate, an aqueous solution of palladium nitrate, etc. In the case of Pt, an aqueous solution of potassium tetrachloride platinum (II) and an aqueous solution of hexachloride platinum (IV) are mentioned. In the case of Mn, an aqueous manganese nitrate solution is used. Moreover, the solvent of a 1st metal containing solution is not limited only to water, An organic solvent can also be used. Further, the first step can be changed to a first metal coprecipitation step using a coprecipitation method instead of the first metal impregnation step S1.
乾燥・焼成工程Ｓ２は、乾燥や焼成の処理雰囲気については特に限定する必要はなく、例えば、空気中で行なうことができる。また、乾燥温度は５０〜１００℃の範囲とし、焼成温度は１５０〜５５０℃の範囲とすることが好ましい。加えて、乾燥工程を行なわずに焼成工程だけを行なってもよい。 The drying / firing step S2 is not particularly limited with respect to the treatment atmosphere for drying or firing, and can be performed, for example, in the air. The drying temperature is preferably in the range of 50 to 100 ° C, and the firing temperature is preferably in the range of 150 to 550 ° C. In addition, you may perform only a baking process, without performing a drying process.
第２工程は、第１ナノ粒子３よりも小さな粒子径をもつ、第２金属または第２金属化合物からなる複数の第２ナノ粒子４を、第１ナノ粒子３の表面上に析出させる工程であって、担体２上に担持される第１ナノ粒子３の表面を、第２金属化合物または第２金属イオンを含有する溶液（以下、単に「第２金属含有溶液」という。）で濡らした状態で光を照射した後に、乾燥および焼成の少なくとも一方を行なう工程を含んでいる。 The second step is a step of depositing a plurality of second nanoparticles 4 made of a second metal or a second metal compound having a smaller particle diameter than the first nanoparticles 3 on the surface of the first nanoparticles 3. The surface of the first nanoparticles 3 supported on the carrier 2 is wetted with a solution containing a second metal compound or a second metal ion (hereinafter simply referred to as “second metal-containing solution”). And after irradiating with light, at least one of drying and baking is included.
図２に示す第２工程は、第１工程を行なった後の担体２を、第２金属含有溶液中に入れて、好適には撹拌等により分散させた状態で光を照射する工程（第２金属含有溶液中での光照射工程Ｓ３）と、遠心分離することによって、生成した複合金属ナノ粒子担持体１の前駆体１Ａを、第２金属含有溶液から分離する工程（遠心分離工程Ｓ４）と、担体２上のナノ複合粒子（第１ナノ粒子３および第２ナノ粒子４）の前駆体７Ａを、第１金属ナノ粒子７に還元等の処理を行うため、乾燥や焼成を行なう工程（乾燥・焼成工程Ｓ５）とで構成されている。 In the second step shown in FIG. 2, the support 2 after the first step is put in a second metal-containing solution and is preferably irradiated with light in a state of being dispersed by stirring or the like (second step). A light irradiation step S3) in a metal-containing solution, a step of separating the precursor 1A of the composite metal nanoparticle carrier 1 produced by centrifugation from the second metal-containing solution (centrifugation step S4), The step of drying or baking the precursor 7A of the nanocomposite particles (the first nanoparticle 3 and the second nanoparticle 4) on the carrier 2 in order to perform a treatment such as reduction on the first metal nanoparticle 7 (drying) -It is comprised by baking process S5).
本発明では、特に、第２金属含有溶液中での光照射工程Ｓ３を行なうことによって、担体２に担持されている、第１金属または第１金属化合物からなる複数の第１ナノ粒子３の表面上で、光照射に起因したプラズモン共鳴を生じさせ、第２金属含有溶液中の第２金属イオンまたは第２金属化合物から、第２金属または第２金属化合物からなる第２ナノ粒子４が、第１ナノ粒子３の表面上に生成し、その後、乾燥・焼成工程Ｓ５を行なうことによって、担体２上に担持されている第１ナノ粒子３と、第１ナノ粒子３の表面上に生成した第２ナノ粒子４とが、それぞれ、結果として、第１金属からなる第１ナノ粒子３と第２金属からなる第２ナノ粒子４になり、それによって、担体２上に複合金属ナノ粒子７を担持した複合金属ナノ粒子担持体１を製造することができる。このとき、複合金属ナノ粒子７を構成する第１ナノ粒子３と第２金属粒子４の界面が活性点となっているものと考えられる。 In the present invention, in particular, the surface of the plurality of first nanoparticles 3 made of the first metal or the first metal compound supported on the carrier 2 by performing the light irradiation step S3 in the second metal-containing solution. Above, the plasmon resonance resulting from light irradiation is generated, and the second nanoparticle 4 made of the second metal or the second metal compound from the second metal ion or the second metal compound in the second metal-containing solution is The first nanoparticle 3 generated on the surface of the first nanoparticle 3 and then the drying / firing step S5 are performed, whereby the first nanoparticle 3 supported on the carrier 2 and the first nanoparticle 3 generated on the surface of the first nanoparticle 3 are formed. 2 nanoparticles 4 respectively become the first nanoparticles 3 made of the first metal and the second nanoparticles 4 made of the second metal, thereby supporting the composite metal nanoparticles 7 on the carrier 2. Composite metal nanoparticle carrier 1 It can be produced. At this time, it is thought that the interface of the 1st nanoparticle 3 and the 2nd metal particle 4 which comprises the composite metal nanoparticle 7 becomes an active point.
第２金属含有溶液としては、第２金属化合物または第２金属イオンを含有する溶液であればよく、特に限定はしないが、第２金属が、例えば、Ａｕの場合には、塩化金酸水溶液、酢酸金水溶液が挙げられ、Ｃｕの場合には、硝酸銅水溶液、塩化銅水溶液等が挙げられ、Ｎｉの場合には硝酸ニッケル水溶液、塩化ニッケル水溶液が挙げられ、Ｆｅの場合には硝酸鉄水溶液、酢酸鉄水溶液が挙げられ、Ｒｕの場合には、アセチルアセトナートルテニウムス水溶液、塩化ルテニウム水溶液が挙げられる。また、第２金属含有溶液の溶媒は、水だけには限定されず、有機溶媒を用いることもできる。 The second metal-containing solution is not particularly limited as long as it is a solution containing a second metal compound or a second metal ion, but when the second metal is, for example, Au, a chloroauric acid aqueous solution, In the case of Cu, an aqueous solution of copper acetate, an aqueous solution of copper chloride, and the like are exemplified. In the case of Ni, an aqueous solution of nickel nitrate, an aqueous solution of nickel chloride, and in the case of Fe, an aqueous solution of iron nitrate, An aqueous solution of iron acetate is used. In the case of Ru, an aqueous solution of acetylacetonate ruthenium and an aqueous solution of ruthenium chloride are used. Moreover, the solvent of a 2nd metal containing solution is not limited only to water, An organic solvent can also be used.
第２金属含有溶液中での光照射工程Ｓ３において、照射する光としては、第１ナノ粒子３の表面上で生じるプラズモンの光吸収率は、紫外光（波長域：２２５〜４００ｎｍ）が最も高く、そこから高波長側（可視光域）に向かうにつれてなだらかに低下していくことから、紫外光を含む光を用いることが、光照射時間を短くできる点で好ましいが、可視光（波長：４００〜７８０ｎｍ）だけであっても、プラズモンの光吸収は生じることから、本発明では、紫外光領域から可視光領域までの波長範囲の光を照射できることが好ましい。照射する光の好適な波長域は、例えば２２５〜６００ｎｍの範囲である。 In the light irradiation step S3 in the second metal-containing solution, as the light to be irradiated, the light absorption rate of the plasmon generated on the surface of the first nanoparticle 3 is highest in the ultraviolet light (wavelength range: 225 to 400 nm). From there, it gradually decreases as it goes to the higher wavelength side (visible light region), so that it is preferable to use light containing ultraviolet light in terms of shortening the light irradiation time, but visible light (wavelength: 400) Even if it is only ˜780 nm), light absorption of plasmons occurs. Therefore, in the present invention, it is preferable that light in a wavelength range from the ultraviolet light region to the visible light region can be irradiated. The suitable wavelength range of the light to irradiate is the range of 225-600 nm, for example.
光源としては、例えば水銀ランプ、キセノンランプ、ハロゲンランプ、ＬＥＤなどが挙げられ、特に、超高圧水銀ランプを用いることが好ましい。光の照射強度としては、５ｍＷ/ｃｍ２以上であることが、照射時間を短時間（例えば３０分以内）にできる点で好ましい。 Examples of the light source include a mercury lamp, a xenon lamp, a halogen lamp, and an LED, and it is particularly preferable to use an ultrahigh pressure mercury lamp. The light irradiation intensity is preferably 5 mW / cm 2 or more in that the irradiation time can be shortened (for example, within 30 minutes).
遠心分離工程Ｓ４は、第２金属含有溶液から、複合金属ナノ粒子担持体１またはその前駆体１Ａを分離して回収する工程であって、公知の遠心分離装置を用いて行うことができる。 Centrifugation step S4 is a step of separating and recovering the composite metal nanoparticle carrier 1 or its precursor 1A from the second metal-containing solution, and can be performed using a known centrifuge.
乾燥・焼成工程Ｓ５は、担体２に担持されている、第１ナノ粒子３と第２ナノ粒子４を、それぞれ、金属である、第１ナノ粒子３と第２ナノ粒子４の状態に揃えるための処理であって、乾燥・焼成工程Ｓ５では、乾燥・焼成工程Ｓ５を行なう前の状態が、第１ナノ粒子３および第２ナノ粒子４の一部または全部が金属の状態になっていない場合には、第１ナノ粒子３および第２ナノ粒子４を金属に還元するため、水素ガス雰囲気中にて１５０〜
５００℃、１〜５時間の条件で焼成工程を行なうことが好ましい。
In the drying / firing step S5, the first nanoparticles 3 and the second nanoparticles 4 supported on the carrier 2 are arranged in the state of the first nanoparticles 3 and the second nanoparticles 4 which are metals, respectively. In the drying / firing step S5, the state before the drying / firing step S5 is the case where a part or all of the first nanoparticles 3 and the second nanoparticles 4 are not in a metal state. In order to reduce the 1st nanoparticle 3 and the 2nd nanoparticle 4 to a metal, in a hydrogen gas atmosphere, 150-
It is preferable to perform a baking process on the conditions of 500 degreeC and 1 to 5 hours.
また、乾燥・焼成工程Ｓ５を行なう前に、担体上に、既に金属の状態である、第１ナノ粒子３と第２ナノ粒子４が生成されていて、還元処理を行う必要がない場合には、大気中で乾燥や焼成を行なってもよい。また、乾燥工程を省略し、焼成工程のみを行うこともできる。乾燥温度は、例えば５０〜１００℃の範囲、焼成は、例えば焼成温度が１５０〜５００℃の範囲、焼成時間が１〜５時間であることが好ましい。 In addition, when the first nanoparticle 3 and the second nanoparticle 4 that are already in a metal state are already formed on the support before the drying / firing step S5, it is not necessary to perform a reduction treatment. Further, drying and baking may be performed in the air. Moreover, a drying process is abbreviate | omitted and only a baking process can also be performed. The drying temperature is, for example, in the range of 50 to 100 ° C., and the firing is preferably in the range of, for example, the firing temperature of 150 to 500 ° C., and the firing time is 1 to 5 hours.
尚、上述したところは、この発明の実施形態の例を示したにすぎず、請求の範囲において種々の変更を加えることができる。 The above description is merely an example of the embodiment of the present invention, and various modifications can be made within the scope of the claims.
次に、本発明の効果をさらに明確にするために、実施例について説明するが、本発明はこの実施例に限定されるものではない。 Next, in order to further clarify the effects of the present invention, examples will be described. However, the present invention is not limited to these examples.
（実施例）
ＨＹ型ゼオライト粉末（東ソー株式会社製、商品名：ＨＳＺ−６６０ＨＯＡ）からなる担体１ｇを、担体に対し、銀金属量が２．０質量％である硝酸銀（ＡｇＮＯ３）水溶液５ｍｌに混入し、撹拌によって溶液中に担体を分散させ、エバポレーターにより含浸させた（第１金属（Ａｇ）含浸工程Ｓ１）。
次いで、６５℃で乾燥を行なった後に、空気中にて５００℃、５時間の焼成を行い、担体上に酸化銀からなる複数の第１ナノ粒子を析出させた（乾燥・焼成工程Ｓ２）。
その後、第１ナノ粒子を析出させた担体を、担体に対し、金金属量が１．０質量％の塩化金酸（ＨＡｕＣｌ４）水溶液１５ｍｌの入ったビーカーに入れ、超高圧水銀ランプ（ウシオ電機、商品名：ＸＳ、５００Ｗ）の光を３０分照射し撹拌することによって、担体上に析出した第１ナノ粒子の表面上に、第２ナノ粒子を析出させて、Ａｇ−Ａｕ複合金属ナノ粒子担持体の前駆体を形成させる（第２金属含有溶液中での光照射工程Ｓ３）。
その後、Ａｇ−Ａｕ複合金属ナノ粒子担持体の前駆体が分散した塩化金酸水溶液を、遠心分離装置（株式会社久保田製作所製、商品名：３７００）を用いて遠心分離することによって、前駆体を塩化金酸水溶液から分離した（遠心分離工程Ｓ４）。
分離したＡｇ−Ａｕ複合金属ナノ粒子担持体の前駆体は、その後、水素ガス雰囲気中で２００℃、１時間の焼成を行ない、Ａｇ−Ａｕ複合金属ナノ粒子担持体を作製した（乾燥・焼成（還元）工程Ｓ５）。Ａｇ−Ａｕ複合金属ナノ粒子担持体は、Ａｇナノ粒子の質量割合が２．０質量％であり、Ａｕナノ粒子の質量割合が１．０質量％であった。
図３（ａ）および図３（ｂ）は、本発明例のＡｇ−Ａｕ複合金属ナノ粒子担持体のＨＡＡＤＦ−ＳＴＥＭ画像であって、図３（ａ）が倍率１０００００倍、図３（ｂ）が倍率４０００００倍で撮像したものであり、図３（ｃ）は、図３（ｂ）の画像を線図で書き表したものである。
(Example)
1 g of a carrier composed of HY-type zeolite powder (trade name: HSZ-660HOA, manufactured by Tosoh Corporation) is mixed in 5 ml of an aqueous silver nitrate (AgNO 3 ) solution having a silver metal amount of 2.0% by mass with respect to the carrier, and stirred. Then, the carrier was dispersed in the solution and impregnated with an evaporator (first metal (Ag) impregnation step S1).
Next, after drying at 65 ° C., baking was performed in air at 500 ° C. for 5 hours to deposit a plurality of first nanoparticles made of silver oxide on the carrier (drying / baking step S2).
Thereafter, the carrier on which the first nanoparticles are deposited is placed in a beaker containing 15 ml of a chloroauric acid (HAuCl 4 ) aqueous solution having a gold metal content of 1.0% by mass with respect to the carrier. , Trade name: XS, 500 W) for 30 minutes by irradiation and stirring, thereby precipitating second nanoparticles on the surface of the first nanoparticles deposited on the carrier, and Ag-Au composite metal nanoparticles A precursor of the carrier is formed (light irradiation step S3 in the second metal-containing solution).
Thereafter, the aqueous solution of chloroauric acid in which the precursor of the Ag-Au composite metal nanoparticle carrier is dispersed is centrifuged using a centrifugal separator (trade name: 3700, manufactured by Kubota Corporation) to thereby obtain the precursor. It isolate | separated from the chloroauric acid aqueous solution (centrifugation process S4).
The separated precursor of the Ag—Au composite metal nanoparticle carrier was then fired in a hydrogen gas atmosphere at 200 ° C. for 1 hour to produce an Ag—Au composite metal nanoparticle carrier (drying / firing ( Reduction) step S5). In the Ag—Au composite metal nanoparticle carrier, the mass ratio of Ag nanoparticles was 2.0 mass%, and the mass ratio of Au nanoparticles was 1.0 mass%.
3 (a) and 3 (b) are HAADF-STEM images of the Ag—Au composite metal nanoparticle carrier of the example of the present invention, in which FIG. 3 (a) is 100000 times magnification, FIG. 3 (b). Is taken at a magnification of 400000 times, and FIG. 3C is a diagram depicting the image of FIG.
本発明例のＡｇ−Ａｕ複合金属ナノ粒子担持体は、図３から明らかなように、２ｎｍ程度の粒子径をもつＡｕ金属からなる第２ナノ粒子が、６ｎｍ程度の粒子径をもつＡｇ金属からなる第１ナノ粒子の表面上に多数析出した、いわゆるタンデム型の複合金属ナノ粒子が担体上に多数存在するのが認められ、また、複合金属ナノ粒子のほとんどが、粒子径３０ｎｍ以下であるＡｇ−Ａｕ複合金属ナノ粒子であり、それらの中で、粒子径１０ｎｍ以下であるＡｇ−Ａｕ複合金属ナノ粒子も多数存在していることもわかる。 As is apparent from FIG. 3, the Ag-Au composite metal nanoparticle carrier of the present invention example is composed of a second nanoparticle made of Au metal having a particle diameter of about 2 nm and an Ag metal having a particle diameter of about 6 nm. A large number of so-called tandem type composite metal nanoparticles deposited on the surface of the first nanoparticles are observed on the support, and most of the composite metal nanoparticles are Ag particles having a particle diameter of 30 nm or less. It can also be seen that there are a large number of Ag-Au composite metal nanoparticles having a particle diameter of 10 nm or less among the -Au composite metal nanoparticles.
１ 複合金属ナノ粒子担持体
２ 担体
３ 第１ナノ粒子
４ 第２ナノ粒子
５ 光源
６ 第２金属含有溶液
７ 複合金属ナノ粒子
DESCRIPTION OF SYMBOLS 1 Composite metal nanoparticle support body 2 Support | carrier 3 1st nanoparticle 4 2nd nanoparticle 5 Light source 6 2nd metal containing solution 7 Composite metal nanoparticle
Claims (5)
該第１ナノ粒子よりも小さな粒子径をもち、第２金属成分を含有する第２ナノ粒子を、前記第１ナノ粒子の表面上に析出させる第２工程と
を含むことを特徴とする複合金属ナノ粒子担持体の製造方法。 A first step of depositing first nanoparticles containing a first metal component on a support;
A second step of depositing second nanoparticles containing a second metal component having a smaller particle diameter than the first nanoparticles on the surface of the first nanoparticles. A method for producing a nanoparticle carrier.
前記第２ナノ粒子の平均粒子径が、１０ｎｍ未満である請求項１に記載の複合金属ナノ粒子担持体の製造方法。 The average particle diameter of the first nanoparticles is 100 nm or less,
The method for producing a composite metal nanoparticle carrier according to claim 1, wherein an average particle diameter of the second nanoparticles is less than 10 nm.
In the second step, at least one of drying and baking is performed after irradiating light with the surface of the first nanoparticles supported on the carrier wet with the solution containing the second metal component. The manufacturing method of the composite metal nanoparticle support | carrier of any one of Claims 1-4 including this.
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