JP5907551B2 - ボロン酸エステル型高分子微粒子、及び貴金属ナノ粒子担持ボロン酸エステル型高分子微粒子複合体、芳香族ニトロ化合物の選択的水素化触媒並びにそれらの製造方法 - Google Patents
ボロン酸エステル型高分子微粒子、及び貴金属ナノ粒子担持ボロン酸エステル型高分子微粒子複合体、芳香族ニトロ化合物の選択的水素化触媒並びにそれらの製造方法 Download PDFInfo
- Publication number
- JP5907551B2 JP5907551B2 JP2011190242A JP2011190242A JP5907551B2 JP 5907551 B2 JP5907551 B2 JP 5907551B2 JP 2011190242 A JP2011190242 A JP 2011190242A JP 2011190242 A JP2011190242 A JP 2011190242A JP 5907551 B2 JP5907551 B2 JP 5907551B2
- Authority
- JP
- Japan
- Prior art keywords
- type polymer
- acid ester
- polymer fine
- boronic acid
- ester type
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- -1 aromatic nitro compounds Chemical class 0.000 title claims description 91
- 229920000642 polymer Polymers 0.000 title claims description 63
- 239000010419 fine particle Substances 0.000 title claims description 51
- 239000003054 catalyst Substances 0.000 title claims description 39
- 238000000034 method Methods 0.000 title claims description 20
- 239000002131 composite material Substances 0.000 title claims description 19
- 229910000510 noble metal Inorganic materials 0.000 title claims description 17
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 13
- 239000010931 gold Substances 0.000 claims description 70
- 229910052737 gold Inorganic materials 0.000 claims description 69
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 65
- 239000002105 nanoparticle Substances 0.000 claims description 60
- 239000002245 particle Substances 0.000 claims description 47
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 229920002873 Polyethylenimine Polymers 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 16
- 238000006722 reduction reaction Methods 0.000 claims description 16
- 239000002082 metal nanoparticle Substances 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 230000009467 reduction Effects 0.000 claims description 9
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 8
- BODYVHJTUHHINQ-UHFFFAOYSA-N (4-boronophenyl)boronic acid Chemical compound OB(O)C1=CC=C(B(O)O)C=C1 BODYVHJTUHHINQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 230000003100 immobilizing effect Effects 0.000 claims description 3
- 239000004570 mortar (masonry) Substances 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 230000003197 catalytic effect Effects 0.000 description 11
- 238000009826 distribution Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- 150000004685 tetrahydrates Chemical class 0.000 description 4
- YFZHODLXYNDBSM-UHFFFAOYSA-N 1-ethenyl-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(C=C)C=C1 YFZHODLXYNDBSM-UHFFFAOYSA-N 0.000 description 3
- LBSXSAXOLABXMF-UHFFFAOYSA-N 4-Vinylaniline Chemical compound NC1=CC=C(C=C)C=C1 LBSXSAXOLABXMF-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- AUFHQOUHGKXFEM-UHFFFAOYSA-N C[Au]C Chemical compound C[Au]C AUFHQOUHGKXFEM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 230000009878 intermolecular interaction Effects 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PIAOLBVUVDXHHL-UHFFFAOYSA-N 2-nitroethenylbenzene Chemical compound [O-][N+](=O)C=CC1=CC=CC=C1 PIAOLBVUVDXHHL-UHFFFAOYSA-N 0.000 description 1
- UWRZIZXBOLBCON-UHFFFAOYSA-N 2-phenylethenamine Chemical compound NC=CC1=CC=CC=C1 UWRZIZXBOLBCON-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- FDWHCGUBEYURBN-UHFFFAOYSA-N [Au].ClC1=C(C(=NC=C1)Cl)Cl Chemical class [Au].ClC1=C(C(=NC=C1)Cl)Cl FDWHCGUBEYURBN-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- UYQMSQMCIYSXOW-UHFFFAOYSA-N benzene-1,2,4,5-tetrol Chemical compound OC1=CC(O)=C(O)C=C1O UYQMSQMCIYSXOW-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000005620 boronic acid group Chemical class 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000002343 gold Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical group O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 229910052720 vanadium Chemical group 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical group [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Description
金は、卑金属酸化物との密着性に乏しく、融点(1063℃)が他の貴金属よりも低いために触媒調製の焼成段階で小さなナノ粒子の融解・凝集が起こり、30nm以上の大きな金ナノ粒子しか得られず、触媒活性が極めて乏しいと考えられていた。ところが、金を好ましくは直径10nm以下の超微粒子として種々の金属酸化物担体上に分散・固定することにより高い触媒活性を発現することが報告され(特許文献1、非特許文献2)、たとえば、TiO2に金ナノ粒子を担持させて、常温CO酸化及びプロピレンオキシドの気相一段合成の触媒として利用すること、及びCeO2に金ナノ粒子を担持させて、水性ガスシフト反応に利用することが提案されている(非特許文献3)。しかし、有機高分子担体に金属微粒子を分散・固定化させた触媒材料の開発はあまり進んでいない(特許文献2、特許文献3)。これは、有機高分子材料が、耐熱性に劣ること及び無機材料と比較して高価であることに起因する。一方、高分子材料は、無機材料にない成型加工性(繊維など)を有するため、ソフトな触媒材料としての応用が期待できる(非特許文献4)。
また、本発明によれば、ベンゼン−1,4−ジボロン酸(式1):
本発明のボロン酸エステル型高分子微粒子担体は、常温・常圧の極めて温和な条件で調製される単分散性の粒子状高分子であり、走査型電子顕微鏡(FE−SEM)写真を観察すると下記のような花型構造を有し、300℃までの耐熱性を有する。
また、本発明のボロン酸エステル型高分子微粒子は、耐熱性に優れ、繊維や膜など種々の形状・形態に容易に加工できるので、本発明のボロン酸エステル型高分子微粒子に貴金属粒子を担持させた触媒材料はソフトな触媒材料として種々の用途に利用できる。
本発明の芳香族ニトロ化合物の選択的水素化触媒は、ニトロ基に対する選択性が極めて高いので、試薬使用量や廃棄物の低減、分離・精製プロセスにおけるエネルギーを節減できる有用な触媒である。
ベンゼン−1,4−ジボロン酸(式1)415mg(2.5mmol)をテトラヒドロフラン(THF)125mLに加えたものとペンタエリスリトール(式2)340mg(2.5mmol)をTHF125mLに加えたものを混合し、室温で48時間静置したところ、溶液が懸濁した(最終濃度は10mMになる)。生成した析出物をろ別し、走査型電子顕微鏡(FE−SEM)観察したところ、粒径2.3±0.3μmの花型粒子であることが確認された(図1)。この粒子を赤外吸収スペクトル測定したところ、ボロン酸エステル構造を有することが示唆された。また、粉末X線回折(PXRD)測定したところ、ジオキサボロール一次元鎖の積層構造:
ペンタエリスリトール(式2)に代えて、1,2,4,5−テトラヒドロキシベンゼンを用いて実施例1と同じ手順を行ったところ、単分散のサブミクロン球状粒子が得られ(図4)、花型形状にはならなかった。
テトラヒドロフランに代えて、メタノールを用いて、実施例1と同じ手順を行ったところ、花型形状にはならなかった(図6)。また、水を溶媒として用いた場合には構造体の生成は認めらなかった。
<吸着還元法>
実施例1で調製した本発明のボロン酸エステル粒子(18.5mg)のメタノール分散液(9.4mL)に塩化金酸四水和物(0.77mg)のメタノール溶液(0.6mL)を加え、ろ別したボロン酸エステル粒子をメタノール(5mL)に分散し、水素化ホウ素ナトリウム(7.7mg)のメタノール溶液(3.3mL)を添加して還元反応を行ったところ、ボロン酸エステル粒子に金ナノ粒子を担持できなかった。
<固相混合法>
[実施例4]4−ニトロスチレンの還元反応
実施例2及び3で調製した金ナノ粒子/ボロン酸エステル型高分子微粒子複合体を4−ニトロスチレンの還元反応に用いて、触媒活性を確認した。
Claims (8)
- 繰り返し単位として下記構造:
- ベンゼン−1,4−ジボロン酸(式1):
- 請求項1に記載の花型形状を有するボロン酸エステル型高分子微粒子に、平均粒径5nm以下の貴金属ナノ粒子又はクラスターを固定化してなる、貴金属ナノ粒子/ボロン酸エステル型高分子微粒子複合体。
- 貴金属ナノ粒子又はクラスターは、金ナノ粒子又はクラスターである、請求項3に記載の複合体。
- 請求項1に記載の花型形状を有するボロン酸エステル型高分子微粒子に、平均粒径5nm以下の金ナノ粒子又はクラスターを固定化してなる、芳香族ニトロ化合物の選択的水素化触媒。
- 前記金ナノ粒子又はクラスターを2〜8wt%の含有量で固定化してなる、請求項5に記載の芳香族ニトロ化合物の選択的水素化触媒。
- ベンゼン−1,4−ジボロン酸(式1):
当該ボロン酸エステル型高分子微粒子を溶媒に分散させてボロン酸エステル型高分子微粒子分散液を調製し、
当該分散液にポリエチレンイミンを添加して、ポリエチレンイミン/ボロン酸エステル分散液を調製し、
当該ポリエチレンイミン/ボロン酸エステル分散液に、塩化金酸を添加して、金イオン/ボロン酸エステル分散液を調製し、
当該金イオン/ボロン酸エステル分散液に、水酸化ホウ素ナトリウムを添加して還元させる、
ことを含む金ナノ粒子/ボロン酸エステル型高分子微粒子複合体を得る方法。 - ベンゼン−1,4−ジボロン酸(式1):
当該ボロン酸エステル型高分子微粒子に対して、金前駆体を添加し、乳鉢にて撹拌混合し、水素の存在下で還元反応を行う、
ことを含む、金ナノ粒子をボロン酸エステル型高分子微粒子に担持させてなる金ナノ粒子/ボロン酸エステル型高分子微粒子複合体を得る方法。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011190242A JP5907551B2 (ja) | 2011-09-01 | 2011-09-01 | ボロン酸エステル型高分子微粒子、及び貴金属ナノ粒子担持ボロン酸エステル型高分子微粒子複合体、芳香族ニトロ化合物の選択的水素化触媒並びにそれらの製造方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011190242A JP5907551B2 (ja) | 2011-09-01 | 2011-09-01 | ボロン酸エステル型高分子微粒子、及び貴金属ナノ粒子担持ボロン酸エステル型高分子微粒子複合体、芳香族ニトロ化合物の選択的水素化触媒並びにそれらの製造方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2013053181A JP2013053181A (ja) | 2013-03-21 |
JP5907551B2 true JP5907551B2 (ja) | 2016-04-26 |
Family
ID=48130471
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2011190242A Active JP5907551B2 (ja) | 2011-09-01 | 2011-09-01 | ボロン酸エステル型高分子微粒子、及び貴金属ナノ粒子担持ボロン酸エステル型高分子微粒子複合体、芳香族ニトロ化合物の選択的水素化触媒並びにそれらの製造方法 |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP5907551B2 (ja) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103273079B (zh) * | 2013-05-10 | 2015-07-22 | 安徽医科大学 | 一种金纳米花的制备方法及其应用 |
JP6327607B2 (ja) * | 2014-03-11 | 2018-05-23 | 公立大学法人首都大学東京 | パラジウム粒子を有機高分子化合物に担持した複合体 |
CN103977776B (zh) * | 2014-04-21 | 2016-04-13 | 苏州康磁医疗科技有限公司 | 一种基于金表面的糖敏智能水凝胶及其合成方法 |
CN110605383B (zh) * | 2019-09-30 | 2021-08-31 | 中国科学院合肥物质科学研究院 | 金纳米针丛材料及其制备方法 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5114008B2 (ja) * | 2006-01-27 | 2013-01-09 | 公立大学法人首都大学東京 | 表面に金微粒子を付着させた高分子材料およびその製造方法 |
KR101474579B1 (ko) * | 2007-01-24 | 2014-12-18 | 더 리전트 오브 더 유니버시티 오브 캘리포니아 | 결정형 3d- 및 2d-공유결합성 유기 골격의 합성, 특성분석 및 디자인 |
JP5290599B2 (ja) * | 2008-03-17 | 2013-09-18 | 公立大学法人首都大学東京 | 金微粒子を担体に分散・固定化する方法 |
JP5543150B2 (ja) * | 2009-08-07 | 2014-07-09 | エヌ・イーケムキャット株式会社 | 芳香族ニトロ化合物の選択的水素化触媒、その製造方法および再生方法並びにこれを用いた芳香族ニトロ化化合物の選択的水素化方法 |
-
2011
- 2011-09-01 JP JP2011190242A patent/JP5907551B2/ja active Active
Also Published As
Publication number | Publication date |
---|---|
JP2013053181A (ja) | 2013-03-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Shahzeydi et al. | Facile and green synthesis of copper nanoparticles loaded on the amorphous carbon nitride for the oxidation of cyclohexane | |
Liu et al. | Metallic cobalt nanoparticles imbedded into ordered mesoporous carbon: A non-precious metal catalyst with excellent hydrogenation performance | |
Cui et al. | Cobalt nanoparticles supported on N-doped mesoporous carbon as a highly efficient catalyst for the synthesis of aromatic amines | |
Cui et al. | Facile preparation of fluffy N-doped carbon modified with Ag nanoparticles as a highly active and reusable catalyst for catalytic reduction of nitroarenes | |
Kadam et al. | Hexagonal mesoporous silica supported ultrasmall copper oxides for oxidative amidation of carboxylic acids | |
Norouzi et al. | Ionic liquid-modified magnetic mesoporous silica supported tungstate: A powerful and magnetically recoverable nanocatalyst | |
JP5907551B2 (ja) | ボロン酸エステル型高分子微粒子、及び貴金属ナノ粒子担持ボロン酸エステル型高分子微粒子複合体、芳香族ニトロ化合物の選択的水素化触媒並びにそれらの製造方法 | |
Seral-Ascaso et al. | Synthesis and application of gold-carbon hybrids as catalysts for the hydroamination of alkynes | |
Tian et al. | Palladium nanoparticles dispersed on the hollow aluminosilicate microsphere@ hierarchical γ-AlOOH as an excellent catalyst for the hydrogenation of nitroarenes under ambient conditions | |
Nandi et al. | Nitrogen-rich graphitic-carbon stabilized cobalt nanoparticles for chemoselective hydrogenation of nitroarenes at milder conditions | |
Zhao et al. | AuPt bimetallic nanoalloys supported on SBA-15: A superior catalyst for quinoline selective hydrogenation in water | |
Babu et al. | Robust Au–Ag/graphene bimetallic nanocatalyst for multifunctional activity with high synergism | |
Sun et al. | Multifunctional dendritic mesoporous silica nanospheres loaded with silver nanoparticles as a highly active and recyclable heterogeneous catalyst | |
WO2013187323A1 (ja) | 金クラスター触媒及びその製造方法 | |
Mao et al. | Facile synthesis of highly stable heterogeneous catalysts by entrapping metal nanoparticles within mesoporous carbon | |
TW201231164A (en) | Catalysts containing nano-materials and methods of making and using same | |
Rostamnia et al. | Polymeric hybrid mesoporous silica hollow nanospheres as a support for palladium and application of the PdNPs@ PANI/HNS nanocomposite for aerobic benzyl alcohol oxidation | |
Peng et al. | Preparation of thermal stable supported metal (Cu, Au, Pd) nanoparticles via cross-linking cellulose gel confinement strategy | |
US8962512B1 (en) | Synthesis of PD particles by alcohols-assisted photoreduction for use in supported catalysts | |
Li et al. | Encapsulating UiO-66-NH2@ Pt with defective PCN-222 as an active armor to fabricate a sandwich-type nanocatalyst for the tandem synthesis via hydrogenation of nitroarenes | |
Zhu et al. | Visible-light-driven carbonylation reaction over palladium supported on spherical-like graphitic carbon nitride | |
CN108097279B (zh) | 一种贵金属纳米颗粒复合羟基磷灰石超长纳米线催化耐火纸 | |
Can et al. | A facile synthesis of monodisperse cobalt–ruthenium alloy nanoparticles as catalysts for the dehydrogenation of morpholine borane and the hydrogenation of various organic compounds | |
JPWO2020175309A1 (ja) | アミド化合物の水素化に用いる水素添加反応用触媒およびこれを用いたアミン化合物の製造方法 | |
KR101263918B1 (ko) | 담지촉매 및 이 촉매의 존재하에 진행되는 셀룰로오스의 소르비톨로의 선택적 촉매 전환 방법 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20140808 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20150521 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20150603 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20150723 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20151009 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20151015 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20160217 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20160317 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 5907551 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |