WO2010115199A1 - Microwave-assisted synthesis of transition metal phosphide - Google Patents
Microwave-assisted synthesis of transition metal phosphide Download PDFInfo
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- WO2010115199A1 WO2010115199A1 PCT/US2010/029978 US2010029978W WO2010115199A1 WO 2010115199 A1 WO2010115199 A1 WO 2010115199A1 US 2010029978 W US2010029978 W US 2010029978W WO 2010115199 A1 WO2010115199 A1 WO 2010115199A1
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- WIPO (PCT)
- Prior art keywords
- transition metal
- mixture
- salt
- lignin
- microwave radiation
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- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 100
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 75
- 238000007144 microwave assisted synthesis reaction Methods 0.000 title description 5
- 238000000034 method Methods 0.000 claims abstract description 87
- 239000000203 mixture Substances 0.000 claims abstract description 49
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 32
- 230000005855 radiation Effects 0.000 claims abstract description 26
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 21
- 229920001732 Lignosulfonate Polymers 0.000 claims abstract description 16
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 229920005610 lignin Polymers 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- -1 transition metal salt Chemical class 0.000 claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 150000003839 salts Chemical class 0.000 claims description 19
- 239000002077 nanosphere Substances 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229910052733 gallium Inorganic materials 0.000 claims description 8
- 229910052738 indium Inorganic materials 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 229920005551 calcium lignosulfonate Polymers 0.000 claims description 4
- RYAGRZNBULDMBW-UHFFFAOYSA-L calcium;3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Ca+2].COC1=CC=CC(CC(CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O RYAGRZNBULDMBW-UHFFFAOYSA-L 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 229910021381 transition metal chloride Inorganic materials 0.000 claims description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052785 arsenic Inorganic materials 0.000 claims description 3
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 229910052798 chalcogen Inorganic materials 0.000 claims description 3
- 150000001787 chalcogens Chemical class 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052696 pnictogen Inorganic materials 0.000 claims description 3
- 150000003063 pnictogens Chemical class 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 239000011669 selenium Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 229910052714 tellurium Inorganic materials 0.000 claims description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910000385 transition metal sulfate Inorganic materials 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 2
- 229910000319 transition metal phosphate Inorganic materials 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 38
- 230000015572 biosynthetic process Effects 0.000 description 18
- 239000000523 sample Substances 0.000 description 17
- 230000008569 process Effects 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- 239000002105 nanoparticle Substances 0.000 description 12
- 235000011007 phosphoric acid Nutrition 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 239000010949 copper Substances 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 7
- 238000001069 Raman spectroscopy Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 238000001237 Raman spectrum Methods 0.000 description 6
- 239000002041 carbon nanotube Substances 0.000 description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000012467 final product Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- ZMWAXVAETNTVAT-UHFFFAOYSA-N 7-n,8-n,5-triphenylphenazin-5-ium-2,3,7,8-tetramine;chloride Chemical compound [Cl-].C=1C=CC=CC=1NC=1C=C2[N+](C=3C=CC=CC=3)=C3C=C(N)C(N)=CC3=NC2=CC=1NC1=CC=CC=C1 ZMWAXVAETNTVAT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- 239000010426 asphalt Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 229910000159 nickel phosphate Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229920001864 tannin Polymers 0.000 description 2
- 235000018553 tannin Nutrition 0.000 description 2
- 239000001648 tannin Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 101100116420 Aedes aegypti DEFC gene Proteins 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- 229910005911 NiSO4-6H2O Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 238000000333 X-ray scattering Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000002717 carbon nanostructure Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 238000010961 commercial manufacture process Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000011896 sensitive detection Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 230000000391 smoking effect Effects 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/187—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- 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
-
- 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
- B01J37/02—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
- B01J37/08—Heat treatment
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/04—Hydrides of silicon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/08—Compounds containing halogen
- C01B33/107—Halogenated silanes
- C01B33/1071—Tetrachloride, trichlorosilane or silicochloroform, dichlorosilane, monochlorosilane or mixtures thereof
Definitions
- the present invention relates generally to a method or process of synthesizing transition metal phosphides, and more particularly to a microwave-assisted method or process of synthesizing transition metal phosphides, and applications of same.
- Transition metal phosphides belong to an important and exciting class of materials with a wide range of emerging applications.
- One of the applications that have attracted a lot of attention recently is in the petroleum industry.
- the hydroprocessing of crude oil containing S and N is of paramount importance to the gas and oil industry. This will play an ever increasing importance in the future due to declining quality of oil produced as well as stricter laws mandating reduced level in gasoline and diesel.
- S-Mo-NiZAl 2 Os has been used in hydrodenitrogenation and hydrodesulfurization of petroleum feedstocks.
- researchers have shown that transition metal phosphides are very active catalysts in hydroprocessing.
- Nickel phosphide, Ni 2 P, on silica support has been shown to exhibit excellent performance characteristics in both hydrodenitrogenation (HDN) as well as hydrodesulfurization (HDS) with activities greater than commercially available mixed transition metal Ni-Mo-SZAl 2 Os catalyst.
- HDN hydrodenitrogenation
- HDS hydrodesulfurization
- 3 A comparison of the different synthetic procedures for transition metal phosphide synthesis, indicates that most are tedious that use highly reactive and expensive precursors, use electrolytic reduction or H 2 gas for the transformation.
- Prior techniques have included the combination of the elements under extreme temperature and pressure, reaction of metal chloride with phosphine gas, decomposition of complex organometallics, electrolysis and reduction of phosphate with gaseous hydrogen. 1
- Xie et.al 5 have reported the synthesis of irregular Nickel phosphide nanocrystals containing Ni, M3P, NisP 2 and Ni] 2 Ps by a milder route using NiCl 2 and sodium hypophosphite as reactants at 190 0 C. The product after reflux was washed with ammonia and ethanol. Copper phosphide hollow spheres have been synthesized in ethylene glycol by a solvothermal process using copper hydroxide and elemental phosphorus as starting material using an autoclave at 200 C for 15 hours. Nevertheless, it is believed that the existing techniques are neither economically attractive nor quick or safe, for large scale commercial manufacture in an industrial setting.
- the present invention provides a method of synthesizing transition metal phosphide.
- the method has the steps of: preparing a transition metal lignosulfonate; mixing the transition metal lignosulfonate with phosphoric acid to form a mixture; and subjecting the mixture to a microwave radiation for a duration of time effective to obtain a transition metal phosphide.
- the preparing step comprises the step of heating a mixture of calcium lignosulfonate and a transition metal sulfate to a first temperature to obtain the transition metal lignosulfonate.
- the first temperature is about 90 0 C.
- the transition metal comprises one of Ni, Cu, Mn, Fe, In, Ga, and Mo.
- the frequency of the microwave radiation is about 2.45 GHz.
- the transition metal phosphide is formed in the form of nano- spheres.
- the average size of the nano-spheres is less than 100 nm.
- the transition metal phosphide is formed in in the form of nano-spheres and nano-sticks, respectively.
- the present invention provides an article of manufacture made by the method set forth immediately above.
- the present invention provides a method of synthesizing transition metal phosphide.
- the method has the steps of: preparing a mixture comprising a salt of lignin, a transition metal salt, phosphoric acid, silica, and carbon black; and subjecting the mixture to a microwave radiation for a duration of time effective to obtain a transition metal phosphide.
- the present invention provides an article of manufacture made by the method set forth immediately above.
- the present invention provides a method of synthesizing transition metal phosphide.
- the method has the steps of: preparing a mixture comprising a salt of lignin, a transition metal salt, and phosphoric acid; and subjecting the mixture to a microwave radiation for a duration of time effective to obtain a transition metal phosphide.
- the present invention provides an article of manufacture made by the method set forth immediately above.
- the present invention provides a method of synthesizing transition metal phosphide.
- the method has the steps of: preparing a mixture comprising a salt of lignin, a transition metal salt, and a compound containing a pnictogen selected from the group consisting of nitrogen, phosphorus, arsenic, antimony, and bismuth; and subjecting the mixture to a microwave radiation for a duration of time effective to obtain a transition metal pnictide.
- the present invention provides a method of synthesizing transition metal chalcogenide.
- the method has the steps of: preparing a mixture comprising a salt of lignin, a transition metal salt, and a compound containing a chalcogen selected from the group consisting of oxygen, sulfur, selenium, and tellurium; and subjecting the mixture to a microwave radiation for a duration of time effective to obtain a transition metal chalcogenide.
- the present invention provides a method of synthesizing transition metal tetrilide.
- the method has the steps of: preparing a mixture comprising a salt of lignin, a transition metal salt, and a compound containing an element selected from the group consisting of carbon, silicon, germanium, tin, and lead; and subjecting the mixture to a microwave radiation for a duration of time effective to obtain a transition metal tetrilide.
- Fig. 1 shows an XRD spectrum OfNi 2 P synthesized according to one embodiment of the present invention.
- Fig. 2 shows SEM images OfNi 2 P synthesized according to one embodiment of the present invention.
- Fig. 3 shows an XRD spectrum OfNi 2 P synthesized in presence of silica according to one embodiment of the present invention.
- Fig. 4 shows SEM image, an EDX spectrum OfNi 2 P and corresponding data for copper phosphide synthesized according to one embodiment of the present invention.
- SEM scanning electron microscope
- X-ray diffraction refers to one of X-ray scattering techniques that are a family of non-destructive analytical techniques which reveal information about the crystallographic structure, chemical composition, and physical properties of materials and thin films. These techniques are based on observing the scattered intensity of an X-ray beam hitting a sample as a function of incident and scattered angle, polarization, and wavelength or energy. In particular, X-ray diffraction finds the geometry or shape of a molecule, compound, or material using X-rays. X-ray diffraction techniques are based on the elastic scattering of X-rays from structures that have long range order.
- the term "Raman spectroscopy” or “Raman techniue” refers to an optical technique that probes the specific molecular content of a sample by collecting in- elastically scattered light. As photons propagate through a medium, they undergo both absorptive and scattering events. In absorption, the energy of the photons is completely transferred to the material, allowing either heat transfer (internal conversion) or re- emission phenomena such as fluorescence and phosphorescence to occur. Scattering, however, is normally an in-elastic process, in which the incident photons retain their energy.
- Raman scattering the photons either donate or acquire energy from the medium, on a molecular level.
- fluorescence where the energy transfers are on the order of the electronic bandgaps
- the energy transfers associated with Raman scattering are on the order of the vibrational modes of the molecule. These vibrational modes are molecularly specific, giving every molecule a unique Raman spectral signature.
- Raman scattering is a very weak phenomena, and therefore practical measurement of Raman spectra of a medium requires high power excitation laser sources and extremely sensitive detection hardware. Even with these components, the Raman spectra from tissue are masked by the relatively intense tissue auto-fluorescence. After detection, post processing techniques are required to subtract the fluorescent background and enable accurate visualization of the Raman spectra.
- Raman spectra are plotted as a function of frequency shift in units of wavenumber (cm " ).
- the region of the Raman spectra where most biological molecules have Raman peaks is from 500 to 2000 cm 1 .
- Raman spectra have sharp spectral features that enable easier identification of the constituent sources of spectral peaks in a complex sample.
- “nanoscopic-scale,” “nanoscopic,” “nanometer-scale,” “nanoscale,” “nanocomposites,” “nanoparticles,” the “nano-” prefix, and the like generally refers to elements or articles having widths or diameters of less than about 1 ⁇ m, preferably less than about 100 nm in some cases.
- specified widths can be smallest width (i.e. a width as specified where, at that location, the article can have a larger width in a different dimension), or largest width (i.e. where, at that location, the article's width is no wider than as specified, but can have a length that is greater).
- carbon nanostructures refer to carbon fibers or carbon nanotubes that have a diameter of 1 ⁇ m or smaller which is finer than that of carbon fibers.
- carbon nanotubes the material whose carbon faces with hexagon meshes are almost parallel to the axis of the corresponding carbon tube is called a carbon nanotube, and even a variant of the carbon nanotube, around which amorphous carbon exists, is included in the carbon nanotube.
- plural means two or more.
- the present invention provides, among other things, a process to prepare transition metal phosphides by microwaving phosphates in presence of lignin with carbon black optionally present in the mixture.
- the process is quick and yields pure well defined compounds in terms of composition.
- the process may yield carbon composites containing transition metal phosphides or pure transition metal phosphides depending on the reaction time.
- the synthesis OfNi 2 P nanospheres, Ni 2 P on silica support, and Cu 3 P on carbon support was successfully performed by a completely novel method that obviates the use of expensive exotic or toxic chemicals and is safe, quick and inexpensive.
- the present invention provides a method of synthesizing transition metal phosphide.
- the method has the steps of: preparing a transition metal lignosulfonate; mixing the transition metal lignosulfonate with phosphoric acid to form a mixture; and subjecting the mixture to a microwave radiation for a duration of time effective to obtain a transition metal phosphide.
- the preparing step comprises the step of heating a mixture of calcium lignosulfonate and a transition metal sulfate to a first temperature to obtain the transition metal lignosulfonate.
- the first temperature is about 90°C.
- the transition metal comprises one of Ni, Cu, Mn, Fe, In, Ga, and Mo.
- the frequency of the microwave radiation is about 2.45 GHz.
- the transition metal phosphide is formed in the form of nano- spheres. The average size of the nano-spheres is less than 100 nm.
- the transition metal phosphide is formed in in the form of nano-spheres and nano-sticks, respectively.
- the present invention provides an article of manufacture made by the method set forth immediately above.
- the present invention provides a method of synthesizing transition metal phosphide.
- the method has the steps of: preparing a mixture comprising a salt of lignin, a transition metal salt, phosphoric acid, silica, and carbon black; and subjecting the mixture to a microwave radiation for a duration of time effective to obtain a transition metal phosphide.
- the salt of lignin comprises sodium salt of lignin.
- the transition metal salt comprises transition metal chloride.
- the transition metal comprises one of Ni, Cu, Mn, Fe, In, Ga, and Mo.
- the frequency of the microwave radiation is about 2.45 GHz.
- the transition metal phosphate coexists with carbon to form a carbon composite.
- the present invention provides an article of manufacture made by the method set forth immediately above.
- the present invention provides a method of synthesizing transition metal phosphide.
- the method has the steps of: preparing a mixture comprising a salt of lignin, a transition metal salt, and phosphoric acid; and subjecting the mixture to a microwave radiation for a duration of time effective to obtain a transition metal phosphide.
- the salt of lignin comprises sodium salt of lignin.
- the transition metal salt comprises a transition metal chloride.
- the transition metal comprises one of Ni, Cu, Mn, Fe, In, Ga, and Mo.
- the frequency of the microwave radiation is about 2.45 GHz.
- the transition metal phosphide is formed in the form of nano- spheres.
- the present invention provides an article of manufacture made by the method set forth immediately above.
- the present invention provides a method of synthesizing transition metal phosphide.
- the method has the steps of: preparing a mixture comprising a salt of lignin, a transition metal salt, and a compound containing a pnictogen selected from the group consisting of nitrogen, phosphorus, arsenic, antimony, and bismuth; and subjecting the mixture to a microwave radiation for a duration of time effective to obtain a transition metal pnictide.
- the present invention provides a method of synthesizing transition metal chalcogenide.
- the method has the steps of: preparing a mixture comprising a salt of lignin, a transition metal salt, and a compound containing a chalcogen selected from the group consisting of oxygen, sulfur, selenium, and tellurium; and subjecting the mixture to a microwave radiation for a duration of time effective to obtain a transition metal chalcogenide.
- the present invention provides a method of synthesizing transition metal tetrilide.
- the method has the steps of: preparing a mixture comprising a salt of lignin, a transition metal salt, and a compound containing an element selected from the group consisting of carbon, silicon, germanium, tin, and lead; and subjecting the mixture to a microwave radiation for a duration of time effective to obtain a transition metal tetrilide.
- EXAMPLE 1 Synthesis ofN ⁇ 2P nanoparticles .
- a process for synthesis OfNi 2 P nanoparticles was performed successfully.
- calcium lignosulfonate (BCA) was obtained from Lignotech, Inc.
- a 1Og sample of Borresperse CA containing 5% Ca + (0.5g, 0.0125 moles) was dissolved in 4OmL H 2 O and heated to 9O 0 C.
- 3.29g of NiSO 4 -6H 2 O (0.0125 moles) was added and stirred for 60 minutes at 9O 0 C.
- the solution was then filtered to remove the CaSO 4 formed through a coarse filter paper (Whatman 4) using vacuum suction.
- the filtrate was then evaporated to dryness by placing the beaker containing Nickel lignosulfonate solution on a hot plate at 70 0 C under the hood. Yield of Nickel lignosulfonate was 10.08g, which was about 87% yield.
- Synthesis ofNi2P nanoparticles on silica support In one embodiment of the present invention, a process for synthesis OfNi 2 P nanoparticles on silica support was performed successfully. In doing so, a Ig sample of Indulin C (Meadwestvaco) was mixed with 0.297g of NiCl 2 .6H 2 O in a mortar and pestle. Then 8 drops of concentrated phosphoric acid (H3PO4, 85%) was added and thoroughly mixed using the mortar and pestle. Then 0.7g of silica gel (Aldrich Chemical Co.) was added and mixed thoroughly. Finally, 0.05g of carbon black (Superior Graphite) was added and mixed.
- Synthesis ofCu ⁇ P nanoparticles In one embodiment of the present invention, a process for synthesis Of Cu 3 P nanoparticles was performed successfully. In doing so, a Ig sample of Indulin C (Meadwestvaco) was mixed with 0.426g of CuQ 2 .2H 2 O (2.5 mmoles) thoroughly in a mortar and pestle. Then 8 drops of concentrated phosphoric acid (H3PO4, 85%) was added and thoroughly mixed with the mortar and pestle. The mixture was micro waved in a Pyrex test tube for a total of 16 minutes in a microwave oven placed under a hood operating at 2.45GHz, IKW power. During the microwave process the mixture started smoking after about 1 minute.
- the reaction mixture started sparkling in about 3 mninutes and then turned red hot. Towards the end no smoke or sparkling was observed.
- the material was cooled, powdered and boiled in 100 mL water. It was filtered and washed with 100 mL water. It was then dried in vacuum and weighed, which yielded 0.44g final product.
- Ni 2 P is formed according to various embodiments of the present invention by the carbothermal reduction of nickel phosphate. It is believed that Ni 2+ lignosulfonate decompose to yield SO 3 , lignin and elemental Ni. There is evidence that Ni 0 is formed, as microwaving Nickel lignosulfonate (with graphite initiator) shows elemental Ni in XPvD (data not shown). It has been shown that the principal pyrolysis gases from lignin are CO, CH4, CO 2 and H 2 . Thus, in theory, it may be proposed that lignin degradation could be a source of hydrogen gas which could reduce Nickel ion to elemental Nickel. Nickel may then react with H 2 , CO, CH 4 or CO +H 2 (all being gases). The overall reaction to explain the transformation taking place in the microwave assisted reaction may be summarized in the possible reactions as follows:
- the fold seen in the middle of the image is probably due to the tape that is used to support the sample.
- Fig. 3 shows the XRD spectrum OfNi 2 P prepared in the presence of silica as produced in EXAMPLE 2. It can be seen that all the peaks expected from Ni 2 P is present in the sample. In addition, the characteristic peak for carbon is also evident. The remaining peaks are due to silica. No other peaks are evident indicating that SiO 2 remains unaffected under the reaction conditions.
- the SEM of the sample as produced in EXAMPLE 2, as shown in Fig.4, shows images of cuprous phosphide made by the process set forth above according to one embodiment of the present invention.
- the EDX of the region shown on the left is shown on the right. It can be seen from the Table in Fig. 4 corresponding to the EDX data that there are three copper atoms to every phosphorus atom.
- the nanoparticles obtained may be described as being comprised of nanospheres decorated with needles.
- the present invention provides novel methods for synthesis OfNi 2 P nanoparticles using a Nickel salt containing a carbon source and H 3 PO 4 .
- the process is inexpensive, easily scalable and quick. It is especially suitable for industrial setting where safety, expense and time is of essence.
- the method also lends itself for synthesis of other transition metal tetrilides, pnictides and chalcogenides.
- transition metals such as Ni, Cu, Mn, Fe, In, Ga, and Mo can be utilized to practice the present invention.
- the resultant different transition metal phophides that can be made according to various embodiments of the present invention can find many applications, some of which are listed in the following Table 1 :
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Abstract
A method of synthesizing transition metal phosphide. In one embodiment, the method has the steps of preparing a transition metal lignosulfonate, mixing the transition metal lignosulfonate with phosphoric acid to form a mixture, and subjecting the mixture to a microwave radiation for a duration of time effective to obtain a transition metal phosphide.
Description
MICROWAVE-ASSISTED SYNTHESIS OF TRANSITION METAL
PHOSPHIDE
This application is being filed as PCT International Patent application in the name of Board of Trustees of the University of Arkansas, a U.S. national corporation, Applicant for all countries except the U.S., and Tito Viswanathan, a U.S. resident, Applicant for the designation of the U.S. only, on April 5, 2010.
STATEMENT OF FEDERALLY-SPONSORED RESEARCH
The present invention was made with Government support under Grant Nos. 08- EPSC0R-009-REU and DEFC 36-06G086072, awarded by National Science Foundation (NSF-EPSCOR SURF) and U.S. Department of Energy (DOE), respectively. The government has certain rights in the invention.
CROSS-REFERENCE TO RELATED PATENT APPLICATION
This application claims the benefit, pursuant to 35 U. S. C. §119(e), of U.S. provisional patent application Serial No. 61/211,807, filed April 3, 2009, entitled "Novel Microwave Assisted Synthesis of Transition Metal Phosphide Nanoparticles ," by Tito Viswanathan, which is incorporated herein by reference in its entirety.
This application also is a continuation-in-part of U.S. patent application Serial No. 12/487,323, filed on June 18, 2009, entitled "Microwave- Assisted Synthesis Of Carbon And Carbon-Metal Composites From Lignin, Tannin And Asphalt Derivatives And Applications Of Same" by Tito Viswanathan, which is incorporated herein by reference in its entirety and itself claims the benefit, pursuant to 35 U. S. C. §119(e), of U.S. provisional patent application Serial No. 61/132,380, filed June 18, 2008, entitled "Microwave-Assisted Synthesis Of Carbon And Carbon-Metal Composites From Lingin, Tannin And Asphalt Derivatives " by Tito Viswanathan, which is incorporated herein by reference in its entirety.
Some references, which may include patents, patent applications and various
publications, are cited in a reference list and discussed in the description of this invention. The citation and/or discussion of such references is provided merely to clarify the description of the present invention and is not an admission that any such reference is "prior art" to the invention described herein. All references, if any, listed, cited and/or discussed in this specification are incorporated herein by reference in their entireties and to the same extent as if each reference was individually incorporated by reference. In terms of notation, hereinafter, superscript "[ ]n" represents the nth reference cited in the reference list. For example, [ J1 represents the first reference cited in the reference list, namely, Oyama, S. Ted, Novel catalysts for advanced hydroprocessing : transition metal phosphides. Journal of Catalysis (2003), 216(1-2), 343-352.
FIELD OF THE INVENTION
The present invention relates generally to a method or process of synthesizing transition metal phosphides, and more particularly to a microwave-assisted method or process of synthesizing transition metal phosphides, and applications of same. BACKGROUND
Transition metal phosphides belong to an important and exciting class of materials with a wide range of emerging applications. One of the applications that have attracted a lot of attention recently is in the petroleum industry. The hydroprocessing of crude oil containing S and N is of paramount importance to the gas and oil industry. This will play an ever increasing importance in the future due to declining quality of oil produced as well as stricter laws mandating reduced level in gasoline and diesel. In view of keeping up with the imposed restrictions it is imperative that improved catalysts for accomplishing these goals be investigated. S-Mo-NiZAl2Os has been used in hydrodenitrogenation and hydrodesulfurization of petroleum feedstocks. Researchers have shown that transition metal phosphides are very active catalysts in hydroprocessing.1'2
Among these catalysts, Nickel phosphide, Ni2P, on silica support has been shown to exhibit excellent performance characteristics in both hydrodenitrogenation (HDN) as well as hydrodesulfurization (HDS) with activities greater than commercially available mixed transition metal Ni-Mo-SZAl2Os catalyst.2 The discovery OfNi2P as an outstanding catalyst for both HDN and HDS has attracted interest in the synthesis of nickel phosphides.3 A comparison of the different synthetic procedures for transition metal phosphide synthesis, indicates that most are tedious that use highly reactive and expensive precursors, use electrolytic reduction or H2 gas for the transformation. Prior techniques have included the combination of the elements under extreme temperature and pressure, reaction of metal chloride with phosphine gas, decomposition of complex organometallics, electrolysis and reduction of phosphate with gaseous hydrogen.1
A different method for controlled synthesis OfNi2P nanocrystals has been reported recently by Liu et al.4 The procedure involves reacting yellow phosphorous and Ni2Sθ4 in ethylene glycol: water solvent in an autoclave at 18O0C for 12 hours. The black solid product is filtered and washed with absolute ethanol, benzene and water. The XRD of the product showed that it was Ni2P and the morphology was dentritic as determined by SEM. The mechanism of the formation of the product was thought to involve the formation OfPH3 upon the reaction of P with water and with H3PO4. Once generated nickel ions were theorized to combine with PH3 to form Ni2P.
Xie et.al5 have reported the synthesis of irregular Nickel phosphide nanocrystals containing Ni, M3P, NisP2 and Ni]2Ps by a milder route using NiCl2 and sodium hypophosphite as reactants at 1900C. The product after reflux was washed with ammonia and ethanol. Copper phosphide hollow spheres have been synthesized in ethylene glycol by a solvothermal process using copper hydroxide and elemental phosphorus as starting material using an autoclave at 200 C for 15 hours.
Nevertheless, it is believed that the existing techniques are neither economically attractive nor quick or safe, for large scale commercial manufacture in an industrial setting.
Therefore, a heretofore unaddressed need exists in the art to address the aforementioned deficiencies and inadequacies.
SUMMARY OF THE INVENTION
In one aspect, the present invention provides a method of synthesizing transition metal phosphide. In one embodiment, the method has the steps of: preparing a transition metal lignosulfonate; mixing the transition metal lignosulfonate with phosphoric acid to form a mixture; and subjecting the mixture to a microwave radiation for a duration of time effective to obtain a transition metal phosphide.
In one embodiment, the preparing step comprises the step of heating a mixture of calcium lignosulfonate and a transition metal sulfate to a first temperature to obtain the transition metal lignosulfonate. The first temperature is about 900C.
The transition metal comprises one of Ni, Cu, Mn, Fe, In, Ga, and Mo.
In one embodiment, the frequency of the microwave radiation is about 2.45 GHz.
In one embodiment, the transition metal phosphide is formed in the form of nano- spheres. The average size of the nano-spheres is less than 100 nm.
In one embodiment, the transition metal phosphide is formed in in the form of nano-spheres and nano-sticks, respectively.
In another aspect, the present invention provides an article of manufacture made by the method set forth immediately above. In yet another aspect, the present invention provides a method of synthesizing transition metal phosphide. In one embodiment, the method has the steps of: preparing a mixture comprising a salt of lignin, a transition metal salt, phosphoric
acid, silica, and carbon black; and subjecting the mixture to a microwave radiation for a duration of time effective to obtain a transition metal phosphide.
In a further aspect, the present invention provides an article of manufacture made by the method set forth immediately above.
In yet a further aspect, the present invention provides a method of synthesizing transition metal phosphide. In one embodiment, the method has the steps of: preparing a mixture comprising a salt of lignin, a transition metal salt, and phosphoric acid; and subjecting the mixture to a microwave radiation for a duration of time effective to obtain a transition metal phosphide.
In a further aspect, the present invention provides an article of manufacture made by the method set forth immediately above.
In yet another aspect, the present invention provides a method of synthesizing transition metal phosphide. In one embodiment, the method has the steps of: preparing a mixture comprising a salt of lignin, a transition metal salt, and a compound containing a pnictogen selected from the group consisting of nitrogen, phosphorus, arsenic, antimony, and bismuth; and subjecting the mixture to a microwave radiation for a duration of time effective to obtain a transition metal pnictide.
In another aspect, the present invention provides a method of synthesizing transition metal chalcogenide. In one embodiment, the method has the steps of: preparing a mixture comprising a salt of lignin, a transition metal salt, and a compound containing a chalcogen selected from the group consisting of oxygen, sulfur, selenium, and tellurium; and subjecting the mixture to a microwave radiation for a duration of time effective to obtain a transition metal chalcogenide.
In yet another aspect, the present invention provides a method of synthesizing transition metal tetrilide. In one embodiment, the method has the steps of: preparing a mixture comprising a salt of lignin, a transition metal salt, and a compound containing an element selected from the group consisting of carbon, silicon, germanium, tin, and lead; and subjecting the mixture to a microwave radiation for a duration of time effective to obtain a transition metal tetrilide.
These and other aspects of the present invention will become apparent from the following description of the preferred embodiment taken in conjunction with the following drawings and their captions, although variations and modifications therein may be affected without departing from the spirit and scope of the novel concepts of the disclosure.
BRIEF DESCRIPTION OF THE DRAWINGS
The drawings described below are for illustration purposes only. The drawings are not intended to limit the scope of the present teachings in any way. The patent or application file may contain at least one drawing executed in color. If so, copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee.
Fig. 1 shows an XRD spectrum OfNi2P synthesized according to one embodiment of the present invention.
Fig. 2 shows SEM images OfNi2P synthesized according to one embodiment of the present invention.
Fig. 3 shows an XRD spectrum OfNi2P synthesized in presence of silica according to one embodiment of the present invention. Fig. 4 shows SEM image, an EDX spectrum OfNi2P and corresponding data for copper phosphide synthesized according to one embodiment of the present invention.
DETAILED DESCRIPTION
The present invention is more particularly described in the following examples that are intended as illustrative only since numerous modifications and variations therein will be apparent to those skilled in the art. Various embodiments of the invention are now described in detail. Referring to the drawings, Figs. 1-4, like numbers, if any, indicate like components throughout the views. As used in the description herein and throughout the claims that follow, the meaning of "a", "an", and "the" includes plural reference unless the context clearly dictates otherwise. Also, as used in the description herein and throughout the claims that follow, the meaning of "in" includes "in" and "on" unless the context clearly dictates otherwise. Moreover, titles or subtitles may be used in the specification for the convenience of a reader, which shall have no influence on the scope of the present invention. Additionally, some terms used in this specification are more specifically defined below.
DEFINITIONS The terms used in this specification generally have their ordinary meanings in the art, within the context of the invention, and in the specific context where each term is used. Certain terms that are used to describe the invention are discussed below, or elsewhere in the specification, to provide additional guidance to the practitioner regarding the description of the invention. For convenience, certain terms may be highlighted, for example using italics and/or quotation marks. The use of highlighting has no influence on the scope and meaning of a term; the scope and meaning of a term is the same, in the same context, whether or not it is highlighted. It will be appreciated that same thing can be said in more than one way. Consequently, alternative language and synonyms may be used for any one or more of the terms discussed herein, nor is any special significance to be placed upon whether or not a term is elaborated or discussed herein. Synonyms for certain terms are provided. A recital of one or more synonyms does not exclude the use
of other synonyms. The use of examples anywhere in this specification including examples of any terms discussed herein is illustrative only, and in no way limits the scope and meaning of the invention or of any exemplified term. Likewise, the invention is not limited to various embodiments given in this specification. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. In the case of conflict, the present document, including definitions will control.
As used herein, "around", "about" or "approximately" shall generally mean within 20 percent, preferably within 10 percent, and more preferably within 5 percent of a given value or range. Numerical quantities given herein are approximate, meaning that the term "around", "about" or "approximately" can be inferred if not expressly stated.
As used herein, the term "scanning electron microscope (SEM)" refers to a type of electron microscope that images the sample surface by scanning it with a high-energy beam of electrons in a raster scan pattern. The electrons interact with the atoms that make up the sample producing signals that contain information about the sample's surface topography, composition and other properties such as electrical conductivity.
As used herein, the term "X-ray diffraction (XRD)" refers to one of X-ray scattering techniques that are a family of non-destructive analytical techniques which reveal information about the crystallographic structure, chemical composition, and physical properties of materials and thin films. These techniques are based on observing the scattered intensity of an X-ray beam hitting a sample as a function of incident and scattered angle, polarization, and wavelength or energy. In particular, X-ray diffraction finds the geometry or shape of a molecule, compound, or material using X-rays. X-ray diffraction techniques are based on the elastic scattering of X-rays from structures that have long range order. The most comprehensive description of scattering from crystals is given by the dynamical theory of diffraction.
As used herein, the term "Raman spectroscopy" or "Raman techniue" refers to an optical technique that probes the specific molecular content of a sample by collecting in- elastically scattered light. As photons propagate through a medium, they undergo both absorptive and scattering events. In absorption, the energy of the photons is completely transferred to the material, allowing either heat transfer (internal conversion) or re- emission phenomena such as fluorescence and phosphorescence to occur. Scattering, however, is normally an in-elastic process, in which the incident photons retain their energy. In Raman scattering, the photons either donate or acquire energy from the medium, on a molecular level. In contrast to fluorescence, where the energy transfers are on the order of the electronic bandgaps, the energy transfers associated with Raman scattering are on the order of the vibrational modes of the molecule. These vibrational modes are molecularly specific, giving every molecule a unique Raman spectral signature. Raman scattering is a very weak phenomena, and therefore practical measurement of Raman spectra of a medium requires high power excitation laser sources and extremely sensitive detection hardware. Even with these components, the Raman spectra from tissue are masked by the relatively intense tissue auto-fluorescence. After detection, post processing techniques are required to subtract the fluorescent background and enable accurate visualization of the Raman spectra. Raman spectra are plotted as a function of frequency shift in units of wavenumber (cm" ). The region of the Raman spectra where most biological molecules have Raman peaks is from 500 to 2000 cm 1. In contrast to fluorescence spectra, Raman spectra have sharp spectral features that enable easier identification of the constituent sources of spectral peaks in a complex sample. As used herein, "nanoscopic-scale," "nanoscopic," "nanometer-scale," "nanoscale," "nanocomposites," "nanoparticles," the "nano-" prefix, and the like generally refers to elements or articles having widths or diameters of less than about 1 μm, preferably less than about 100 nm in some cases. In all embodiments, specified widths can be smallest width (i.e. a width as specified where, at that location, the article can have a larger width in a different dimension), or largest width (i.e. where, at that
location, the article's width is no wider than as specified, but can have a length that is greater).
As used herein, "carbon nanostructures" refer to carbon fibers or carbon nanotubes that have a diameter of 1 μm or smaller which is finer than that of carbon fibers. However, there is no particularly definite boundary between carbon fibers and carbon nanotubes. By a narrow definition, the material whose carbon faces with hexagon meshes are almost parallel to the axis of the corresponding carbon tube is called a carbon nanotube, and even a variant of the carbon nanotube, around which amorphous carbon exists, is included in the carbon nanotube. As used herein, "plurality" means two or more.
As used herein, the terms "comprising," "including," "carrying," "having," "containing," "involving," and the like are to be understood to be open-ended, i.e., to mean including but not limited to.
OVERVIEW OF THE INVENTION The present invention provides, among other things, a process to prepare transition metal phosphides by microwaving phosphates in presence of lignin with carbon black optionally present in the mixture. The process is quick and yields pure well defined compounds in terms of composition. The process may yield carbon composites containing transition metal phosphides or pure transition metal phosphides depending on the reaction time. In various embodiments of the present invention, the synthesis OfNi2P nanospheres, Ni2P on silica support, and Cu3P on carbon support was successfully performed by a completely novel method that obviates the use of expensive exotic or toxic chemicals and is safe, quick and inexpensive.
Thus, in one aspect, the present invention provides a method of synthesizing transition metal phosphide. In one embodiment, the method has the steps of: preparing a transition metal lignosulfonate;
mixing the transition metal lignosulfonate with phosphoric acid to form a mixture; and subjecting the mixture to a microwave radiation for a duration of time effective to obtain a transition metal phosphide. In one embodiment, the preparing step comprises the step of heating a mixture of calcium lignosulfonate and a transition metal sulfate to a first temperature to obtain the transition metal lignosulfonate. The first temperature is about 90°C.
The transition metal comprises one of Ni, Cu, Mn, Fe, In, Ga, and Mo.
In one embodiment, the frequency of the microwave radiation is about 2.45 GHz. In one embodiment, the transition metal phosphide is formed in the form of nano- spheres. The average size of the nano-spheres is less than 100 nm.
In one embodiment, the transition metal phosphide is formed in in the form of nano-spheres and nano-sticks, respectively.
In another aspect, the present invention provides an article of manufacture made by the method set forth immediately above.
In yet another aspect, the present invention provides a method of synthesizing transition metal phosphide. In one embodiment, the method has the steps of: preparing a mixture comprising a salt of lignin, a transition metal salt, phosphoric acid, silica, and carbon black; and subjecting the mixture to a microwave radiation for a duration of time effective to obtain a transition metal phosphide.
In one embodiment, the salt of lignin comprises sodium salt of lignin.
In one embodiment, the transition metal salt comprises transition metal chloride.
The transition metal comprises one of Ni, Cu, Mn, Fe, In, Ga, and Mo. In one embodiment, the frequency of the microwave radiation is about 2.45 GHz.
In one embodiment, the transition metal phosphate coexists with carbon to form a carbon composite.
In a further aspect, the present invention provides an article of manufacture made by the method set forth immediately above.
In yet a further aspect, the present invention provides a method of synthesizing transition metal phosphide. In one embodiment, the method has the steps of: preparing a mixture comprising a salt of lignin, a transition metal salt, and phosphoric acid; and subjecting the mixture to a microwave radiation for a duration of time effective to obtain a transition metal phosphide.
In one embodiment, the salt of lignin comprises sodium salt of lignin. In one embodiment, the transition metal salt comprises a transition metal chloride.
In one embodiment, the transition metal comprises one of Ni, Cu, Mn, Fe, In, Ga, and Mo.
In one embodiment, the frequency of the microwave radiation is about 2.45 GHz.
In one embodiment, the transition metal phosphide is formed in the form of nano- spheres.
In a further aspect, the present invention provides an article of manufacture made by the method set forth immediately above.
In yet another aspect, the present invention provides a method of synthesizing transition metal phosphide. In one embodiment, the method has the steps of: preparing a mixture comprising a salt of lignin, a transition metal salt, and a compound containing a pnictogen selected from the group consisting of nitrogen, phosphorus, arsenic, antimony, and bismuth; and subjecting the mixture to a microwave radiation for a duration of time effective to obtain a transition metal pnictide. In another aspect, the present invention provides a method of synthesizing transition metal chalcogenide. In one embodiment, the method has the steps of: preparing a mixture comprising a salt of lignin, a transition metal salt, and a compound containing a chalcogen selected from the group consisting of oxygen, sulfur,
selenium, and tellurium; and subjecting the mixture to a microwave radiation for a duration of time effective to obtain a transition metal chalcogenide.
In yet another aspect, the present invention provides a method of synthesizing transition metal tetrilide. In one embodiment, the method has the steps of: preparing a mixture comprising a salt of lignin, a transition metal salt, and a compound containing an element selected from the group consisting of carbon, silicon, germanium, tin, and lead; and subjecting the mixture to a microwave radiation for a duration of time effective to obtain a transition metal tetrilide.
Additional details are set forth below.
EXAMPLES
Without intent to limit the scope of the invention, exemplary methods and their related results according to the embodiments of the present invention are given below. Note again that titles or subtitles may be used in the examples for convenience of a reader, which in no way should limit the scope of the invention. Moreover, certain theories are proposed and disclosed herein; however, in no way they, whether they are right or wrong, should limit the scope of the invention.
EXAMPLE 1 Synthesis ofNΪ2P nanoparticles . In one embodiment of the present invention, a process for synthesis OfNi2P nanoparticles was performed successfully. In doing so, calcium lignosulfonate (BCA) was obtained from Lignotech, Inc. A 1Og sample of Borresperse CA containing 5% Ca + (0.5g, 0.0125 moles) was dissolved in 4OmL H2O and heated to 9O0C. Then 3.29g of NiSO4-6H2O (0.0125 moles) was added and stirred for 60 minutes at 9O0C. The solution was then filtered to remove the CaSO4 formed through a coarse filter paper (Whatman 4) using vacuum suction. The filtrate was then evaporated to
dryness by placing the beaker containing Nickel lignosulfonate solution on a hot plate at 700C under the hood. Yield of Nickel lignosulfonate was 10.08g, which was about 87% yield.
To 1.Og of the Nickel lignosulfonate, 4 drops of 85% H3PO4 was added and mixed thoroughly using a mortar and pestle. Then 2 additional drops of phosphoric acid was added without mixing and the mixture was microwaved in a SiO2 crucible in a microwave oven placed under a hood operating at 2.45GHz, IKW power. In a matter of 30 seconds there was sparkling, followed by a red glow and the process was continued for a total of 14 minutes. The resultant material was cooled, powdered and then suspended in 15mL OfH2O and boiled for 30 minutes. It was then filtered through suction and washed with additional 40OmL OfH2O. The final product, a collection of Ni2P nanoparticles, was dried and then weighed, which yielded 0.26g final product.
EXAMPLE 2
Synthesis ofNi2P nanoparticles on silica support. In one embodiment of the present invention, a process for synthesis OfNi2P nanoparticles on silica support was performed successfully. In doing so, a Ig sample of Indulin C (Meadwestvaco) was mixed with 0.297g of NiCl2.6H2O in a mortar and pestle. Then 8 drops of concentrated phosphoric acid (H3PO4, 85%) was added and thoroughly mixed using the mortar and pestle. Then 0.7g of silica gel (Aldrich Chemical Co.) was added and mixed thoroughly. Finally, 0.05g of carbon black (Superior Graphite) was added and mixed. The mixture was then microwaved in a microwave oven placed under a hood operating at 2.45GHz, IKW power for a total of 20 minutes. The resultant material was cooled , powdered and boiled in 100 mL water for 10 minutes. It was then filtered using a coarse filter paper using suction and washed with 200 mL water. It was finally dried under vacuum and weighed, which yielded 1.02g final product.
EXAMPLE 3
Synthesis ofCuϊP nanoparticles . In one embodiment of the present invention, a process for synthesis Of Cu3P nanoparticles was performed successfully. In doing so, a Ig sample of Indulin C (Meadwestvaco) was mixed with 0.426g of CuQ2.2H2O (2.5 mmoles) thoroughly in a mortar and pestle. Then 8 drops of concentrated phosphoric acid (H3PO4, 85%) was added and thoroughly mixed with the mortar and pestle. The mixture was micro waved in a Pyrex test tube for a total of 16 minutes in a microwave oven placed under a hood operating at 2.45GHz, IKW power. During the microwave process the mixture started smoking after about 1 minute. The reaction mixture started sparkling in about 3 mninutes and then turned red hot. Towards the end no smoke or sparkling was observed. The material was cooled, powdered and boiled in 100 mL water. It was filtered and washed with 100 mL water. It was then dried in vacuum and weighed, which yielded 0.44g final product.
EXAMPLE 4 Formation of Nickel phosphide . It is believed that Ni2P is formed according to various embodiments of the present invention by the carbothermal reduction of nickel phosphate. It is believed that Ni2+ lignosulfonate decompose to yield SO3, lignin and elemental Ni. There is evidence that Ni0 is formed, as microwaving Nickel lignosulfonate (with graphite initiator) shows elemental Ni in XPvD (data not shown). It has been shown that the principal pyrolysis gases from lignin are CO, CH4, CO2 and H2. Thus, in theory, it may be proposed that lignin degradation could be a source of hydrogen gas which could reduce Nickel ion to elemental Nickel. Nickel may then react with H2, CO, CH4 or CO +H2 (all being gases). The overall reaction to explain the transformation taking place in the microwave assisted reaction may be summarized in the possible reactions as follows:
4Ni + 2H3PO4 + 5H2^ 2Ni2P + 8H2O
or Ni3(PO4)2 + H2 -> Ni2P + H2O .
Other possible reactions theorized are:
4Ni + 2H3PO4 + 5CO^ 2Ni2P + 5CO2 + 3H2O
4Ni + 2H3PO4 + 5C^ 2Ni2P + 5CO + 3H2O
8Ni + 4H3PO4 + 5C^ 4Ni2P + 5CO2 + 6H2O
12Ni + 6H3PO4+ 8CO + 7H2^ 6Ni2P + 8CO2 + 16H2O
Ni + H3PO4 + CH4^ Ni2P + CO2 + H2O.
As shown in Fig. 1, the XRD spectrum of the sample as produced in EXAMPLE
1 indicates that pure Ni2P is produced. There is an exact match with Ni2P standard file with no other impurities. Surprisingly, it is not observed any carbon peaks (either crystalline or amorphous) in the XRD spectrum.
The SEM of the sample as produced in EXAMPLE 1, as shown in Fig. 2, shows that the morphology of the sample is in the form of nanospheres, with an average nanosphere size of <100nm. The fold seen in the middle of the image is probably due to the tape that is used to support the sample.
There is also evidence of nanosticks but there is strong reason to believe that they are also in fact Ni2P. Liu et.al. have observed the formation of such nanosticks projecting from nanospheres in the sample of Ni2P they prepared in an aqueous environment. They propose that aggregated nanoparticles form nanospheres after which the sticks decorate them. The sticks then propagate to give dendritic structures.
EXAMPLE 5
Formation ofNi2P on silica support. Fig. 3 shows the XRD spectrum OfNi2P prepared in the presence of silica as produced in EXAMPLE 2. It can be seen that all the peaks expected from Ni2P is present in the sample. In addition, the characteristic peak for carbon is also evident. The remaining peaks are due to silica. No other peaks are evident indicating that SiO2 remains unaffected under the reaction conditions.
The SEM of the sample as produced in EXAMPLE 2, as shown in Fig.4, shows images of cuprous phosphide made by the process set forth above according to one embodiment of the present invention. The EDX of the region shown on the left is shown on the right. It can be seen from the Table in Fig. 4 corresponding to the EDX data that there are three copper atoms to every phosphorus atom. The nanoparticles obtained may be described as being comprised of nanospheres decorated with needles.
Accordingly, among other things, the present invention provides novel methods for synthesis OfNi2P nanoparticles using a Nickel salt containing a carbon source and H3PO4. The process is inexpensive, easily scalable and quick. It is especially suitable for industrial setting where safety, expense and time is of essence. The method also lends itself for synthesis of other transition metal tetrilides, pnictides and chalcogenides. In particular, transition metals such as Ni, Cu, Mn, Fe, In, Ga, and Mo can be utilized to practice the present invention. The resultant different transition metal phophides that can be made according to various embodiments of the present invention can find many applications, some of which are listed in the following Table 1 :
Table 1. A few applications of metal phosphides
The foregoing description of the exemplary embodiments of the invention has been presented only for the purposes of illustration and description and is not intended to be exhaustive or to limit the invention to the precise forms disclosed. Many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to explain the principles of the invention and their practical application so as to enable others skilled in the art to utilize the invention and various embodiments and with various modifications as are suited to the particular use contemplated. Alternative embodiments will become apparent to those skilled in the art to which the present invention pertains without departing from its spirit and scope. Accordingly, the scope of the present invention is defined by the appended claims rather than the foregoing description and the exemplary embodiments described therein.
List of References:
1. Oyama, S. Ted. Novel catalysts for advanced hydroprocessing : transition metal phosphides. Journal of Catalysis (2003), 216(1-2), 343-352. 2. Oyama, S. T.; Wang, X.; Requejo, F. G.; Sato, T.; Yoshimura, Y.
Hydrodesulfurization of Petroleum Feedstocks with a New Type of Nonsulfϊde Hydrotreating Catalyst. Journal of Catalysis (2002), 209(1), 1-5.
3. Oyama, S. Ted; Lee, Yong-Kul. Mechanism of Hydrodenitrogenation on Phosphides and Sulfides. Journal of Physical Chemistry B (2005), 109(6), 2109- 2119.
4. Liu, Shuling; Liu, Xinzheng; Xu, Liqiang; Qian, Yitai; Ma, Xicheng. Controlled synthesis and characterization of nickel phosphide nanocrystal. Journal of Crystal Growth (2007), 304(2), 430-434.
5. Xie, Songhai; Qiao, Minghua; Zhou, Wuzong; Luo, Ge; He, Heyong; Fan, Kangnian; Zhao, Tiejun; Yuan, Weikang. Controlled synthesis , characterization , and crystallization of Ni - P nanospheres. Journal of Physical Chemistry B (2005), 109(51), 24361-24368.
6. Wang, Xinjun; Han, Kun; Gao, Youjun; Wan, Fuquan; Jiang, Kai. Fabrication of novel copper phosphide (CU3P) hollow spheres by a simple solvothermal method. Journal of Crystal Growth (2007), 307(1), 126-130.
Claims
1. A method of for synthesizing transition metal phosphide, comprising the steps of:
(a) preparing a transition metal lignosulfonate;
(b) mixing the transition metal lignosulfonate with phosphoric acid to form a mixture; and
(c) subjecting the mixture to a microwave radiation for a duration of time effective to obtain a transition metal phosphide.
2. The method of claim 1, wherein the preparing step comprises the step of heating a mixture of calcium lignosulfonate and a transition metal sulfate to a first temperature to obtain the transition metal lignosulfonate.
3. The method of claim 2, wherein the first temperature is about 900C.
4. The method of claim 2, wherein the transition metal comprises one of Ni, Cu, Mn, Fe, In, Ga, and Mo.
5. The method of claim 1 , wherein the frequency of the microwave radiation is about 2.45 GHz.
6. The method of claim 1 , wherein the transition metal phosphide is in the form of nano-spheres.
7. The method of claim 6, wherein the average size of the nano-spheres is less than 100 nm.
8. The method of claim 1 , wherein the transition metal phosphide is in the form of nano-spheres and nano-sticks.
9. An article of manufacture made by the method of claim 1.
10. A method of synthesizing transition metal phosphide, comprising the steps of: (a) preparing a mixture comprising a salt of lignin, a transition metal salt, phosphoric acid, silica, and carbon black; and (b) subjecting the mixture to a microwave radiation for a duration of time effective to obtain a transition metal phosphide.
11. The method of claim 10, wherein the salt of lignin comprises sodium salt of lignin.
12. The method of claim 10, wherein the transition metal salt comprises transition metal chloride.
13. The method of claim 10, wherein the transition metal comprises one of Ni, Cu, Mn, Fe, In, Ga, and Mo.
14. The method of claim 10, wherein the frequency of the microwave radiation is about 2.45 GHz.
15. The method of claim 10, wherein the transition metal phosphate coexists with carbon to form a carbon composite.
16. An article of manufacture made by the method of claim 10.
17. A method of synthesizing transition metal phosphide, comprising the steps of:
(a) preparing a mixture comprising a salt of lignin, a transition metal salt, and phosphoric acid; and
(b) subjecting the mixture to a microwave radiation for a duration of time effective to obtain a transition metal phosphide.
18. The method of claim 17, wherein the salt of lignin comprises sodium salt of lignin.
19. The method of claim 17, wherein the transition metal salt comprises a transition metal chloride.
20. The method of claim 17, wherein the transition metal comprises one of Ni, Cu, Mn, Fe, In, Ga, and Mo.
21. The method of claim 17, wherein the frequency of the microwave radiation is about 2.45 GHz.
22. The method of claim 17, wherein the transition metal phosphide is in the form of nano-spheres.
23. An article of manufacture made by the method of claim 17.
24. A method of synthesizing transition metal pnictide, comprising the steps of:
(a) preparing a mixture comprising a salt of lignin, a transition metal salt, and a compound containing a pnictogen selected from the group consisting of nitrogen, phosphorus, arsenic, antimony, and bismuth; and
(b) subjecting the mixture to a microwave radiation for a duration of time effective to obtain a transition metal pnictide.
25. A method of synthesizing transition metal chalcogenide, comprising the steps of:
(a) preparing a mixture comprising a salt of lignin, a transition metal salt, and a compound containing a chalcogen selected from the group consisting of oxygen, sulfur, selenium, and tellurium; and
(b) subjecting the mixture to a microwave radiation for a duration of time effective to obtain a transition metal chalcogenide.
26. A method of synthesizing transition metal tetrilide, comprising the steps of:
(a) preparing a mixture comprising a salt of lignin, a transition metal salt, and a compound containing an element selected from the group consisting of carbon, silicon, germanium, tin, and lead; and
(b) subjecting the mixture to a microwave radiation for a duration of time effective to obtain a transition metal tetrilide.
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CN102847548A (en) * | 2012-08-25 | 2013-01-02 | 东北石油大学 | Method for preparing hydrodesulfurization catalyst for oil product under mild condition |
CN112028043A (en) * | 2020-09-03 | 2020-12-04 | 中国科学院地球化学研究所 | Ni2Carbon thermal reduction preparation method of P, product and application |
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CN112028042A (en) * | 2020-09-03 | 2020-12-04 | 中国科学院地球化学研究所 | Carbon thermal reduction preparation method of CoP, product and application |
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