Indicator for detecting a photocatalyst

• US 20070029527A1
• Filed: 03/11/2004
• Published: 02/08/2007
• Est. Priority Date: 03/12/2003
• Status: Abandoned Application

• Current Assignee: University of Strathclyde
• Original Assignee: University of Strathclyde
• Inventors: Mills, Andrew, Lee, Soo-Keun
• Application Number:
  US10/548,766
• Publication Number:
  US 20070029527A1
• Time in Patent Office: Days
• US Class Current: 252/408.100
• CPC Class Codes: G01N 21/78 producing a change of colour
• CPC Class Codes: G01N 31/22 using chemical indicators G01N31/02 takes precedence

Abstract

This invention relates to an indicator for detecting a photocatalyst wherein the indicator comprises at least one redox-sensitive material and either at least one electron donor or at least one electron acceptor. The invention also relates to a method for detecting a photocatalyst using an indicator. In particular, the photocatalyst may be a semiconductor such as titanium dioxide on a glass substrate.

Claims

1-38. -38. (canceled)

39. An indicator for detecting a photocatalyst material, the indicator comprising:

at least one redox sensitive material which displays different physical properties in the oxidised and reduced forms; and

either at least one electron donor or at least one electron acceptor;

wherein the at least one redox sensitive material and either the at least one electron donor or the at least one electron acceptor are substantially in contact with one another; and

wherein in use irradiation of any photocatalyst material with light of greater than or equal to the energy necessary to electronically excite the photocatalyst material, the redox sensitive material becomes reduced and changes colour and/or luminescence light intensity.

40. An indicator according to claim 39 that operates via a reductive electron transfer mechanism and wherein there is at least one electron donor.

41. An indicator according to claim 39 that operates via an oxidative electron transfer mechanism and wherein there is at least one electron acceptor.

42. An indicator according to claim 39, wherein the light used for irradiating the photocatalyst material has a wavelength in the region of less than about 1000 nm, about 200-1000 nm, about 300-700 nm or less than or equal to about 420 nm.

43. An indicator according to claim 39, wherein the indicator is activated by light of energy greater than or equal to the bandgap energy of the photocatalyst material.

44. An indicator according to claim 39, wherein the indicator operates via a reductive mechanism and the electronically excited photocatalyst material is able to oxidise the electron donor present in the indicator.

45. An indicator according to claim 39, wherein a reduced form of the photocatalyst material reduces the redox-sensitive material in the indicator to its reduced form which is of a different colour and/or fluorescence intensity compared to its original oxidised form.

46. An indicator according to claim 39, wherein when the redox sensitive material is sensitive towards oxygen then, under normal aerobic conditions, the light activation step causes the reduction of the redox sensitive material to its less coloured (and/or less fluorescent) oxygen sensitive material.

47. An indicator according to claim 39, wherein when the redox sensitive material is in its reduced form and is substantially insensitive towards oxygen, then following the light activation step and the conversion of the redox sensitive material from its usually high coloured form to its less coloured, or differently coloured form, there is no subsequent change in colour due to air oxidation, so that the photoinduced colour change in the redox sensitive material is irreversible.

48. An indicator according to claim 39, wherein the indicator, coated onto the surface of an appropriate photocatalyst, exposed to light of greater than or equal to the bandgap of the photocatalyst results in the redox-sensitive material changing in colour and/or fluorescence intensity as it is changed from its original oxidised form to its reduced (usually non-coloured and/or fluorescent) form.

49. An indicator according to claim 39, wherein the reduction of the redox-sensitive material is a photocatalyst indicating step, as it results in a substantially observable optical (i.e. coloured and/or fluorescent) change in the indicator upon irradiation of the underlying photocatalyst.

50. An indicator according to claim 39, wherein the indicator operates via an oxidative mechanism in a light activation step that turns the redox indicator present in the indicator from its initially usually coloured (and/or non-fluorescent) form into an oxidised form which has a different colour and/or fluorescence intensity.

51. An indicator according to claim 39, wherein for the photocatalytic reaction to occur, and the associated colour and/or luminescent change in the redox-sensitive material, the components of the indicator are brought into substantially intimate contact with the photocatalytic material.

52. An indicator according to claim 39, wherein the indicator takes the form of an ink containing the basic components of the indicator.

53. An indicator according to claim 39, wherein the photocatalyst material is a coating on a substrate, such as glass and the indicator forms a thin dry surface on the photocatalyst material.

54. An indicator according to claim 39, wherein the indicator is in the form of an ink and dries into a highly coloured stain, or label, on the surface of the photocatalytic material.

55. An indicator according to claim 39, wherein the redox sensitive material is a dye such as:

a thiazine dyestuff, oxazene dyestuff, oxazone dyestuff, tetrazolium dyestuff, triarlymethane dyestuff, azine dyestuff, azo dyestuff, trihalomethane dyestuff, indophenol dyestuff and indigo dyestuff, viologen and/or mixtures thereof.

56. An indicator according to claim 39, wherein the electron donor is a mild reducing agent and is selected from any of the following:

an amine (e.g. NaEDTA or TEOA), a reducing saccharide (such as glucose or fructose), readily oxidisable polymers (such as polyvinyl alcohol), and other general anti-oxidants (such as ascorbic and citric acid), or easily oxidisable materials such as glycerol and/or mixtures thereof.

57. An indicator according to claim 39, wherein the electron acceptor is a mild oxidising agent, such as oxygen in air, peroxides, persulphates or metal ions such as, for example, Ag+.

58. An indicator according to claim 39, wherein the photocatalyst material is a semiconductor.

59. An indicator according to claim 39, wherein the photocatalyst material is selected from any of the following:

an oxide of titanium (e.g. titanium (IV) oxide;

TiO₂ and strontium titanate i.e. SrTiO₃), an oxide of tin (e.g. tin (IV) oxide; and

SnO₂), an oxide of tungsten (such as tungsten (VI) oxide; and

WO₃), an oxide of zinc (e.g. zinc (II) oxide; and

ZnO) and mixtures thereof;

a metal chalcogenide such as, cadmium oxide, cadmium sulfide, cadmium selanide, cadmium telluride, chalcogenides of zinc and mercury; and

a doped version of a metal oxide such as, nitrogen doped titanium (IV) oxide.

60. An indicator according to claim 39, wherein the photocatalyst material is in the form of a nanocrystalline film coated on an inert substrate such as glass, ceramic, metal or inert polymeric material such as silica coated silicon with a thickness of about 15 nm.

61. An indicator according to claim 39, wherein the indicator further comprises a binder which binds the components of the photocatalyst indicator together such as:

a polymeric material such as gelatin, hydroxyethyl, cellulose (HEC), polyvinyl alcohol (PVA), ethyl cellulose (EC), cellulose acetate (CEA), polypyrolidone (PVP), polyethylene oxide and polymethylmethacrylate (PMMA).

62. An indicator according to claim 39, wherein the weight ratios for the composition of the redox sensitive material:

electron donor;

electron acceptor;

binder and solvent is about 0.001 to 0.1;

0.05 to 4.0;

0.01 to 1.0;

1 to 10;

about 0.005 to 0.05;

0.1 to 1.0;

0.05 to 0.5;

3 to 6;

or about 0.01;

0.4;

0.1;

4.

75. A method of measuring the photocatalytic activity of a photocatalytic material using an indicator according to claim 39.

63. A method of detecting a photocatalyst material comprising the steps of providing an indicator comprising:

at least one redox-sensitive material which displays different physical properties in the oxidised and reduced forms;

either at least one electron donor or at least one electron acceptor;

wherein the at least one redox sensitive material and either the at least one electron donor or the at least one electron acceptor are substantially in contact with one another; and

wherein in use irradiation of any photocatalyst material with light of greater than or equal to the energy necessary to electronically excite the photocatalyst material, the photosensitive material becomes reduced and changes colour and/or luminescent light intensity.

64. A method according to claim 63, wherein the photocatalyst indicator operates via a reductive mechanism the indicator comprises at least one electron donor.

65. A method according to claim 63, wherein by irradiating the underlying photocatalyst under test with light of energy greater than or equal to its bandgap, the redox material in the indicator is converted into its reduced form, which may be stable under oxidising or non-oxidising conditions, and even if unstable under oxidising conditions such as found in air, only reacts sufficiently slowly with the oxygen present to make the initial, light-induced, optical change apparent.

66. A method according to claim 63, wherein when the reduced form of the redox indicator is stable in air, then the ultra-bandgap irradiation step produces a permanent colour light intensity change in the redox-sensitive material.

67. A method according to claim 63, wherein the photocatalyst to be detected is titanium dioxide and, since titanium dioxide has a large bandgap, near ultra violet light (i.e. 300-420 nm) is used.

68. A method according to claim 63, wherein the light activated redox indicator is oxygen sensitive and once exposed to an oxidising agent returns back to its original colour and/or fluorescence intensity.

69. A method according to claim 63, wherein the change in colour associated with the light activation step is irreversible and so persists indefinitely under either oxidising and/or non-oxidising conditions provided the indicator is not over-exposed to ultra bandgap light during the light activation step.

70. A method according to claim 69, wherein the change in colour is achieved using a redox indicator material that is reduced irreversibly to its reduced form, which is of a different colour and/or fluorescence intensity to its original oxidised form.

71. A method according to claim 63, wherein when the photocatalyst indicator operates via an oxidative mechanism, the indicator comprises at least one electron acceptor.

72. A method according to claim 71, wherein by irradiating the underlying photocatalyst under test with light of energy greater than or equal to its bandgap, the redox material in the indicator is converted into its oxidised form, which is usually stable under oxidising and non-oxidising conditions.

73. A method according to claim 63, wherein when the photocatalyst material is only coated to one side of glass the indicator may not only identify the presence of the photocatalyst material but also which side of the glass is coated.

74. A method according to claim 63, wherein the method also is used to ensure that photocatalyst material adhered to a glass surface is still present and active many years after the glass has been installed.

76. A method of detecting a photocatalyst material comprising the steps of providing an indicator comprising:

at least one redox-sensitive material which displays different physical properties in the oxidised and reduced forms;

either at least one electron donor or at least one electron acceptor;

wherein the at least one redox sensitive material and either the at least one electron donor or the at least one electron acceptor are substantially in contact with one another; and

wherein in use irradiation of any photocatalyst material with light of greater than or equal to the energy necessary to electronically excite the photocatalyst material, the photosensitive material becomes reduced and changes colour and/or luminescent light intensity and wherein when the photocatalyst material is only coated to one side of glass the indicator may not only identify the presence of the phtocatalyst material but also which side of the glass is coated.