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WO2009065180A1 - Nanofeuilles d'oxyde métallique à dopage non métallique et leur procédé de production - Google Patents

Nanofeuilles d'oxyde métallique à dopage non métallique et leur procédé de production Download PDF

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WO2009065180A1
WO2009065180A1 PCT/AU2008/001728 AU2008001728W WO2009065180A1 WO 2009065180 A1 WO2009065180 A1 WO 2009065180A1 AU 2008001728 W AU2008001728 W AU 2008001728W WO 2009065180 A1 WO2009065180 A1 WO 2009065180A1
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metal
metal oxide
value greater
less
nanosheets
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Gao Qing Lu
Lianzhou Wang
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University of Queensland UQ
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University of Queensland UQ
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    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the present invention generally relates to nanosheets and a method of production thereof. More particularly, the invention relates to non-metal doped metal oxide nanosheets, their use and methods of production thereof.
  • titania nanosheets Exfoliated titania (Ti 0 . 9 i ⁇ 2 ) nanosheets have been extensively investigated due to their unique physicochemical properties and potential functionalities (Sasaki, T., et al. J. Am. Chem. Soc. 1996, 118, 8329-8335; Sasaki, T., et al. Chem. Mater. 1997, 9, 602-608; Sasaki, T. Watanabe, M. J. Am. Chem. Soc. 1998, 120, 4682-4689; and Tanaka, T.; et al. Chem. Mater.
  • Exfoliated Ti 0.9 iO 2 nanosheets generally have a lateral length of about several hundred nanometres and thickness of about 0.75 nm. These nearly two-dimensional nanosheets can be thought of as paper-like building blocks for the fabrication of a variety of nanostructures.
  • T ⁇ ' o .9 iO 2 nanosheets have been studied for applications in photocatalysis, photoelectrochemical water splitting, photodegradation and superhydrophilicity (Choy, J-H., et al. J. Mater. Chem. 2001 , 11 , 2232-2234; Choy, J-H., et al. Chem. Mater.
  • metal oxide nanosheets are ineffective as photocatalysts in the visible light range and/or are expensive to produce.
  • the invention provides a method of producing non-metal doped metal oxide nanosheets.
  • a method of producing non-metal doped metal oxide nanosheets including the steps of: a) doping a metal oxide precursor with a non-metal dopant to form a non- metal doped metal oxide; b) protonating the non-metal doped metal oxide to form a protonated non- metal doped metal oxide; and c) exfoliating the protonated non-metal doped metal oxide to form non- metal doped metal oxide nanosheets.
  • the metal oxide precursor is preferably a compound having the formula (I):
  • A is a cation selected from the group comprising lithium, sodium, potassium, rubidium, calcium, magnesium, caesium and francium; M is one or more metal ions selected from the group comprising titanium, lanthanium, niobium, tungsten, nickel, iron, cobalt, calcium, barium, zirconium, hafnium, molybdenum, chromium, tantalum and vanadium; n is a value greater than or equal to 0 and equal to or less than 8; and y and z are independently a value greater than 0 and equal to or less than 8.
  • the metal oxide precursor of formula (I) is Cs n TJyO 2 wherein n is a value greater than 0 and equal to or less than 8; y is a value greater than 0 and equal to or less than 8; and z is a value greater than 0 and equal to or less than 8.
  • the metal oxide precursor of formula (I) is Cso .68 Ti1 .83 O4.
  • the dopant may be any chemical, compound or composition which is capable of donating the appropriate dopant atoms to form a non-metal doped metal oxide.
  • the non-metal dopant may be an inorganic or organic compound, in solid, liquid or gaseous form.
  • the non-metal dopant when it is a gas it may be selected from one or more of the following: nitrogen, ammonia, methane, ethane, propane, butane, gas comprising B x H y , carbon monoxide, carbon dioxide, hydrogen sulphide or fluorine.
  • the non-metal dopant is a gas it is preferably supplied with an inert or non-reactive gas, such as air, argon, helium or hydrogen.
  • an inert or non-reactive gas such as air, argon, helium or hydrogen.
  • the dopant gas and the non-reactive gas are present in a 1 :1 volume ratio.
  • the non-metal dopant when it is an organic compound it may comprise one or more of the following: C 6 H 12 N 4 , CO(NH 2 ) 2 , CS(NH 2 ) 2 , triethylamine, (NH 4 ) 2 CO 3 , C 25 H 3 iN 3 , Ci 2 H 22 On, C ⁇ HsoOs, CeHi 2 , CeHi 2 O 2 , CeHi 2 BNOa, C 7 HsBF 4 O 2 , C 7 H 7 BO 4, H 3 N BH 3 , C 6 H 5 N(C 2 Hg) 2 BH 3 , CS(NH 2 ) 2 , C 7 H 7 SO 2 , C 7 Hi 2 O 2 S, C 6 H 4 S, C 4 CI 2 F 6 , C 4 H 2 F 2 N 2 , C 4 H 8 BrF, C 4 H 9 I, C 5 H 3 IO 2 , C 5 H 3 FI, C 6 H 13 I.
  • the dopant also may be selected from one or more inorganic compounds or solutions including carbon, boron, H 3 BO 3 , sulphur, (NH 4 ) 2 S, iodine, HIO 3 , HIO 4 , NH 4 I 1 Or NH 4 IO 3 .
  • the metal oxide precursor is doped with the non-metal dopant by calcining the metal oxide precursor in contact with the non-metal dopant.
  • the doping step is preferably carried out in the presence of one or more non- reactive or inert gases, selected from the group comprising, for example, oxygen, hydrogen, argon, helium, and air.
  • the metal oxide precursor is calcined with the non-metal dopant at a temperature of between 200 0 C to 1800 0 C for a period of between 30 minutes and 5 days.
  • the metal oxide precursor is calcined in contact with the non- metal dopant at a temperature of between 600 0 C and 1000 0 C for a period of between 30 minutes and 3 days.
  • the metal oxide precursor may be calcined in contact with the non-metal dopant at a temperature of about 700 0 C for a period of about 60 minutes.
  • the non-metal doped metal oxide formed using the method preferably has a formula (II):
  • A is a cation selected from the group comprising lithium, sodium, potassium, rubidium, calcium, magnesium, caesium and francium;
  • M is one or more metal ions selected from the group comprising titanium, lanthanium, niobium, tungsten, nickel, iron, cobalt, calcium, barium, zirconium, hafnium, molybdenum, chromium, tantalum and vanadium;
  • D is a non-metal dopant selected from the group comprising boron, carbon, nitrogen, fluorine, sulphur, phosphorus and iodine;
  • n is a value greater than or equal to 0 and equal to or less than 8;
  • x is a value greater than 0 and less than 8;
  • y and z are independently a value greater than 0 and equal to or less than 8; and
  • z-x is a value greater than 0.
  • the non-metal doped metal oxide of formula (II) is Cs n TiyO z-x D x , wherein n is a value greater than 0 and equal to or less than 8; x is a value greater than 0 and less than 8; y is a value greater than 0 and equal to or less than 8; z is a value greater than 0 and equal to or less than 8; and z-x is a value greater than 0.
  • the non-metal doped metal oxide of formula (II) is Cso. 6 ⁇ Tii . 83 O 4-X N x , wherein x is a value greater than 0 and less than 4.
  • the protonated non-metal doped metal oxide produced in the method preferably has a formula (III):
  • A is a cation selected from the group comprising lithium, sodium, potassium, rubidium, caesium and francium;
  • M is one or more metal ions selected from the group comprising titanium, lanthanium, niobium, tungsten, nickel, iron, cobalt calcium, barium, zirconium, hafnium, molybdenum, chromium, tantalum and vanadium;
  • D is a non-metal dopant selected from the group comprising boron, carbon, nitrogen, fluorine, sulphur, phosphorus and iodine;
  • m, y, and z are independently a value greater than 0 and equal to or less than 8;
  • n is a value either equal to m or greater than m and a value which is greater than 0 and less than or equal to 8;
  • x is a value greater than 0 and less and 8; and
  • z-x is a value greater than 0 and less than 8.
  • the protonated non-metal doped metal oxide of formula (III) is Ho ⁇ sTii 8 3 ⁇ 4-x N x wherein x is a value greater than 0 and less than 4.
  • the protonating step of the method is preferably carried out by mixing the non- metal doped metal oxide with an acidic solution.
  • the acidic solution may be selected from the group comprising hydrochloric acid, nitric acid, sulphuric acid, phosphoric acid, hydroflouric acid, hydroiodic acid, hydrobromic acid, acetic acid (HAC), perchloric acid, iodic acid (HIO 3 ) and periodic acid (HIO 4 ).
  • the acidic solution is hydrochloric acid.
  • the acidic solution is 0.001 M to 15M hydrochloric acid.
  • the exfoliating step of the method is preferably carried out by mixing the protonated non-metal doped metal oxide with an exfoliating agent.
  • the exfoliating agent is preferably an organic compound selected from the group comprising tetraalkylammonium hydroxides including tetrabutylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetramethylammonium hydroxide.
  • the protonated non-metal doped metal oxide of formula (III) is preferably in contact with the exfoliating agent for a period of between 1 hour and two weeks, more preferably for 1 to 10 days, and most preferably for approximately 7 days.
  • the exfoliation step is preferably carried out at a temperature of between room temperature and 6O 0 C. Most preferably the exfoliation step is carried out at room temperature.
  • non-metal doped metal oxide nanosheets are formed in a suspension.
  • the method may further include the step of re-ordering the non-metal doped metal oxide nanosheets to form a layered or pillared non-metal doped metal oxide.
  • the re-ordering step may be achieved by drying the nanosheets or adding a cationic solution.
  • the re-ordering step is carried out by evaporating any solvent present in the non-metal doped metal oxide nanosheet suspension, and drying the solid non-metal doped metal oxide nanosheets.
  • the cationic solution may be an acidic solution, a solution comprising inorganic or organic salts which may provide cations such as Li + , Na + , K + , Mg 2+ , Ca 2+ , Al 3+ and the like; nanoclusters, such as Keggin type ions; inorganic nanoparticles; organic macromolecules such as dyes and the like, which are capable of providing cations to the non-metal doped metal oxide nanosheets or capable of inducing the re-ordering of the nanosheets.
  • inorganic or organic salts which may provide cations such as Li + , Na + , K + , Mg 2+ , Ca 2+ , Al 3+ and the like
  • nanoclusters such as Keggin type ions
  • inorganic nanoparticles such as dyes and the like, which are capable of providing cations to the non-metal doped metal oxide nanosheets or capable of inducing the re-ordering of the nanosheets.
  • the cationic solution is an acidic solution selected from the group comprising hydrochloric acid, nitric acid, sulphuric acid, phosphoric acid, hydrofluoric acid, hydroiodic acid, hydrobromic acid, acetic acid (HAC), perchloric acid, iodic acid (HIO 3 ) and periodic acid (HIO 4 ).
  • the cationic solution is selected from hydrochloric acid, nitric acid, sulphuric acid and phosphoric acid. More preferably the cationic solution is hydrochloric acid.
  • the method may further include the step of separating and drying the layered or pillared non-metal doped metal oxide.
  • the separation may require the addition of one or more suitable flocculant.
  • the flocculant may be selected from the group comprising: inorganic acids, bases and salts; organic natural products, such as starch, guar and the like; or synthetic organic compounds such as polymers.
  • M is one or more metal ions selected from the group comprising titanium, lanthanium, niobium, nickel, iron, cobalt, calcium, barium, zirconium, hafnium, molybdenum, chromium, tungsten, tantalum and vanadium;
  • D is a non-metal dopant selected from the group comprising boron, carbon, nitrogen, fluorine, sulphur, phosphorus and iodine; x is a value greater than 0 and less than 8; y and z are independently a value greater than 0 and equal to or less than 8; and z-x is a value greater than 0.
  • the nanosheets have a formula (IV) wherein M is titanium; D is nitrogen; y is a value greater than 0 and equal to or less than 8; z is a value greater than 0 and equal to or less than 8; x is a value greater than 0 and less than 8; and z-x is a value greater than 0.
  • the nanosheets have a formula (IV) wherein M is titanium; D is nitrogen; y is a value greater than 0 and equal to or less than 1 ; z is 2; and x is a value greater than 0 and less than 2.
  • the nanosheets have a formula Tio .91 O 2 .xN x , wherein x is a value greater than 0 and less than 2.
  • the invention provides for the use of non-metal doped metal oxide nanosheets of formula (IV) as photocatalysts.
  • the substrate may be any substrate suitable for supporting a photocatalytic film.
  • the substrate is glass, quartz glass, silicon wafer or ITO glass.
  • the method of coating substrates with non-metal doped metal oxide nanosheets of formula (IV) may further include the step of adding one or more layers of binder.
  • the layers of binder are preferably applied onto the substrate prior to coating with a layer of non-metal doped metal oxide nanosheets of formula (IV) and/or between layers of non-metal doped metal oxide nanosheets of formula (IV).
  • the binder preferably includes an organic polyelectrolyte or charged inorganic nanoclusters.
  • the polyelectrolyte may be selected from the group comprising polyethylenimine (PEI), poly(allylamine hydrochloride), and poly(diallyldimethylammonium) chloride.
  • the charged inorganic nanoclusters may be selected from the group comprising partially hydrolysed nanoclusters of metal hydroxides and oxides including aluminium oxides and hydroxides, chromium oxides and hydroxides, cobalt oxides and hydroxides, ferric oxides and hydroxides, ferrous oxides and hydroxides, nickel oxides and hydroxides, tungsten oxides and hydroxides manganese oxides and hydroxides, titanium oxides and hydroxides, zirconium oxides and hydroxides and vanadium oxides and hydroxides.
  • metal hydroxides and oxides including aluminium oxides and hydroxides, chromium oxides and hydroxides, cobalt oxides and hydroxides, ferric oxides and hydroxides, ferrous oxides and hydroxides, nickel oxides and hydroxides, tungsten oxides and hydroxides manganese oxides and hydroxides, titanium oxides and hydroxides, zirconium oxides and hydroxides and vanadium oxides and hydroxides.
  • the binder may be applied to the substrate using a dip-coating method, in which the substrate is placed in a solution of the polyelectrolyte or inorganic nanoclusters for period of between 1 minute and 2 hours.
  • the substrate is placed in the solution of polyelectrolyte or inorganic nanoclusters for a period of between 15 to 60 minutes. More preferably the substrate remains in the solution of polyelectrolyte or inorganic nanoclusters for approximately 20 minutes before being rinsed and dried.
  • the non-metal doped metal oxide nanosheets of formula (IV) are preferably applied to the substrate by providing the nanosheets in suspension and coating the substrate with the nanosheets.
  • the substrate remains in the nanosheet suspension for a period of between 1 minute to 2 hours. More preferably the substrate is placed in the suspension for a period of between 15 to 60 minutes. Most preferably the substrate remains in the suspension for approximately 20 minutes before being rinsed and dried.
  • the invention provides a substrate coated with non-metal doped metal oxide nanosheets of formula (IV).
  • Fig. 1 is a schematic representation of an embodiment of the invention
  • Fig. 2A is a tapping-mode AFM image of a PEI/Tio .9 i ⁇ 2-X N X bilayer deposited on a silicon wafer chip;
  • Fig. 2B is an XRD pattern of (a) an intermediate, layered Ho . ⁇ sTh .83 O 4-X N x and (b) restacked T ⁇ o .9 iO 2-x N x nanosheets of the invention formed by drying the colloidal suspension of nanosheets at 5O 0 C;
  • Fig. 3 is a zeta potential graph for a) non-doped T ⁇ O.91 O 2 nanosheets and b) Tio .9 i ⁇ 2-X N X nanosheets;
  • Fig. 4 ⁇ is a UV-visible light absorbance spectra for the colloidal suspension of (a) T ⁇ 0.9 iO 2 ; and (b) Ti 0.9 iO2 -x N x nanosheets a concentration of 0.014g dm 3 ;
  • Fig 4B is a plot of transformed Kubelka-Munk function versus the energy of the light absorbed of (a) T ⁇ 0 .9iO 2 ; and (b) Ti 0 . 9 iO 2-x N ⁇ .
  • Fig. 4C is a high resolution XPS spectra of (a) (PEI/T ⁇ o. 9 iO 2 )io and (b)
  • Fig. 5A is a UV-visible absorption spectra for multilayer films of
  • Fig. 5B is a graph showing the dependence of peak absorbance at 262nm on the number of deposition cycles
  • Fig. 5C is XRD patterns for multilayer films of (PEI/ 11 0 .91O 2 -XNx) 1 O (a) as grown sample and (b) sample kept at room temperature in air for one week;
  • Fig. 6 is a graph of photocurrent-applied potential curves of photoanodes on ITO substrates vs. Ag/AgCI reference electrode: (a) T1O .91 O 2 nanosheet film in dark; (b) Ti O g 1 O 2 nanosheet film under the irradiation of visible light from 420 nm to 770 nm; and (c) Tio .9 i ⁇ 2 -X N X nanosheet film under the irradiation of visible light from 420 nm to 770 nm; and
  • Fig. 7 illustrates a comparative hydrophilicity test of thin films fabricated with undoped Tio .9 iO 2 and doped Ti 09I O 2-X N x nanosheets.
  • the non-metal doped metal oxide nanosheets of formula (IV) may be formed by mixing and calcining at least one metal oxide precursor with a non-metal dopant, conducting a protonation or ion exchange step followed by exfoliating the protonated non-metal doped metal oxide to form non-metal doped metal oxide nanosheets.
  • reaction mechanism can be summarised as follows:
  • Step 2 A n M y O z . x D x ⁇ H n A W nMyO ⁇ x D x Exfoliating agent
  • Step 3 H n Aw n MyOz- X D x ⁇ MyO z-x D x
  • the doping reaction of step 1 is preferably carried out by contacting the metal oxide precursor (A n M y O z ) with a non-metal dopant (D) and calcining at a temperature between 200 0 C to 1800 0 C for a period of between 30 minutes to 5 days.
  • the non-metal doped metal oxide (A n M y O z-x D x ) produced by step 1 , above, has a layered structure in which metal oxide layers may be intercalated with a cation (A).
  • the non-metal dopant (D) stoichiometrically replaces oxygen from the metal oxide layers to form the non-metal doped metal oxide of formula (II).
  • step 1 the conditions for the doping of step 1 will vary depending on the type of dopant used to exchange with oxygen in the metal oxide precursor.
  • the metal oxide precursor may be calcined in a gaseous atmosphere containing ammonia gas or nitrogen, or in contact with a nitrogen containing organic substance such as CeH 12 N 4 , CO(NH 2 ) 2 , CS(NH 2 ) 2 , triethylamine, (NH 4 ) 2 CO 3 , and C 25 H 31 N 3 .
  • the gaseous atmosphere may be a gas comprising lower straight chain alkanes (C x H y ) such as methane, ethane, propane and butane; carbon monoxide (CO); and/or carbon dioxide (CO 2 ).
  • C x H y lower straight chain alkanes
  • CO carbon monoxide
  • CO 2 carbon dioxide
  • any simple organic substance such as an alkane, an alkene, C 12 H 22 O 11 , C 2 sH 3 o ⁇ 5 , CeHi 2 , or CeHi 2 O 2 , may be in contact with the metal oxide precursor during calcination.
  • the gaseous atmosphere may be a gas comprising B x H y
  • boron, H 3 BO 3 , or an organic substance containing boron such as C 6 H 12 BNO 3 , C 7 H 5 BF 4 O 2 , C 7 H 7 BO 4 , H 3 N BH 3 or C 6 H 5 N(C 2 Hs) 2 BH 3 may be in contact with the metal oxide precursor during calcination.
  • the gaseous atmosphere may comprise H 2 S.
  • sulphur, (NH 4 ) 2 S, or sulphur containing organic substances, such as CS(NH 2 ) 2 , C 7 H 7 SO 2 , C 7 Hi 2 O 2 S or C 6 H 4 S may be in contact with the metal oxide precursor.
  • the cation intercalated titanate may be in contact with NH 4 F or fluorine containing organic substances, such as C 4 CI 2 F 6 , C 4 H 2 F 2 N 2 or C 4 H 8 BrF.
  • the metal oxide precursor may be contacted with HIO 3 , HIO 4 , NH 4 I, NH 4 IO 3 , or organic substances containing iodine, such as C 4 H 9 I, C 5 H 3 IO 2 , C 5 H 3 FI, or C 6 H 13 I.
  • step 2 leads to the complete or partial replacement of the intercalated cations (A) by protons in the layered metal oxide precursor to form protonated non-metal doped metal oxide of formula (III).
  • the protonated non-metal doped metal oxide nanosheets may be separated and dried.
  • step 3 The addition of the exfoliating agent in step 3 to the protonated non-metal doped metal oxide of formula (III) is preferably, though not necessarily, carried out in suspension.
  • This step results in the exfoliation of the protonated non- metal doped metal oxide through the exchange of protons with cations from the exfoliating agent which reduces and/or eliminates the attractive forces between the layers of non-metal doped metal oxide to form non-metal doped metal oxide nanosheets of formula (IV).
  • the exfoliated non-metal doped metal oxide nanosheets may be used in suspension to form coatings and films. Alternatively, they may be reordered or restacked to form a layered non-metal doped metal oxide structure which can be separated and dried prior to use.
  • the layered non-metal doped metal oxides are dried at temperatures below approximately 100 0 C.
  • Step 3 of the method as described above and subsequent use of the non-metal doped metal oxide nanosheets is schematically represented in Figure 1.
  • the non-metal doped metal oxide nanosheets may be used in photocatalytic applications, such as self cleaning coatings, decomposition of organic compounds, and hydrogen production from the photocatalytic splitting of water.
  • the metal oxide precursor of formula (I) contains intercalated cations within the layered structure of the metal oxide they may be formed by heating a cation donor precursor with a metal oxide.
  • the reaction can be summarised as follows: calcination Step 1a Cation donor precursor + Metal oxide donor ⁇ A n M y O z
  • the cation donor precursor is an alkali earth metal salt or an alkali metal salt selected from the group comprising alkali metal halides; alkali earth metal halides; alkali metal sulphides; alkali earth metal sulphides; alkali metal sulphates; alkali earth metal sulphates; alkali metal carbonates; alkali earth metal carbonates; alkali metal nitrates; alkali earth metal nitrates; alkali metal hydroxides; alkali earth metal hydroxides; alkali metal acetates; alkali earth metal acetates; alkali metal dimethenylamine (AN(CH 2 )2); alkali earth metal dimethenylamine (AN(CH 2 ⁇ ); alkali metal oxide; alkali earth metal oxides; alkali metal chlorate; alkali earth metal chlorate; alkali metal phosphate and/or alkali earth metal phosphate.
  • alkali metal halides alkali
  • the metal oxide donor is selected from the group comprising metal oxides or hydroxides, including TiO, Ti 2 ⁇ 3 , Ti 3 O 5 , Ti ⁇ 2 , TiO x Ny, TiO x Cy, Ti(OH) 4 .xH 2 O; mixed oxides of titanium, such as lanthanum titanium oxide; niobium oxides and mixed oxides thereof, such as calcium niobium oxide; nickel oxides, cobalt oxides, ferric and ferrous oxides, tantalum oxides; vanadium oxides; and tungsten oxides; metal nitride compounds, such as titanium nitride (TiN), niobium nitride, tantalum nitride and vanadium nitride; metal carbide compounds, including titanium carbide (TiC); metal cyanamide compounds, including titanium cyanamide (TiC x N y ); metal boride compounds including titanium diboride (TiB 2 ); metal sulphide compounds, including
  • the cation donor precursor and the at least one metal oxide donor may be calcined at a temperature of between 500 0 C to 1200 0 C for a period between of 0.5 and 40 hours.
  • the at least one cation donor precursor and said at least one metal oxide donor are calcined at a temperature of between 600 0 C to 1000 0 C for a period of between 2 hours to 30 hours.
  • the cation donor precursor and the metal oxide donor are more suitably calcined at a temperature of about 75O 0 C for a period of about 20 hours.
  • a metal oxide precursor of Cso.6 8 Ti 1 .8 3 O 4 was prepared by mixing caesium carbonate (CS2CO 3 ), with titania (T ⁇ O2), and calcined at 75O 0 C in air for 20 hours. Approximately 60 - 70 grams of white crystalline caesium titanate (Cso .68 Ti 1.83 O 4 ) was collected.
  • a nitrogen doped caesium titanate was formed by calcining the white Cso.68Ti1. 8 3O4 powder at about 75O 0 C in an ammonia atmosphere for 2 hrs.
  • the resultant bright yellow powder of nitrogen doped metal oxide has a formula Cso .68 Tii .83 ⁇ 4-x N ⁇ , wherein x is a value greater than 0 and less than 4.
  • the protonated form of the nitrogen doped titanate (H 0.68 Ti 1. e 3 O 4 .xN x ) was prepared by the ion-exchange of the caesium in Cso .68 Tii .83 ⁇ 4 -x N x with protons by placing the Cso.6 8 Ti1.
  • the H 0 . 68 Ti 1.83 O4.xNx was separated and dried.
  • the resultant yellow H 06S Ti 1 8S O 4 - X N x (1.2g) was dispersed in an exfoliating agent, tetrabutylammonium hydroxide (TBA + OH ' ) solution (300 cm 3 , 0.2M), and was shaken for more than 7 days at room temperature to exfoliate the protonated nitrogen doped titanate into a yellow colloidal suspension of Tio .9 i ⁇ 2-x N ⁇ nanosheets.
  • TSA + OH ' tetrabutylammonium hydroxide
  • the exfoliated nitrogen doped titania nanosheets (Tio. 91 O 2 .xNx) were used to create a thin film by dip coating onto a silicon wafer substrate, via an electrostatic layer-by-layer (LBL) self-assembly method.
  • PEI polyethylenimine solution
  • Fig 2A shows an atomic force microscopy (AFM) image of the first layer of Ti 0.9 i ⁇ 2 - ⁇ N ⁇ nanosheets deposited onto a silicon wafer.
  • AFM atomic force microscopy
  • Fig 2B is an XRD pattern of the restacked Tio .9 i ⁇ 2 - X N X nanosheets compared to the HTiON intermediate. It can be deduced from Fig 2B that the restacked nanosheets are well-defined layered structures with an interlayer distance of 1.81 nm. This interlayer distance is quite different from that of the parent layered precursor (Ho .68 Tii .83 ⁇ 4-x N x ) shown by in the comparison of traces (a) and (b) in Fig 2B.
  • Fig 4A is a UV-visible absorption spectra for a colloidal suspension of exfoliated nitrogen doped titania nanosheets that revealed the intrinsic absorption edge of titania nanosheets had a distinct red-shift, in addition to a shoulder absorption up to 450 nm after nitrogen doping.
  • the band gap of the titania nanosheets determined from the corresponding transformed Kubelka-Munk function (K-M) plots (shown in Fig 4B) shifted from 4.38 eV to 4.25 eV after nitrogen doping, which differs from the reported 3.8 eV of Ti 0 9I O 2 nanosheets derived from photoelectrochemical measurements.
  • the state of dopant N in the nanosheets was investigated by XPS spectra (see Fig. 4C).
  • the N 1s spectra of both films fabricated from doped and un-doped nanosheets exhibited two peaks (1 and 2), which are assignable to the molecularly chemisorbed Y-N 2 and N species in polyelectrolyte PEI 1 respectively.
  • an addition peak at about 396 eV was observed in the N 1s spectrum for Tio .9 i ⁇ 2-X N X nanosheets.
  • This peak can be assignable to the atomic ⁇ -N in the network of Ti-O-Ti, namely the substitution of lattice O with N, strongly supporting the nitrogen doping in the architecture of nanosheets.
  • the ratio of N to O in Ti 09 iO 2-x N x nanosheets was estimated to be about 4.5 atom%.
  • First-principle calculations further confirmed that the mixture of O 2p with N 2p states instead of isolated states in the band gap is responsible for a decreased band gap of nitrogen doped Tio .9 iO 2 nanosheets by elevating the top of the valence band.
  • the role of concomitant oxygen vacancies with the replacement of lattice O with N atoms should be considered.
  • nitrogen doped bulk titania oxygen vacancies can be formed to keep the charge balance and the generated localized states are located between 0.75 and 1.18 eV below the conduction band bottom, which can be contributed to the additional visible light absorbance.
  • the generation of oxygen vacancies is inevitable and hence renders such an additional absorption shoulder.
  • Figure 5A presents the UV-visible absorbance spectra of multilayer films of (PEI/Tio .9 i0 2 - ⁇ N ⁇ nanosheets).
  • the absorption measurements conducted immediately after each cycle showed nearly linear increments (see Fig. 5B) of peak-top absorbance at ca. 262 nm, which strongly indicates the success of multilayer thin film growth of Tio .91 O 2 .xN x nanosheets.
  • the peak absorbance of the films based on Tio .9 i ⁇ 2-X N X nanosheets is comparable to that from un-doped T1 0 .91O 2 nanosheets, indicating Tio. 9 i ⁇ 2 - ⁇ N x nanosheets are also an excellent 2D building block.
  • Fig 5C illustrates the XRD pattern for a multilayered film of (PEI/Ti 0 . 9 i0 2 - ⁇ N x )io.
  • the as-prepared multilayer film of (PEI/Ti 0 . 9 i ⁇ 2 - ⁇ N ⁇ )io presented a broad XRD diffraction peak centring at around 6.5° (2 ⁇ ), which is associated with an interlayer spacing of -1.4 nm, a similar value to that for the multilayer films of Tio.9i0 2 nanosheets using both organic and inorganic binders, such as those reported in Wang, L.Z., et al., J. Phys. Chem.
  • Fig. 6 presents the applied potential dependence of photocurrent densities for the photoanode.
  • the measurements were taken with the electrodes in a 0.1 mol-dm "3 NaOH electrolyte solution and a scan rate of 5 mVs "1 .
  • the illuminated photoanode surface area with the deposition of 10 layers of nanosheets was 1 cm 2 .
  • the turn-on potential of the photocurrent for the photoanode with Ti 0 9 i ⁇ 2 nanosheets was about 0.45 V, while the turn-on potential was about 0.15 V for Ti 0 9 i ⁇ 2 - ⁇ N x nanosheets using a Ag/AgCI reference electrode.
  • the different turn-on potential determined by the flat- potential of a semiconductor anode (Bard, A. J. J. Phys. Chem. 1982, 86, 172- 177) can be attributed to the derivation of the Fermi level in the Ti 0 9 iO 2- ⁇ N x nanosheets with the elevated valence band top.
  • the photocurrent of the photoanode with Tio 9 iO 2- ⁇ N x nanosheets significantly increased, while only a slight increment for the un-doped photoanode was observed.
  • the limited localized states in the band gap of n-type Ti 0 9 iO 2 nanosheets should be responsible for the observed slightly enhanced photoresponse to the visible light in the film of un-doped Ti 09 i ⁇ 2 nanosheets.
  • the significant photocurrent enhancement in the film of Ti 09 i ⁇ 2 - ⁇ N x nanosheets can be assignable to the visible light absorption of nitrogen doped nanosheets and possibly together with a small proportion of O vacancies related states photoexcitation.
  • Fig 7 shows the hydrophilicity property test of (PEI/Tio 9 i ⁇ 2 - ⁇ N x ) 10 film compared to a (PEI/Ti 0 9i ⁇ 2)io multilayer film.
  • Quartz glass slides were prepared with multilayer films of (PEI/Ti 0 9i ⁇ 2 -x N x )io and (PEI/Tiogi ⁇ 2)io using the methods described above.
  • the hydrophilicity of these films was assessed by placing a drop of water on each film and irradiating for 30 minutes with visible light.
  • the improved hydrophilicity properties of films made from the non-metal doped metal oxide nanosheets indicate they may be suitable as defogging or anti- fogging coatings.
  • non-metal doped metal oxide nanosheets have been prepared for the first time by the inventors.
  • the optical absorption of the non-metal doped metal oxide nanosheets has been extended to a longer wavelength up into the visible light range.
  • Multilayer films formed with these nanosheets show remarkable enhancement of photocurrent compared to that of undoped metal oxide nanosheets under visible light irradiation.
  • Non-metal doped metal oxide nanosheets may be used as visible light photocatalysis in photoelectric areas. They may also be useful as antifogging and anti-reflective coatings.

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Abstract

L'invention concerne des nanofeuilles d'oxyde métallique à dopage non métallique de la formule (IV) : MyOz-xDx (IV), M représentant un ou plusieurs ions métalliques choisis dans le groupe constitué des métaux suivants : titane, lanthane, niobium, tungstène, nickel, fer, cobalt, calcium, baryum, zirconium, hafnium, molybdène, chrome, tantale, et vanadium; D représentant un dopant non métallique choisi dans le groupe constitué du bore, du carbone, de l'azote, du fluor, du soufre, du phosphore et de l'iode; y représentant une valeur supérieure à 0 et égale ou inférieure à 8; z représentant une valeur supérieure à 0 et égale ou inférieure à 8;x représentant une valeur supérieure à 0 et inférieure à 8; et z-x représentant toujours une valeur supérieure à 0, et un procédé de production de celles-ci.
PCT/AU2008/001728 2007-11-23 2008-11-21 Nanofeuilles d'oxyde métallique à dopage non métallique et leur procédé de production Ceased WO2009065180A1 (fr)

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CN102219179A (zh) * 2010-04-19 2011-10-19 中国科学院理化技术研究所 一种银掺杂二氧化钛薄膜及其制备方法
US8551906B2 (en) 2007-08-16 2013-10-08 The University Of Queensland Titanate photocatalyst
CN103721737A (zh) * 2014-01-07 2014-04-16 福州大学 一种高效可见光驱动催化分解水的非金属材料
WO2014063009A1 (fr) * 2012-10-18 2014-04-24 Texas State University-San Marcos Nanorevêtements multifonctionnels de grande efficacité provenant d'un procédé facile de co-assemblage
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CN108947529A (zh) * 2018-06-25 2018-12-07 华南理工大学 一种非金属离子掺杂的钨酸镧型混合质子-电子导体透氢材料及其制备方法与应用
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CN113603155A (zh) * 2021-07-30 2021-11-05 蜂巢能源科技有限公司 掺杂包覆方法、采用该方法对三元正极材料改性的方法和应用
CN113800555A (zh) * 2021-09-02 2021-12-17 重庆大学 新型一硫化钛纳米材料及其复合材料的制备与吸波用途
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CN115954273A (zh) * 2023-03-13 2023-04-11 山东科技大学 一种气相碘掺杂的金属氧化物薄膜晶体管及制备方法
WO2024045408A1 (fr) * 2022-09-02 2024-03-07 深圳先进技术研究院 Photoanode à hétérojonction semi-conductrice homologue au titane et son procédé de préparation
WO2025043374A1 (fr) * 2023-08-25 2025-03-06 广东邦普循环科技有限公司 Oxyde cobaltosique dopé et son procédé de préparation
CN120504346A (zh) * 2025-07-22 2025-08-19 山东海化集团有限公司 一种溴掺杂的二维镍铁氧化物的制备方法及其应用

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