WO2012035507A9 - Production method of hydrogel-metal composite - Google Patents
Production method of hydrogel-metal composite Download PDFInfo
- Publication number
- WO2012035507A9 WO2012035507A9 PCT/IB2011/054033 IB2011054033W WO2012035507A9 WO 2012035507 A9 WO2012035507 A9 WO 2012035507A9 IB 2011054033 W IB2011054033 W IB 2011054033W WO 2012035507 A9 WO2012035507 A9 WO 2012035507A9
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hydrogel
- metal
- production method
- metal composite
- hydrogels
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 43
- 239000002905 metal composite material Substances 0.000 title claims abstract description 31
- 239000000017 hydrogel Substances 0.000 claims abstract description 110
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 230000007613 environmental effect Effects 0.000 claims abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 34
- 239000000178 monomer Substances 0.000 claims description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000012279 sodium borohydride Substances 0.000 claims description 22
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 239000004971 Cross linker Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 11
- 238000006722 reduction reaction Methods 0.000 claims description 11
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 230000009467 reduction Effects 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
- 230000005855 radiation Effects 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 4
- 238000010894 electron beam technology Methods 0.000 claims description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 2
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 claims description 2
- YYPNJNDODFVZLE-UHFFFAOYSA-N 3-methylbut-2-enoic acid Chemical compound CC(C)=CC(O)=O YYPNJNDODFVZLE-UHFFFAOYSA-N 0.000 claims description 2
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004160 Ammonium persulphate Substances 0.000 claims description 2
- 239000012448 Lithium borohydride Substances 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 150000001412 amines Chemical group 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 230000005865 ionizing radiation Effects 0.000 claims description 2
- 229920005615 natural polymer Polymers 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical group [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Chemical group 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 238000007717 redox polymerization reaction Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 2
- 150000003573 thiols Chemical group 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- 238000010521 absorption reaction Methods 0.000 claims 2
- 238000006460 hydrolysis reaction Methods 0.000 claims 2
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 claims 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 7
- 230000005923 long-lasting effect Effects 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 description 6
- 239000002609 medium Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 3
- -1 poly(2- acrylamido-2-methyl-l-propansulphonic acid) Polymers 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229920001477 hydrophilic polymer Polymers 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 150000004804 polysaccharides Chemical class 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 206010035777 Poisoning and toxicity Diseases 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004836 anionic polysaccharides Chemical group 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- WZMUUWMLOCZETI-UHFFFAOYSA-N azane;borane Chemical class B.N WZMUUWMLOCZETI-UHFFFAOYSA-N 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000012457 nonaqueous media Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- 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
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/065—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents from a hydride
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
- H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
- H01M8/065—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants by dissolution of metals or alloys; by dehydriding metallic substances
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the present invention relates to a production method of hydrogel-metal composite which is prepared in order to be used in hydrogen production and various environmental practices, and prepared in the form of hydrogels comprising metal nanoparticles or metal nanoclusters.
- metal catalysts which are commonly used in catalytic applications, are very-high in proportion to their volumes they are generally preferred at nano-dimension in applications. Metals at nano-dimension provide superior properties in comparison to solid bulk phase. For example, gold (Au) does not display catalytic action in bulk form whereas it has a very-high catalytic activity at nano-dimension.
- Au gold
- a number of problems are experienced in preparing metal catalysts, which are prepared at nano-dimension, and using them as catalyst. The fact that metal particles or metal nanoclusters are unstable in solution medium, they are prone to aggregation (conglomeration), they lose their catalytic activities and precipitate easily are among problems confronted. Another important problem is that nano structures, which will be used as catalyst, particularly leave the solution medium or the product after they perform their functions.
- Hydrogels with these properties have significant advantages in preparing catalysts.
- Hydrogels are network structures which are formed by cross-linking of hydrophilic polymers. Upon the water enters the hydrogel network structure, dimensions of the hydrogel broadens and it may act as a reactor vessel depending on its dimension.
- hydrogels can be synthesized from hydrophilic polymer chains and they can be synthesized from monomers comprising functional group which can form charged ion in aqueous solution as well. Hydrogels comprising these functional chemical groups can uptake oppositely charged metal ions in themselves by incorporating them. Thus, the hydrogel network structure swollen in water become woven by metal ions.
- metal nanoparticles By reducing these metal ions via sodium borohydride reducer, their metal nanoparticles can be synthesized in hydrogel network structure. As a result, metal nanoparticles which are synthesized in hydrogel become stable because they cannot leave the hydrogel structure. These structures can serve as a reactor which contains the catalyst in itself for many aqueous reactions.
- catalysts can be used in order to conduct reactions in hydrogen production. These catalysts are prepared by a variety of methods such as crushing, grinding. Metal nanoparticles or metal nanoclusters with high surface areas can also be prepared by using detergents (surfactants) or linear polymers. These prepared metal particles can be used for production of hydrogen from aqueous NaBH 4 solutions.
- the International patent document no. WO2010010123 discloses synthesis of composites and use thereof consisting of a polysaccharide matrix and metal nanoparticles.
- the method in the document discloses dispersion of metal nanoparticles homogeneously by putting these metal nanoparticles into neutral or charged biologically-based polymer (polysaccharide) and that the composite neutral or anionic polysaccharide forms gel by means of physical and chemical cross-linking.
- JP2007100117 discloses preparation of metal nanoparticles by reducing metals such as Ru, Co, Rh, Ni, Pd, Pt, Os, Ag, etc. by surfactant surface active agents. It is stated that hydrogen can produced via hydrogenation of these metal nanoparticles generated in a reaction matrix.
- the objective of the present invention is to realize a production method of hydrogel-metal composite which can form long-lasting catalytic systems via catalysts embedded into hydrogel support material.
- Another objective of the present invention is to realize a production method of hydrogel-metal composite which does not lose its activity fast.
- a further objective of the present invention is to realize a production method of hydrogel-metal composite which can remove products, to be formed as a result of reaction in the presence of magnetic field, from medium easily.
- Figure 1 is the Cryo-SEM image of the 1% cross-linked poly(2- acrylamido-2-methyl-l-propansulphonic acid) (p(AMPS)) hydrogel.
- Figure 2 is the transmission electron microscope (TEM) image of the p(AMPS)-Ni hydrogel metal composite.
- Figure 3 is the changing of hydrogen production rate in temperature
- Figure 4 is the change in the amount of the hydrogen gas produced with the used amount of NaBH 4
- Figure 5 is the volume of hydrogen gas production with time in the presence of different by weight %NaOH
- Figure 6 is the change in amount of hydrogen gas production of in time usingdifferent amounts of catalysts
- Figure 7 is the % conversion and activities of Poly(2-acrylamido-2- methyl-l-propansulphonic acid)-Nickel (p(AMPS)-Ni) hydrogel composites by as they are used for 5 times repeatedly for same reaction conditions
- Figure 8 is the graph of coversion and activities of p(AMPS)-Ni hydrogel composites in time upon they are kept in pure water for different periods of time
- the inventive production method of hydrogel-metal composite comprises the steps of:
- hydrogel-metal composite which is the final product after the drying process.
- aqueous sodium borohydnde (NaBH 4 ) of 50 ml 0.05-0.5 M is used for reduction of metal ions which are absorbed by the hydrogel.
- hydrogen gas, bases such as NaOH, KOH, acids such as citric acid and hydrazine hydrate are used in order to reduce metal ions which are absorbed by the hydrogel.
- synthesis of hydrogels comprises the steps of:
- hydrogels are synthesized by polymerization techniques such as photopolymerization and redox polymerization where high-energy ionizing radiations such as gamma, electron-beams, X-rays, UV applied on monomer, monomer mixtures or aqueous and/or non-aqueous polymer solutions are used.
- hydrogels are synthesized from monomers, which have different functional groups, in varying amounts and in the presence of different cross-linkers.
- Monomers or polymers which have functional groups such as sulfonyl, amine, carboxylic acid, phosphate, thiol with hydrophilic characteristic or comprise their salts or various forms can be used in synthesis of hydrogels.
- monomers comprising acid group such as acrylic acid (AAc), methacrylic acid (MAc), 2-acrylamido-2-methyl-l-propansulphonic acid (AMPS), 2-acrylamido glycolic (AAGA) or monomers with basic characteristic such as N-vinyl imidazole (VIM), 4- vinyl pyridine (VP), allyl amine (AA) or monomers with acidic characteristic such as boric acid or monomer mixtures created by two or more of these monomers are used.
- acid group such as acrylic acid (AAc), methacrylic acid (MAc), 2-acrylamido-2-methyl-l-propansulphonic acid (AMPS), 2-acrylamido glycolic (AAGA) or monomers with basic characteristic such as N-vinyl imidazole (VIM), 4- vinyl pyridine (VP), allyl amine (AA) or monomers with acidic characteristic such as boric acid or monomer mixtures created by two or more of these monomers are used.
- acidic characteristic such as boric acid or monomer mixtures created
- Hydrogels with network structure obtained by polymerization are polymers that have pore sizes ranging from micrometers to nanometers in order that the metal ions are absorbed. Changing the pore size varies by type and amount of the cross- linker used.
- At least one compound selected from a group generated by ethylene glycol dimethacrylate (EGDMA), polyethylene glycol dimethylacrylate (PEGDA), N,N'-methylenebisacrylamide (MBA) and divinylbenzene (DVB) is used as cross-linker for hydrogel synthesis.
- solvents which are renewed at regular intervals and enable impurities to be removed from the medium such that they will not damage the structure of the hydrogel -such as water, acetone, ethanol, dimethyl formamide (DMF), tetrahydrofurane (THF), toluene, chloroform, benzene- are used.
- hydrogel cross-linked p(AMPS) in pipette with 5 mm radius is synthesized by photo-polymerization method using UV initiator.
- Aqueous solution is prepared from 50 wt% monomer by volume (2-acrylomide-2- methyl-l-propansulphonic acid- AMPS).
- cross-linker N, N'- methylene bis acrylamide - MBA
- initiator 2, 2'-azobis (2- methylpropionamidine) dihydrochloride
- irradiation is carried out onto pipettes via photo reactor for 2 hours.
- impurities such as monomer, cross-linker, initiator which did not incorporated in hydrogel after radiation; they are removed through washing procudure by replacing at wash water every 8 hour for 3 days.
- the hydrogels After the hydrogels are cleaned, they are dried in drying ovens at 40°C, and are kept in a closed container (vessels) in order to be used for generating metal nanoparticles.
- a closed container vessels
- metal nanoparticles are formed by reducing Ni ions within the hydrogel by means of appropriate reducers such as NaBH 4 .
- Hydrogels which have absorbed Ni ions are reduced at a constant mixing speed (200 rpm) by being put into NaBH 4 solution of 0.1-0.5 M.
- Hydrogel comprising nickel particles is washed with distilled water by being changed in every 4 hours for at least 12 hours in order to eliminate impurities.
- the final black metal composite hydrogel is made ready to be used in production of hydrogel from sodium borohydride.
- p(AMPS) hydrogel containing 0.2 g Ni (II) ion is put into 50 ml water at 30°C and it is mixed with aqueous sodium borohydride of 50 ml 0.05-0.5 M comprising 0- 10% NaOH by weight.
- hydrogel which has metal nanoparticles displaying catalytic activity as, hydrogen gas is generated from water reacting with sodium borohydride.
- Metal borohydrides such as LiBH 4 , NaBH 4 , KBH 4 , A1(BH 4 ) 3 , Mg(BH 4 ) 2 and ammonia borane (H 3 NBH 3 ) are also used as hydrogen resource in production of hydrogen gas and hydrogen gas can be obtained from aqueous solutions of these hydrogen resources by means of the inventive hydrogel-metal catalysis.
- nanoparticle-hydrogel composites are used in production of hydrogen gas from metal hydrides and ammonia boranes. Reaction mechanisms occurring during application of the invention are given below:
- n 1, 2, 3, 4, 5, 6, 7.
- general representation of a hydrogel network which is prepared by -S0 3 H functional groups, keeping the metal ion and formation of metal nanoparticles as a consequence of reduction reaction occurring in the presence of sodium borohydride (NaBH 4 ) can be seen.
- Metal ions absorbed by hydrogel are provided from aqueous solution of at least one transition metal selected from a group consisting of Ag, Ru, Co, Ni, Rh, Pd, Os, Fe (II), Fe (III). Metal ions are bound inside the hydrogel structure as a result of interaction of the functional groups on the hydrogel with the metal ions. With the composites which are obtained by preparation of metal nanoparticles as catalyst in hydrogels, great advantages are provided in production of hydrogen. Aqueous NaBH 4 or H 3 NBH 3 to be catalyzed with catalysts embedded into
- hydrogel support materials are contacted without any limitation. Thus, long- lasting catalytic systems are obtained. In addition, for the reason that the reactions occur in the hydrogel structure, no additional reactor is needed and metal interactions that may be hazardous on environment and human health are prevented as well. As the active centers of catalysts are placed in support materials causes a reaction with high yield and has a higher reaction rate can be ontained, by changing the amount of catalyst within hydrogel. In addition, the fact that the catalyst and its active centers are embedded into support material provides advantage in terms of catalyst poisoning and toxicity. Thus, life-span of the catalyst can be longer and the catalyst can be used repeatedly owing to flexible hydrogel network structure around it.
- Metal nanoparticle-hydrogel composites are grinded into small particles and they are placed into basic aqueous sodium borohydride which is 5% NaOH by weight in different concentrations and then mixed. Hydrogen is produced from this mixture at room temperature. Parameters such as NaBH 4 concentration, amount of the catalyst, base concentration and temperature affect production rate of the hydrogen gas.
- p(AMPS)-Ni catalyst is stored in pure water for 1 month, conversion is provided for 100% and its activity is around 75%.
- concentration of metal ion solution can be arranged as desired.
- Metal nanoparticles which will be formed in the hydrogel network structure can be synthesized in appropriate size and amount by analyzing TEM images. The size can be controlled by loading metal ion into the hydrogel. Loading amount of metal ion into hydrogel is directly proportionate to functional groups in the hydrogel structure. And this can be controlled by ratio of monomers to be used.
- p(AMPS) hydrogels has a porous structure and pore dimensions can be increased further by reducing the cross-linker amount.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Medicinal Chemistry (AREA)
- Combustion & Propulsion (AREA)
- General Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a production method of hydrogel-metal composite which is prepared in order to be used in hydrogen production and various environmental practices, and prepared in the form of hydrogels comprising synthesized metal nanoparticles or metal nanoclusters. The objective of the present invention is to realize a production method of hydrogel-metal composite and preparation of hydrogel-metal composites which can form long-lasting catalytic systems via catalysts embedded into hydrogel support material; does not lose its activity fast; can remove products, to be formed as a result of reaction in the presence of magnetic field, from medium easily.
Description
PRODUCTION METHOD OF HYDROGEL-METAL COMPOSITE
Field of the Invention The present invention relates to a production method of hydrogel-metal composite which is prepared in order to be used in hydrogen production and various environmental practices, and prepared in the form of hydrogels comprising metal nanoparticles or metal nanoclusters. Background of the Invention
Because surface areas of metal catalysts, which are commonly used in catalytic applications, are very-high in proportion to their volumes they are generally preferred at nano-dimension in applications. Metals at nano-dimension provide superior properties in comparison to solid bulk phase. For example, gold (Au) does not display catalytic action in bulk form whereas it has a very-high catalytic activity at nano-dimension. A number of problems are experienced in preparing metal catalysts, which are prepared at nano-dimension, and using them as catalyst. The fact that metal particles or metal nanoclusters are unstable in solution medium, they are prone to aggregation (conglomeration), they lose their catalytic activities and precipitate easily are among problems confronted. Another important problem is that nano structures, which will be used as catalyst, particularly leave the solution medium or the product after they perform their functions.
Various methods were developed in order to make catalytic nanoparticles stable. Using surfactant as surface active agent or adsorption of stabilizer agents via electrostatic interaction onto the surface of metal nanoparticles are the some of these primary methods. Metal nanoparticles are made stable by employing these methods. However, due to the fact that new structures entered into the medium this causes high catalytic effects of the particles to be reduced and may lead no
new problems. A support material is needed in order that metal particles to be used at nano-dimension are used as catalyst. Zeolites and silicates of different kinds are the leading foremost support materials used. Because most of the chemical reaction occurs in water; metal nanoparticles which are stable, dispersible in water and can be prepared without any stabilizer can present many superior properties. Hydrogels with these properties have significant advantages in preparing catalysts. Hydrogels are network structures which are formed by cross-linking of hydrophilic polymers. Upon the water enters the hydrogel network structure, dimensions of the hydrogel broadens and it may act as a reactor vessel depending on its dimension. In addition, hydrogels can be synthesized from hydrophilic polymer chains and they can be synthesized from monomers comprising functional group which can form charged ion in aqueous solution as well. Hydrogels comprising these functional chemical groups can uptake oppositely charged metal ions in themselves by incorporating them. Thus, the hydrogel network structure swollen in water become woven by metal ions. By reducing these metal ions via sodium borohydride reducer, their metal nanoparticles can be synthesized in hydrogel network structure. As a result, metal nanoparticles which are synthesized in hydrogel become stable because they cannot leave the hydrogel structure. These structures can serve as a reactor which contains the catalyst in itself for many aqueous reactions.
Various catalysts can be used in order to conduct reactions in hydrogen production. These catalysts are prepared by a variety of methods such as crushing, grinding. Metal nanoparticles or metal nanoclusters with high surface areas can also be prepared by using detergents (surfactants) or linear polymers. These prepared metal particles can be used for production of hydrogen from aqueous NaBH4 solutions.
The International patent document no. WO2010010123 discloses synthesis of composites and use thereof consisting of a polysaccharide matrix and metal nanoparticles. The method in the document discloses dispersion of metal
nanoparticles homogeneously by putting these metal nanoparticles into neutral or charged biologically-based polymer (polysaccharide) and that the composite neutral or anionic polysaccharide forms gel by means of physical and chemical cross-linking.
The Japanese patent document no. JP2007100117 discloses preparation of metal nanoparticles by reducing metals such as Ru, Co, Rh, Ni, Pd, Pt, Os, Ag, etc. by surfactant surface active agents. It is stated that hydrogen can produced via hydrogenation of these metal nanoparticles generated in a reaction matrix.
Summary of the Invention
The objective of the present invention is to realize a production method of hydrogel-metal composite which can form long-lasting catalytic systems via catalysts embedded into hydrogel support material.
Another objective of the present invention is to realize a production method of hydrogel-metal composite which does not lose its activity fast.
A further objective of the present invention is to realize a production method of hydrogel-metal composite which can remove products, to be formed as a result of reaction in the presence of magnetic field, from medium easily.
Detailed Description of the Invention
"Preparation of hydrogel-metal composites" in order to fulfill the objectives of the present invention is illustrated in the accompanying figures, in which:
Figure 1 is the Cryo-SEM image of the 1% cross-linked poly(2- acrylamido-2-methyl-l-propansulphonic acid) (p(AMPS)) hydrogel.
Figure 2 is the transmission electron microscope (TEM) image of the p(AMPS)-Ni hydrogel metal composite.
Figure 3 is the changing of hydrogen production rate in temperature Figure 4 is the change in the amount of the hydrogen gas produced with the used amount of NaBH4
Figure 5 is the volume of hydrogen gas production with time in the presence of different by weight %NaOH
Figure 6 is the change in amount of hydrogen gas production of in time usingdifferent amounts of catalysts
Figure 7 is the % conversion and activities of Poly(2-acrylamido-2- methyl-l-propansulphonic acid)-Nickel (p(AMPS)-Ni) hydrogel composites by as they are used for 5 times repeatedly for same reaction conditions
Figure 8 is the graph of coversion and activities of p(AMPS)-Ni hydrogel composites in time upon they are kept in pure water for different periods of time
The inventive production method of hydrogel-metal composite comprises the steps of:
- preparation of hydrogels with chemical and physical structure which can contain metal ions in itself;
- putting the hydrogels into aqueous solution having metal ions;
- the hydrogels absorbing the metal ions from the metal ion solutions;
- in order to remove the metal ions which are not bind to the hydrogel and cannot be hold by the hydrogel can be removed putting the hydrogel into washing bath where there is solvent that will be able to remove the unbind metal ions from hydrogel structure;
- taking the hydrogels out of the washing bath;
- putting the metal ions absorbed hydrogel into reducing solution;
- reduction of metal ions, which exist within the structure of the hydrogel, via reducers inside the solution;
- obtaining metal nanoparticles and/or metal nanoclusters after reduction in the hydrogel structure;
- drying hydrogels which are taken out of the reducing solution and have metal nanoparticles and/or metal nanoclusters;
obtaining hydrogel-metal composite which is the final product after the drying process. In the preferred embodiment of the invention, aqueous sodium borohydnde (NaBH4) of 50 ml 0.05-0.5 M is used for reduction of metal ions which are absorbed by the hydrogel. In another embodiment of the invention, hydrogen gas, bases such as NaOH, KOH, acids such as citric acid and hydrazine hydrate are used in order to reduce metal ions which are absorbed by the hydrogel.
In the preferred embodiment of the invention, synthesis of hydrogels comprises the steps of:
preparing a mixture which consists of monomer, cross-linker and UV initiator and/or a redox such as ammonium persulphate or free radical initiator;
- putting the mixture prepared into reactor;
- carrying out photo-polymerization process by application of UV radiation to the mixture, or polymerization and cross-linking by high-energy radiation such as gamma, electron-beam, X-rays or any polymerization technique;
passing the hydrogel through washing bath in order to eliminate impurities by removing the hydrogel formed after the photo-polymerization process; drying the hydrogel cleaned;
storing the hydrogel cleaned and dried in a closed container.
In another embodiment of the invention, polymers obtained as a consequence of subjecting natural polymers and/or linear polymers to radiation without using cross-linker are used as hydrogel. In a further embodiment of the invention, hydrogels are synthesized by polymerization techniques such as photopolymerization and redox polymerization where high-energy ionizing radiations such as gamma, electron-beams, X-rays, UV applied on monomer, monomer mixtures or aqueous and/or non-aqueous polymer solutions are used.
In synthesis of hydrogels; hydrogels are synthesized from monomers, which have different functional groups, in varying amounts and in the presence of different cross-linkers. Monomers or polymers which have functional groups such as sulfonyl, amine, carboxylic acid, phosphate, thiol with hydrophilic characteristic or comprise their salts or various forms can be used in synthesis of hydrogels.
In synthesis of hydrogels; monomers comprising acid group such as acrylic acid (AAc), methacrylic acid (MAc), 2-acrylamido-2-methyl-l-propansulphonic acid (AMPS), 2-acrylamido glycolic (AAGA) or monomers with basic characteristic such as N-vinyl imidazole (VIM), 4- vinyl pyridine (VP), allyl amine (AA) or monomers with acidic characteristic such as boric acid or monomer mixtures created by two or more of these monomers are used.
Hydrogels with network structure obtained by polymerization are polymers that have pore sizes ranging from micrometers to nanometers in order that the metal ions are absorbed. Changing the pore size varies by type and amount of the cross- linker used.
In the preferred embodiment of the invention, at least one compound selected from a group generated by ethylene glycol dimethacrylate (EGDMA),
polyethylene glycol dimethylacrylate (PEGDA), N,N'-methylenebisacrylamide (MBA) and divinylbenzene (DVB) is used as cross-linker for hydrogel synthesis.
In the step of passing the hydrogel through washing bath; solvents which are renewed at regular intervals and enable impurities to be removed from the medium such that they will not damage the structure of the hydrogel -such as water, acetone, ethanol, dimethyl formamide (DMF), tetrahydrofurane (THF), toluene, chloroform, benzene- are used. In synthesis process of hydrogels, hydrogel cross-linked p(AMPS) in pipette with 5 mm radius is synthesized by photo-polymerization method using UV initiator. Aqueous solution is prepared from 50 wt% monomer by volume (2-acrylomide-2- methyl-l-propansulphonic acid- AMPS). For solution, cross-linker (N, N'- methylene bis acrylamide - MBA) and initiator (2, 2'-azobis (2- methylpropionamidine) dihydrochloride) are solved in an amount corresponding to 0.5-2% of monomer and monomers inside distilled water and vortex mixture is carried out. In order to form hydrogel network structure, irradiation is carried out onto pipettes via photo reactor for 2 hours. In order to eliminate impurities such as monomer, cross-linker, initiator which did not incorporated in hydrogel after radiation; they are removed through washing procudure by replacing at wash water every 8 hour for 3 days. After the hydrogels are cleaned, they are dried in drying ovens at 40°C, and are kept in a closed container (vessels) in order to be used for generating metal nanoparticles. In order that the hydrogels stored in the container absorb Ni (II) ions, they are kept in nickel chloride solution of 0.1 M 100 ml for 24 hours. Then, metal nanoparticles are formed by reducing Ni ions within the hydrogel by means of appropriate reducers such as NaBH4. Hydrogels which have absorbed Ni ions are reduced at a constant mixing speed (200 rpm) by being put into NaBH4 solution of 0.1-0.5 M. Hydrogel comprising nickel particles is washed with distilled water by being changed in every 4 hours for at least 12 hours in order to
eliminate impurities. The final black metal composite hydrogel is made ready to be used in production of hydrogel from sodium borohydride. p(AMPS) hydrogel containing 0.2 g Ni (II) ion is put into 50 ml water at 30°C and it is mixed with aqueous sodium borohydride of 50 ml 0.05-0.5 M comprising 0- 10% NaOH by weight. By means of hydrogel which has metal nanoparticles displaying catalytic activity as, hydrogen gas is generated from water reacting with sodium borohydride. Metal borohydrides such as LiBH4, NaBH4, KBH4, A1(BH4)3, Mg(BH4)2 and ammonia borane (H3NBH3) are also used as hydrogen resource in production of hydrogen gas and hydrogen gas can be obtained from aqueous solutions of these hydrogen resources by means of the inventive hydrogel-metal catalysis.
With using the metal nanoparticle-hydrogel composites synthesized as catalyst, nanoparticle-hydrogel composites are used in production of hydrogen gas from metal hydrides and ammonia boranes. Reaction mechanisms occurring during application of the invention are given below:
M: Ag, Ru, Co, Ni, Rh, Pd, Os, Fe (II), Fe (III),
n: 1, 2, 3, 4, 5, 6, 7.
In the reaction mechanism above; general representation of a hydrogel network, which is prepared by -S03H functional groups, keeping the metal ion and formation of metal nanoparticles as a consequence of reduction reaction occurring in the presence of sodium borohydride (NaBH4) can be seen.
Metal ions absorbed by hydrogel are provided from aqueous solution of at least one transition metal selected from a group consisting of Ag, Ru, Co, Ni, Rh, Pd, Os, Fe (II), Fe (III). Metal ions are bound inside the hydrogel structure as a result of interaction of the functional groups on the hydrogel with the metal ions.
With the composites which are obtained by preparation of metal nanoparticles as catalyst in hydrogels, great advantages are provided in production of hydrogen. Aqueous NaBH4 or H3NBH3 to be catalyzed with catalysts embedded into
t
hydrogel support materials are contacted without any limitation. Thus, long- lasting catalytic systems are obtained. In addition, for the reason that the reactions occur in the hydrogel structure, no additional reactor is needed and metal interactions that may be hazardous on environment and human health are prevented as well. As the active centers of catalysts are placed in support materials causes a reaction with high yield and has a higher reaction rate can be ontained, by changing the amount of catalyst within hydrogel. In addition, the fact that the catalyst and its active centers are embedded into support material provides advantage in terms of catalyst poisoning and toxicity. Thus, life-span of the catalyst can be longer and the catalyst can be used repeatedly owing to flexible hydrogel network structure around it.
Experimental studies and analysis Metal nanoparticle-hydrogel composites are grinded into small particles and they are placed into basic aqueous sodium borohydride which is 5% NaOH by weight in different concentrations and then mixed. Hydrogen is produced from this mixture at room temperature. Parameters such as NaBH4 concentration, amount of the catalyst, base concentration and temperature affect production rate of the hydrogen gas.
Production rate of the hydrogen increases as the temperature increases for the same reaction conditions. For example, in order to produce same of hydrogen gas approximately 50 min. is needed at 30°C whereas approximately 8 min. is sufficient at 70°C. (Figure 3)
As the amount of NaBH4 increases, the total amount of the produced hydrogen gas increases. (Figure 4)
It was studied under reaction conditions carried out using NaBH4 solution of 50 mM 50 mL at a mixing speed of 1500 rpm at 30°C using 0.2 g p(AMPS)-Ni composite comprising 24.4 mg Ni catalyst calculated based on TGA analysis, and it was observed that the amount of NaOH in the NaBH4 solution does not have much effect on production rate or the produced amount of the hydrogen gas after 2.5% by weight. Therefore, it was determined that amount of the NaOH should be at least 2.5% or more by weight. (Figure 5)
It is observed that production rate of hydrogen gas increases with the increase amount of catalyst under reaction conditions where NaOH amount is 5% by weight using 50 mL 50 mM NaBH4 solution at a mixing speed of 1500 rpm at 30°C using p(AMPS)-Ni composite comprising Ni catalyst in varying amounts according to the value determined by TGA analysis under same reaction conditions. (Figure 6)
Even when the p(AMPS)-Ni catalyst is reused 5 times in a row, it gives 100% yield with over 75% activity. (Figure 7)
Although the p(AMPS)-Ni catalyst is stored in pure water for 1 month, conversion is provided for 100% and its activity is around 75%. (Figure 8) To control size of metal nanoparticles, concentration of metal ion solution can be arranged as desired. Metal nanoparticles which will be formed in the hydrogel network structure can be synthesized in appropriate size and amount by analyzing TEM images. The size can be controlled by loading metal ion into the hydrogel. Loading amount of metal ion into hydrogel is directly proportionate to functional groups in the hydrogel structure. And this can be controlled by ratio of monomers to be used. p(AMPS) hydrogels has a porous structure and pore dimensions can be
increased further by reducing the cross-linker amount. Thus, this enable that the reactants contact metal nanoparticles inside the hydrogel by passing through the pores easily and the reaction to occur fast. So, diffusion problem is eliminated. The fact that the hydrogels increase pore dimension by getting swollen in aqueous media and decreases the pore dimension by shrinking in non-aqueous media enables them to be used as a flexible material and thus provides great advantage in being used in production of hydrogen gas (Figure 1).
The TEM image of Ni particles prepared in hydrogel materials is given in Figure 2. Image of p(AMPS)-Ni hydrogel metal composite, which is obtained and displayed by transmission electron microscope (TEM) is shown in Figure 2. Dark spots with approximately 100 nm dimension and in the form of sphere in the figure indicate metal nanoclusters/metal nanoparticles. Within the framework of these basic concepts, it is possible to develop a wide variety of embodiments of the inventive "production method of hydrogel-metal composite". The invention cannot be limited to the examples described herein; it is essentially according to the claims.
Claims
1. Hydro gel-metal catalysis with composite structure and hydrogen production method by this catalysis prepared to be used in hydrolysis reactions and reduction reactions as catalyst and characterized by steps of:
- preparation of hydrogels with chemical and physical structure which can contain metal ions in itself;
- putting the hydrogels into aqueous solution having metal ions;
- the hydrogels absorbing the metal ions from the solution;
- in order to remove the metal ions which are located on the hydrogel and not bind to the hydrogel, putting the hydrogel into washing bath where there is solvent that will be able to remove the unbind metal ions from its structure;
- taking the hydrogels out of the washing bath;
- putting the metal ions absorbed hydrogei into reducing solution;
- reduction of metal ions, which exist within the structure of the hydrogel, via reducers inside the solution;
- obtaining metal nanoparticles and/or metal nanoclusters after reduction in the hydrogel structure;
- drying hydrogels which are taken out of the reducing solution and have metal nanoparticles and/or metal nanoclusters;
- obtaining hydrogel -metal composite which is the final product after the drying process.
2. A production method of hydrogel-metal composite according to Claim 1, characterized by aqueous sodium borohydride (NaBH4) solution of 50 ml 0.05-0.5 M which is used for reduction of metal ions absorbed by the hydrogel.
18
3. A production method of hydrogel-metal composite according to Claim 1 , characterized by using at least one reducing which is selected from a group consisting of hydrogen gas, bases such as NaBH4, NaOH, KOH, acids such as citric acid and hydrazine hydrate in order to reduce metal ions absorbed by the hydrogel in reduction of metal ions absorbed by the hydrogel.
4. A production method of hydrogel-metal composite according to any of the preceding claims, characterized by step of hydrogel synthesis comprising the steps of:
- preparing a mixture which consists of monomer, cross-linker, UV initiator and/or a redox such as ammonium persulphate or free radical initiator;
- putting the mixture prepared into reactor;
- carrying out photo-polymerization process by application of UV radiation to the mixture, or polymerization and cross-linking by high-energy radiation such as gamma, electron-beam, X-rays or any polymerization technique;
- passing the hydrogel through washing bath in order to eliminate impurities by removing the hydrogel formed after the photo-polymerization process;
- drying the hydrogel cleaned;
- storing the hydrogel cleaned and dried in a closed container (vessels).
5. A production method of hydrogel-metal composite according to Claim 4, characterized by hydrogel which is synthesized by polymerization techniques such as photopolymerization and redox polymerization where high-energy ionizing radiations such as gamma, electron-beams, X-rays, UV applied on monomer, monomer mixtures or aqueous and/or nonaqueous polymer solutions are used.
6. A production method of hydrogel-metal composite according to Claim 4 and 5, characterized by hydrogel which is synthesized using monomers
19 or polymers that have functional groups such as sulfonyl, amine, carboxylic acid, phosphate, thiol with hydrophilic characteristic or comprise their salts or various forms.
7. A production method of hydrogel-metal composite according to any of
Claim 4 to 6, characterized by hydrogel which is synthesized using monomers comprising acid group such as acrylic acid (AAc), methacrylic acid (MAc), 2-acrylamido-2-methyl-l-propansulphonic acid (AMPS), 2- acrylamido glycolic (AAGA) or monomers with basic characteristic such as N-vinyl imidazole (VIM), 4-vinyl pyridine (VP), allyl amine (AA) or monomers with acidic characteristic such as boric acid or monomer mixtures created by two or more of these monomers.
8. A production method of hydrogel-metal composite according to any of Claim 4 and 7, characterized by hydrogel which is synthesized using at least one cross-linker which is selected from a group generated by ethylene glycol dimethacrylate (EGDMA), polyethylene glycol dimethylacrylate (PEGDA), Ν,Ν'-methylenebisacrylamide (MBA) and divinylbenzene (DVB).
9. A production method of hydrogel-metal composite according to any of Claim 4 to 7, characterized in that solvents such as water, acetone, ethanol, dimethyl formamide, tetrahydrofurane, toluene, chloroform, benzene which are replaced at regular intervals to removeimpurities from the hydrogel network such that they will not damage the structure of the hydrogel, are used in washing bath.
10. A production method of hydrogel-metal composite according to any of Claim 4 to 9, characterized by the step of absorption of metal ions where at least one transition metal selected from a group consisting of Ag, Ru,
20 Co, Ni, Rh, Pd, Os, Fe (II), Fe (III) is used as metal ion absorbed by hydrogei.
11. A production method of hydrogel-metal composite according to any of Claim 4 to 10, characterized by the step of absorption of metal ions where hydrogels are kept in nickel chloride solution of 0.1 M 100 ml for 24 hours in order to absorb Ni (II) ions.
12. A production method of hydrogel-metal composite according to any of Claim 1 to 3, characterized by hydrogei which is synthesized in the form of polymers that are obtained as a consequence of subjecting natural polymers and/or linear polymers to radiation without using cross-linker.
13. A production method of hydrogel-metal composite any of the preceding claims, characterized in that it is used as catalysis in hydrolysis reactions in production of hydrogen.
14. A production method of hydrogel-metal composite any of the preceding claims, characterized in that metal borohydrides such as LiBH4, NaBH , KBH4, A1(BH4)3, Mg(BH )2 and ammonia borane (H3NBH3) are used as hydrogen resource in production of hydrogen gas.
15. A production method of hydrogel-metal composite any of the preceding claims, characterized in that it is used in environmental practices such as nitro-phenol reduction.
21
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TR2010/07612 | 2010-09-16 | ||
| TR2010/07612A TR201007612A2 (en) | 2010-09-16 | 2010-09-16 | Preparation of hydrogel-metal composites. |
| TR2011/08984 | 2011-09-13 | ||
| TR201108984 | 2011-09-13 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| WO2012035507A2 WO2012035507A2 (en) | 2012-03-22 |
| WO2012035507A9 true WO2012035507A9 (en) | 2012-05-10 |
| WO2012035507A3 WO2012035507A3 (en) | 2012-06-28 |
Family
ID=44903295
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/IB2011/054033 WO2012035507A2 (en) | 2010-09-16 | 2011-09-15 | Production method of hydrogel-metal composite |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO2012035507A2 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2512950C2 (en) * | 2012-07-06 | 2014-04-10 | Общество с ограниченной ответственностью "Магнитные и криоэлектронные системы" (ООО "МаКриЭл системс") | Method for biocompatible polymeric structure formation |
| CN103551145B (en) * | 2013-07-22 | 2015-08-26 | 西安交通大学 | A kind of preparation method of Nano Silver/Graphene/P25 composite |
| CN107008330B (en) * | 2017-04-19 | 2019-06-21 | 河南农业大学 | Preparation method and application based on the NiCoB nanometer alloy catalyst for urging infiltration principle |
| CN107596436A (en) * | 2017-09-26 | 2018-01-19 | 天津大学 | A kind of DNA fluorescence hydrogel and preparation method thereof |
| CN109553728B (en) * | 2018-11-06 | 2021-06-08 | 安庆北化大科技园有限公司 | Preparation method and application of water-soluble self-initiated nanogel |
| CN109876782A (en) * | 2019-01-23 | 2019-06-14 | 河南师范大学 | A kind of aqueous phase preparation method of kitasamycin tartrate molecular imprinted polymer on surface and its application |
| CN112079960B (en) * | 2020-08-10 | 2021-10-29 | 西北大学 | Flexible hydrogel based on orthogonal photochemical reaction and preparation method thereof |
| CN112846224A (en) * | 2021-01-04 | 2021-05-28 | 董荣雪 | Nano porous metal material and preparation method and application thereof |
| CN112718004A (en) * | 2021-01-18 | 2021-04-30 | 西京学院 | Nano catalyst Cu2O/p (SBMA) and methods and uses |
| CN113736100B (en) * | 2021-08-12 | 2023-04-14 | 湖南工业大学 | Nano metal organic framework toughened high-strength fluorescent hydrogel and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3997472A (en) * | 1974-11-11 | 1976-12-14 | Polymeric Enzymes, Inc. | Novel catalyst systems and methods of preparation |
| US6534033B1 (en) * | 2000-01-07 | 2003-03-18 | Millennium Cell, Inc. | System for hydrogen generation |
-
2011
- 2011-09-15 WO PCT/IB2011/054033 patent/WO2012035507A2/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012035507A3 (en) | 2012-06-28 |
| WO2012035507A2 (en) | 2012-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2012035507A9 (en) | Production method of hydrogel-metal composite | |
| Sahiner et al. | Superabsorbent hydrogels for cobalt nanoparticle synthesis and hydrogen production from hydrolysis of sodium boron hydride | |
| Zhang et al. | Highly efficient and selective removal of trace lead from aqueous solutions by hollow mesoporous silica loaded with molecularly imprinted polymers | |
| Kamal et al. | Nickel nanoparticles-chitosan composite coated cellulose filter paper: an efficient and easily recoverable dip-catalyst for pollutants degradation | |
| Ozay et al. | Hydrogen production from ammonia borane via hydrogel template synthesized Cu, Ni, Co composites | |
| Ajmal et al. | Simultaneous catalytic degradation/reduction of multiple organic compounds by modifiable p (methacrylic acid-co-acrylonitrile)–M (M: Cu, Co) microgel catalyst composites | |
| Dinu et al. | Chitosan-based ion-imprinted cryo-composites with excellent selectivity for copper ions | |
| Han et al. | Ag-nanoparticle-loaded mesoporous silica: spontaneous formation of Ag nanoparticles and mesoporous silica SBA-15 by a one-pot strategy and their catalytic applications | |
| CN102335628B (en) | Load-type nanometer duplex metal composite catalyst and preparation method thereof | |
| Ai et al. | Environmentally friendly light-driven synthesis of Ag nanoparticles in situ grown on magnetically separable biohydrogels as highly active and recyclable catalysts for 4-nitrophenol reduction | |
| Ali et al. | Enhanced H2 generation from NaBH4 hydrolysis and methanolysis by cellulose micro-fibrous cottons as metal templated catalyst | |
| Zhang et al. | Silver nanoparticles grown on the surface of PAN nanofiber: Preparation, characterization and catalytic performance | |
| Corain et al. | Generating palladium nanoclusters inside functional cross-linked polymer frameworks | |
| Gao et al. | Alginate and polyethyleneimine dually mediated synthesis of nanosilver-containing composites for efficient p-nitrophenol reduction | |
| Khan et al. | Metal nanoparticles supported on polyacrylamide water beads as catalyst for efficient generation of H2 from NaBH4 methanolysis | |
| Su et al. | Magnetic hydrogel derived from wheat straw cellulose/feather protein in ionic liquids as copper nanoparticles carrier for catalytic reduction | |
| Bashir et al. | Highly uniform and porous polyurea microspheres: clean and easy preparation by interface polymerization, palladium incorporation, and high catalytic performance for dye degradation | |
| Gao et al. | Enhanced catalytic activity of nanosilver with lignin/polyacrylamide hydrogel for reducing p-nitrophenol | |
| Gao et al. | Highly efficient and stable catalysis of p-nitrophenol via silver/lignin/polyacrylic acid hydrogel | |
| Liu et al. | Selective capture of toxic anionic dyes of a novel prepared DMDAAC-grafted chitosan/genipin/cellulose hydrogel beads with antibacterial activity | |
| Wu et al. | Macrosphere-supported nanoscale Prussian blue analogues prepared via self-assembly as multi-functional heterogeneous catalysts for aqueous oxidative and reductive reactions | |
| Jabeen et al. | Synthesis and characterization of cobalt nanoparticles containing anionic polymer hydrogel nanocomposite catalysts for fast reduction of nitrocompounds in water | |
| Zheng et al. | A crescent-shaped imprinted microgel adsorbent with near-infrared light-responsive performance for selective adsorption of Lead (II) | |
| CN102847555B (en) | Polymer supported Pd-Ni-B nano-catalyst, preparation method and application thereof | |
| Yang et al. | Epichlorohydrin and triethylenetetramine functionalized electrosprayed Fe3O4/Chitosan magnetic microspheres for removal and separation of Congo red |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11776868 Country of ref document: EP Kind code of ref document: A2 |
|
| WWE | Wipo information: entry into national phase |
Ref document number: 2013/03162 Country of ref document: TR |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 11776868 Country of ref document: EP Kind code of ref document: A2 |