公开(公告)号：US20090123769A1

公开(公告)日：2009-05-14

申请号：US12295101

申请日：2007-03-22

申请人： Yasuhiro Masaki ,  Katsuhiro Nishihara ,  Tadashi Fukuda ,  Katsumi Okada ,  Masahito Tasaka ,  Shinji Shimosaki ,  Hideaki Kanno ,  Sadanobu Nagaoka ,  Kazuomi Azuma ,  Tadashi Ogasawara

发明人： Yasuhiro Masaki ,  Katsuhiro Nishihara ,  Tadashi Fukuda ,  Katsumi Okada ,  Masahito Tasaka ,  Shinji Shimosaki ,  Hideaki Kanno ,  Sadanobu Nagaoka ,  Kazuomi Azuma ,  Tadashi Ogasawara

IPC分类号： B32B15/04 ,  B01J27/24

CPC分类号： C01G23/053 ,  B01D53/885 ,  B01D2255/20707 ,  B01D2255/802 ,  B01D2257/206 ,  B01D2257/30 ,  B01D2257/404 ,  B01D2257/406 ,  B01D2257/70 ,  B01D2257/91 ,  B01D2259/802 ,  B01J21/063 ,  B01J35/002 ,  B01J35/004 ,  B01J37/0209 ,  B01J37/0219 ,  B01J37/0225 ,  B01J37/0244 ,  B01J37/03 ,  B01J37/031 ,  B01J37/10 ,  C01P2002/54 ,  C01P2002/84 ,  C01P2002/85 ,  Y02P20/154 ,  Y10T428/31678

摘要： A titanium oxide photocatalyst responsive to visible light which can exhibit a high photocatalytic activity in response to visible light is produced by subjecting titanium oxide and/or titanium hydroxide obtained by neutralizing an acidic titanium compound with a nitrogen-containing base to heat treatment in an atmosphere containing a hydrolyzable metal compound (e.g., a titanium halide) and then to additional heat treatment in a gas having a moisture content of 0.5-4.0 volume % at a temperature of 350° C. or above. The photocatalyst which is a nitrogen-containing titanium oxide has no substantial peak at a temperature of 600° C. or above in a mass fragment spectrum obtained by thermal desorption spectroscopy in which the ratio m/e of the mass number m to the electric charged e of ions is 28, and the peak having the smallest half band width is in the range of 400-600° C. in the spectrum. The nitrogen content calculated from the peak appearing at 400 eV±1.0 eV in the N1s shell bonding energy spectrum obtained by XPS measurement of this photocatalyst is at least 20 times larger than the nitrogen content obtained by chemical analysis.

摘要翻译： 通过将通过用含氮碱中和酸化钛化合物得到的氧化钛和/或氢氧化钛在大气中进行热处理来制造响应于可见光而具有高光催化活性的可见光的氧化钛光催化剂 含有可水解金属化合物（例如，卤化钛），然后在350℃或更高的温度下在含水量为0.5-4.0体积％的气体中进行额外的热处理。 作为含氮氧化钛的光催化剂在600℃以上的温度下，在通过热解吸光谱法获得的质量碎片光谱中没有显着的峰值，其中质量数m与电荷的比率m / e e的离子是28，并且具有最小半带宽的峰在光谱中在400-600℃的范围内。 在通过该光催化剂的XPS测定得到的N1s壳结合能谱中，以400eV±1.0eV出现的峰计算出的氮含量比通过化学分析获得的氮含量大至少20倍。

公开(公告)号：US20070248831A1

公开(公告)日：2007-10-25

申请号：US11578874

申请日：2005-04-19

申请人： Katsuhiro Nishihara ,  Yasuhiro Masaki ,  Tadashi Fukuda ,  Katsumi Okada ,  Shinji Shimosaki ,  Sadanobu Nagaoka ,  Hideaki Kanno ,  Kazuomi Azuma ,  Tadashi Ogasawara

发明人： Katsuhiro Nishihara ,  Yasuhiro Masaki ,  Tadashi Fukuda ,  Katsumi Okada ,  Shinji Shimosaki ,  Sadanobu Nagaoka ,  Hideaki Kanno ,  Kazuomi Azuma ,  Tadashi Ogasawara

IPC分类号： B01J35/02 ,  B32B9/00

CPC分类号： C01G23/0536 ,  B01J21/063 ,  B01J35/002 ,  B01J35/004 ,  B01J37/031 ,  C01P2006/12 ,  Y10T428/31678

摘要： A highly active titanium oxide photocatalyst of the type responsive to visible light is prepared by subjecting a titanium (hydr)oxide raw material obtained by neutralizing an acidic titanium compound in ammonia or an amine under conditions such that the final pH is 7 or below to heat treatment in an atmosphere containing a hydrolyzable compound followed by contact with water and additional heat treatment at a temperature of at least 350° C. The resulting titanium oxide photocatalyst comprises titanium oxide with a specific surface area of at most 120 m2/g and with the amount of surface hydroxyl groups being at least 600 μeq/g. Preferably the density of surface hydroxyl groups is at least 8 μeq/m2, and the ratio of the amount of terminal type hydroxyl groups (T) to the amount of bridge type hydroxyl groups (B) in the surface hydroxyl groups satisfies T/B≧0.20. This titanium oxide photocatalyst has an ESR spectrum having two types of triplet signal for which the g values of the main spectra are 1.993-2.003 and 2.003-2.011, respectively, and it is also identified by having ratios of the strengths of these signals before irradiation with visible light, under irradiation, and immediately after the stop of irradiation which are different from conventional products.

摘要翻译： 通过使在最终pH为7以下的条件下将氨基或胺中的酸性钛化合物得到的钛（氢化物）氧化物原料进行加热，制备对可见光敏感的高活性氧化钛光催化剂 在含有可水解化合物的气氛中进行处理，然后与水接触，并在至少350℃的温度下进行额外的热处理。所得到的氧化钛光催化剂包括比表面积至多为120μm2的氧化钛， / SUP / g，表面羟基的量为至少600mueq / g。 优选地，表面羟基的密度为至少8mueq / m 2，并且末端型羟基（T）的量与桥型羟基的量的比例（B）在 表面羟基满足T / B> = 0.20。 该氧化钛光催化剂具有ESR谱，其具有两种类型的三重态信号，其主要光谱的g值分别为1.993-2.003和2.003-2.011，并且还通过在照射前具有这些信号的强度比来鉴定 具有可见光，照射下，以及在与常规产品不同的照射停止之后。

公开(公告)号：US20090239738A1

公开(公告)日：2009-09-24

申请号：US12371196

申请日：2009-02-13

申请人： Katsumi Okada ,  Katsuhiro Nishihara ,  Yasuhiro Masaki ,  Haruhiko Kajimura ,  Michiyasu Takahashi ,  Tadashi Yao ,  Tadashi Ogasawara ,  Munetoshi Watanabe ,  Shiji Shimosaki ,  Kouji Oda ,  Sadanobu Nagaoka

发明人： Katsumi Okada ,  Katsuhiro Nishihara ,  Yasuhiro Masaki ,  Haruhiko Kajimura ,  Michiyasu Takahashi ,  Tadashi Yao ,  Tadashi Ogasawara ,  Munetoshi Watanabe ,  Shiji Shimosaki ,  Kouji Oda ,  Sadanobu Nagaoka

IPC分类号： B01J27/135

CPC分类号： B01J35/004 ,  B01D53/8609 ,  B01D53/8612 ,  B01D53/8628 ,  B01D53/8634 ,  B01D53/8662 ,  B01D2255/802 ,  B01J21/063 ,  B01J23/18 ,  B01J27/132 ,  B01J27/135 ,  B01J35/002 ,  B01J37/0238 ,  B01J37/22

摘要： Titanium oxide-based photocatalysts which contain a metal halide in titanium oxide and which are prepared from titanium oxide and/or its precursor, which may optionally be heat treated, by contact with a reactive gas containing a metal halide of the formula MXn or MOXn (wherein M=a metal, X=a halogen, and n=an integer) with heating stably develop a high photocatalytic activity with visible light irradiation. The photocatalysts may subsequently be stabilized by contact with water or by heat treatment, and/or promoted by contact with a heteropoly acid and/or an isopoly acid so as to include a metal complex in the titanium oxide. Photocatalysts prepared in this manner exhibit novel ESR features. The present invention also provides methods for preparing these photocatalysts, a photocatalyst dispersion and a photocatalytic coating fluid containing such a photocatalyst, and photocatalytic functional products and methods for their manufacture using the photocatalyst.

摘要翻译： 二氧化钛基光催化剂，其在二氧化钛中含有金属卤化物，并且可以通过与含有式MXn或MOXn的金属卤化物的反应性气体接触而由氧化钛和/或其前体制备，其可以任选地进行热处理（ 其中M =金属，X =卤素，n =整数），加热可稳定地产生可见光照射的高光催化活性。 可以随后通过与水接触或通过热处理来稳定光催化剂，和/或通过与杂多酸和/或异多酸接触来促进光催化剂，以在氧化钛中包括金属络合物。 以这种方式制备的光催化剂显示出新的ESR特征。 本发明还提供了制备这些光催化剂的方法，光催化剂分散体和含有这种光催化剂的光催化涂布液，以及光催化功能产物及其使用该光催化剂的制造方法。

公开(公告)号：US07521133B2

公开(公告)日：2009-04-21

申请号：US10508871

申请日：2003-03-20

申请人： Katsumi Okada ,  Katsuhiro Nishihara ,  Yasuhiro Masaki ,  Haruhiko Kajimura ,  Michiyasu Takahashi ,  Tadashi Yao ,  Tadashi Ogasawara ,  Munetoshi Watanabe ,  Shiji Shimosaki ,  Kouji Oda ,  Sadanobu Nagaoka

发明人： Katsumi Okada ,  Katsuhiro Nishihara ,  Yasuhiro Masaki ,  Haruhiko Kajimura ,  Michiyasu Takahashi ,  Tadashi Yao ,  Tadashi Ogasawara ,  Munetoshi Watanabe ,  Shiji Shimosaki ,  Kouji Oda ,  Sadanobu Nagaoka

IPC分类号： B32B9/00 ,  C09D1/00 ,  C04B35/00

CPC分类号： B01J35/004 ,  B01D53/8609 ,  B01D53/8612 ,  B01D53/8628 ,  B01D53/8634 ,  B01D53/8662 ,  B01D2255/802 ,  B01J21/063 ,  B01J23/18 ,  B01J27/132 ,  B01J27/135 ,  B01J35/002 ,  B01J37/0238 ,  B01J37/22

摘要： Titanium oxide-based photocatalysts which contain a metal halide in titanium oxide and which are prepared from titanium oxide and/or its precursor, which may optionally be heat treated, by contact with a reactive gas containing a metal halide of the formula MXn or MOXn (wherein M=a metal, X=a halogen, and n=an integer) with heating stably develop a high photocatalytic activity with visible light irradiation. The photocatalysts may subsequently be stabilized by contact with water or by heat treatment, and/or promoted by contact with a heteropoly acid and/or an isopoly acid so as to include a metal complex in the titanium oxide. Photocatalysts prepared in this manner exhibit novel ESR features. The present invention also provides methods for preparing these photocatalysts, a photocatalyst dispersion and a photocatalytic coating fluid containing such a photocatalyst, and photocatalytic functional products and methods for their manufacture using the photocatalyst.

摘要翻译： 二氧化钛基光催化剂，其在氧化钛中含有金属卤化物，其可由可选择地经过热处理的氧化钛和/或其前体制备，所述氧化钛和/或其前体通过与含有式MXn或MOXn的金属卤化物的反应性气体接触 其中M =金属，X =卤素，n =整数），加热可稳定地产生可见光照射的高光催化活性。 可以随后通过与水接触或通过热处理来稳定光催化剂，和/或通过与杂多酸和/或异多酸接触来促进光催化剂，以在氧化钛中包括金属络合物。 以这种方式制备的光催化剂显示出新的ESR特征。 本发明还提供了制备这些光催化剂的方法，光催化剂分散体和含有这种光催化剂的光催化涂布液，以及光催化功能产物及其使用该光催化剂的制造方法。

公开(公告)号：US20050227008A1

公开(公告)日：2005-10-13

申请号：US10508871

申请日：2003-03-20

申请人： Katsumi Okada ,  Katsuhiro Nishihara ,  Yasuhiro Masaki ,  Haruhiko Kajimura ,  Michiyasu Takahashi ,  Tadashi Yao ,  Tadashi Ogasawara ,  Munetoshi Watanabe ,  Shiji Shimosaki ,  Kouji Oda ,  Sadanobu Nagaoka

发明人： Katsumi Okada ,  Katsuhiro Nishihara ,  Yasuhiro Masaki ,  Haruhiko Kajimura ,  Michiyasu Takahashi ,  Tadashi Yao ,  Tadashi Ogasawara ,  Munetoshi Watanabe ,  Shiji Shimosaki ,  Kouji Oda ,  Sadanobu Nagaoka

IPC分类号： B01D53/86 ,  B01J21/06 ,  B01J23/18 ,  B01J27/132 ,  B01J27/135 ,  B01J35/00 ,  B01J37/02 ,  B01J37/22 ,  B05D3/02

CPC分类号： B01J35/004 ,  B01D53/8609 ,  B01D53/8612 ,  B01D53/8628 ,  B01D53/8634 ,  B01D53/8662 ,  B01D2255/802 ,  B01J21/063 ,  B01J23/18 ,  B01J27/132 ,  B01J27/135 ,  B01J35/002 ,  B01J37/0238 ,  B01J37/22

摘要： Titanium oxide-based photocatalysts which contain a metal halide in titanium oxide and which are prepared from titanium oxide and/or its precursor, which may optionally be heat treated, by contact with a reactive gas containing a metal halide of the formula MXn or MOXn (wherein M=a metal, X=a halogen, and n=an integer) with heating stably develop a high photocatalytic activity with visible light irradiation. The photocatalysts may subsequently be stabilized by contact with water or by heat treatment, and/or promoted by contact with a heteropoly acid and/or an isopoly acid so as to include a metal complex in the titanium oxide. Photocatalysts prepared in this manner exhibit novel ESR features. The present invention also provides methods for preparing these photocatalysts, a photocatalyst dispersion and a photocatalytic coating fluid containing such a photocatalyst, and photocatalytic functional products and methods for their manufacture using the photocatalyst.

摘要翻译： 二氧化钛基光催化剂，其在氧化钛中含有金属卤化物，并且其可由氧化钛和/或其前体制备，其可任选地被热处理，通过与含有式MX的金属卤化物的反应性气体接触， （其中M =金属，X =卤素，n =整数）与可见光照射一起稳定地产生高的光催化活性。 可以随后通过与水接触或通过热处理来稳定光催化剂，和/或通过与杂多酸和/或异多酸接触来促进光催化剂，以在氧化钛中包括金属络合物。 以这种方式制备的光催化剂显示出新的ESR特征。 本发明还提供了制备这些光催化剂的方法，光催化剂分散体和含有这种光催化剂的光催化涂布液，以及光催化功能产物及其使用该光催化剂的制造方法。

公开(公告)号：US20070054044A1

公开(公告)日：2007-03-08

申请号：US10564015

申请日：2004-07-06

申请人： Shinji Shimosaki ,  Tadashi Ogasawara ,  Sadanobu Nagaoka ,  Yasuhiro Masaki

发明人： Shinji Shimosaki ,  Tadashi Ogasawara ,  Sadanobu Nagaoka ,  Yasuhiro Masaki

IPC分类号： C23C16/00

CPC分类号： C23C16/45502 ,  B01J21/06 ,  B01J21/063 ,  B01J35/004 ,  B01J37/0238 ,  C01G23/07 ,  C23C16/405 ,  C23C16/455 ,  C23C16/45568 ,  C23C16/545

摘要： A photocatalytic composite material having a photocatalytic titanium oxide film on the surface of a substrate is produced by a CVD method in which TiCl4 vapor is reacted with water vapor. The TiCl4 vapor and the water vapor are injected into a vapor deposition chamber (9) through nozzles (5) and (6), respectively, such that the resulting two injected vapor streams meet before reaching the substrate, thereby mixing the two vapors. Within 3 seconds after this mixing, the mixed vapors are brought into contact with a substrate (1) which is moving in one direction. Preferably the TiCl4 vapor is injected in a reverse direction with respect to the direction of movement of the substrate through a multi-orifice nozzle (5), while the water vapor is injected through a slit nozzle (6) disposed at a smaller angle with respect to the substrate.

摘要翻译： 在基板表面上具有光催化氧化钛膜的光催化复合材料是通过使TiCl 4气体与水蒸气反应的CVD法制备的。 分别通过喷嘴（5）和（6）将TiCl 4 H 2和水蒸气分别注入蒸镀室（9）中，使得所得到的两个注入的蒸气流在到达衬底 ，从而混合两种蒸气。 在该混合后3秒钟内，使混合蒸气与沿一个方向移动的基板（1）接触。 优选地，相对于基板通过多孔喷嘴（5）的运动方向，反向喷射TiCl 4·4H 2，同时通过狭缝喷嘴（6）注入水蒸汽 ）相对于衬底以较小的角度设置。