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1. 发明授权

US07108935B2 Ion conducting composite membrane materials containing an optionally modified zirconium phosphate dispersed in a polymeric matrix, method for preparation of the membrane material and its use 有权
标题翻译：含有分散在聚合物基质中的任选改性的磷酸锆的离子导电复合膜材料，膜材料的制备方法及其用途
公开(公告)号：US07108935B2
公开(公告)日：2006-09-19
申请号：US10507432
申请日：2003-03-12
申请人： Bernd Bauer , Jacques Roziere , Deborah Jones , Giulio Alberti , Mario Casciola , Monica Pica
发明人： Bernd Bauer , Jacques Roziere , Deborah Jones , Giulio Alberti , Mario Casciola , Monica Pica
IPC分类号： H01M8/10
CPC分类号： H01M8/1009 , H01M8/102 , H01M8/1025 , H01M8/1027 , H01M8/103 , H01M8/1032 , H01M8/1039 , H01M8/1048 , H01M8/1067 , H01M8/1081 , Y02E60/523 , Y02P70/56
摘要： The invention provides composite membrane materials comprising a polymer of the state of art uniformly filled with a zirconium phosphate, preferably α-zirconium phosphate or zirconium phosphate sulfoarylenphosphonate particels. The composite membrane materials are preferably prepared starting from a solution of a polymer of the state of art and from a colloidal dispersion of α-zirconium phosphate or a zirconium phosphate sulfoarylenphosphonate. The colloidal particles are transferred into the solution of the polymer preferably by mixing the dispersion with the solution or by means of phase transfer. The membrane material is preferably obtained by removing the solvent by evaporation or by a suitable non-solvent. Besides the composite membrane materials and the preparation methods, the use of the above membrane materials is claimed as ionomeric membranes with high overall performance in high tempreature, especially hydrogen, and in indirect methanol fuel cells and with decreased methanol crossover in direct methanol fuel cells.
摘要翻译：本发明提供了复合膜材料，其包括均匀填充有磷酸锆，优选α-磷酸锆或磷酸锆磺基亚芳基膦酸盐颗粒的现有技术的聚合物。复合膜材料优选是从现有技术的聚合物的溶液和由α-磷酸锆的磷酸酯或磷酸亚烷基膦酸磷酸酯的胶体分散体开始制备的。优选通过将分散体与溶液混合或通过相转移将胶体颗粒转移到聚合物的溶液中。膜材料优选通过蒸发除去溶剂或通过合适的非溶剂来获得。除了复合膜材料和制备方法外，上述膜材料的使用要求是在高温下，特别是氢气和间接甲醇燃料电池中具有高总体性能的离聚物膜，并且在直接甲醇燃料电池中甲醇交换量降低。

2. 发明申请

US20050118480A1 Ion conducting composite membrane materials containing an optionally modified zirconium phosphate dispersed in a polymeric matrix, method for preparation of the membrane material and its use 有权
标题翻译：含有分散在聚合物基质中的任选改性的磷酸锆的离子导电复合膜材料，膜材料的制备方法及其用途
公开(公告)号：US20050118480A1
公开(公告)日：2005-06-02
申请号：US10507432
申请日：2003-03-12
申请人： Bernd Bauer , Jacques Roziere , Deborah Jones , Giulio Alberti , Mario Casciola , Monica Pica
发明人： Bernd Bauer , Jacques Roziere , Deborah Jones , Giulio Alberti , Mario Casciola , Monica Pica
IPC分类号： C08K3/32 , C08L101/06 , H01B1/06 , H01M8/10 , C08J5/22 , H01B1/24
CPC分类号： H01M8/1009 , H01M8/102 , H01M8/1025 , H01M8/1027 , H01M8/103 , H01M8/1032 , H01M8/1039 , H01M8/1048 , H01M8/1067 , H01M8/1081 , Y02E60/523 , Y02P70/56
摘要： The invention provides composite membrane materials comprising a polymer of the state of art uniformly filled with a zirconium phosphate, preferably α-zirconium phosphate or zirconium phosphate sulfoarylenphosphonate particels. The composite membrane materials are preferably prepared starting from a solution of a polymer of the state of art and from a colloidal dispersion of α-zirconium phosphate or a zirconium phosphate sulfoarylenphosphonate. The colloidal particles are transferred into the solution of the polymer preferably by mixing the dispersion with the solution or by means of phase transfer. The membrane material is preferably obtained by removing the solvent by evaporation or by a suitable non-solvent. Besides the composite membrane materials and the preparation methods, the use of the above membrane materials is claimed as ionomeric membranes with high overall performance in high tempreature, especially hydrogen, and in indirect methanol fuel cells and with decreased methanol crossover in direct methanol fuel cells.
摘要翻译：本发明提供了复合膜材料，其包括均匀填充有磷酸锆，优选α-磷酸锆或磷酸锆磺基亚芳基膦酸盐颗粒的现有技术的聚合物。复合膜材料优选是从现有技术的聚合物的溶液和由α-磷酸锆的磷酸酯或磷酸亚烷基膦酸磷酸酯的胶体分散体开始制备的。优选通过将分散体与溶液混合或通过相转移将胶体颗粒转移到聚合物的溶液中。膜材料优选通过蒸发除去溶剂或通过合适的非溶剂来获得。除了复合膜材料和制备方法外，上述膜材料的使用要求是在高温下，特别是氢气和间接甲醇燃料电池中具有高总体性能的离聚物膜，并且在直接甲醇燃料电池中甲醇交换量降低。

3. 发明授权

US5892080A Mesoporous crystalline acid composition of a diphosphonate-phosphite of a tetravalent metal which can be used as a catalyst 失效
标题翻译：可用作催化剂的四价金属的二膦酸盐 - 亚磷酸盐的介孔结晶酸组合物
公开(公告)号：US5892080A
公开(公告)日：1999-04-06
申请号：US942484
申请日：1997-10-02
申请人： Giulio Alberti , Riccardo Vivani , Chiara Antonini Vitali , Piergiorgio Zapelli
发明人： Giulio Alberti , Riccardo Vivani , Chiara Antonini Vitali , Piergiorgio Zapelli
IPC分类号： B01J31/38 , B01J31/18 , B01J35/10 , C01B25/163 , C07F9/38 , C07F7/00 , B01J31/00
CPC分类号： C07F9/3839 , B01J31/1691 , B01J31/185 , B01J35/1019 , B01J35/1061 , B01J2231/52 , B01J2531/42 , B01J2531/46 , B01J2531/48 , B01J2540/32 , B01J2540/525 , B01J31/069 , B01J31/10
摘要： Solid mesoporous crystalline composition of diphospho-nate-phosphite of a tetravalent metal, with a limited distribution of mesopores having the formulaM�(O.sub.3 P--R--PO.sub.3).sub.1-x-y (HPO.sub.3).sub.2x (O.sub.3 P--R--PO.sub.3 H.sub.2).sub.2y !wherein: M is a tetravalent metal, R is a bivalent organic radical, x varies from 0.3 to 0.6, y varies from 0.05 to 0.3. The process for its production is described, together with its uses and a solid catalyst containing --SO.sub.3 H acid groups, active in the conversion processes of hydrocarbons, which can be obtained from said mesoporous crystalline composition by treatment with a sulfonicphosphonic or arylphosphonic acid, followed, only in the case of treatment with arylphosphonic acid, by sulfonation with a sulfonating agent.
摘要翻译：具有式M [（O3P-R-PO3）1-xy（HPO3）2x（O3P-R-PO3H2）2y]的中孔分布有限的四价金属的双磷酸 - 亚磷酸酯的固体介孔结晶组合物其中： M为四价金属，R为二价有机基团，x为0.3至0.6，y为0.05至0.3。描述了其生产方法及其用途和含有-SO 3 H酸基团的固体催化剂，其在烃的转化过程中有活性，其可以通过用磺酸基膦酸或芳基膦酸处理从所述介孔结晶组合物获得，仅在用芳基膦酸处理的情况下，通过用磺化剂磺化。

4. 发明授权

US5166380A Mesoporous crystalline solid compound of a diphosphonate/phosphite of a tetravalent metal, with a narrow distribution of mesopores 失效
标题翻译：两相金属的二磷酸盐/磷酸盐的多孔结晶固体化合物，具有MESOPORES的窄幅分布
公开(公告)号：US5166380A
公开(公告)日：1992-11-24
申请号：US738891
申请日：1991-08-01
申请人： Giulio Alberti , Umberto Costantino , Riccardo Vivani , Piergiorgio Zappelli , Antonio Rossodivita , Luciano Bassignani
发明人： Giulio Alberti , Umberto Costantino , Riccardo Vivani , Piergiorgio Zappelli , Antonio Rossodivita , Luciano Bassignani
IPC分类号： C07F9/40 , B01J20/02 , B01J29/03 , B01J29/04 , C07F7/00 , C07F9/02 , C07F9/38
CPC分类号： C07F9/3843 , B01J20/223 , B01J29/049 , C07F9/02
摘要： The present invention discloses a compound comprising a diphosphonate/phosphite of a tetravalent metal:M[(O.sub.3 P--R--PO.sub.3).sub.1-(x+y) (HPO.sub.3).sub.2X (O.sub.3 P--R--PO.sub.3 H.sub.2).sub.2y ](where M, R, x and y have the meaning given in the description), in the form of a crystalline solid with an alpha-type lamellar structure with a distance between layers of 7.4 to 20.ANG. (depending on the dimensions of radical R), a BET surface area of 250 to 400m.sup.2 /g, and porosity within the mesopore range, with at least 50% of the pores measuring 20 to 30.ANG.. The compound, depending on the radical R used, may or may not have microporosity in the region between layers. Such a diphosphonate/phosphite of a tetravalent metal is obtained by reaction between diphosphonic acid, phosphorous acid and an oxyhalide of a tetravalent metal, in a solvent comprising dimethyl-sulphoxide/water containing hydrofluoric acid.
摘要翻译：本发明公开了包含四价金属的二膦酸盐/亚磷酸盐的化合物：M [（O3P-R-PO3）1-（x + y）（HPO3）2X（O3P-R-PO3H2）2y]（其中M，R ，x和y具有在描述中给出的含义），具有α层型结构的结晶固体形式，层间距离为7.4至20安培（取决于基团R的尺寸），BET表面面积为250〜400m2 / g，孔隙度在中孔范围内，孔中至少有50％为20〜30 ANGSTROM。取决于所使用的基团R的化合物在层之间的区域中可能具有或可以不具有微孔性。在包含二甲基亚砜/含有氢氟酸的水的溶剂中，通过二膦酸，亚磷酸和四价金属的卤氧化物之间的反应获得四价金属的二膦酸盐/亚磷酸酯。

5. 发明申请

US20070224483A1 Presursor Organic of Tetravalent Metal Phosphates and Pyrophosphates and Their Use for Electrode Modification and for the Preparation of Composite Membrane for Fuel Cells Working at Temperatures>90c and / or at Low Relative Humidity 审中-公开
标题翻译：四价金属磷酸盐和焦磷酸盐的有机物及其用于电极修饰和用于制备温度> 90℃和/或低相对湿度的燃料电池的复合膜的用途
公开(公告)号：US20070224483A1
公开(公告)日：2007-09-27
申请号：US11579146
申请日：2004-08-18
申请人： Giulio Alberti , Monica Pica , Tiziano Tarpanelli
发明人： Giulio Alberti , Monica Pica , Tiziano Tarpanelli
IPC分类号： C01B25/37 , B01D71/02 , C01B25/42 , H01M8/00 , H01G9/00 , B01J27/16
CPC分类号： C01B25/372 , C01B25/42
摘要： The invention is based on the preparation of precursor organic solutions of tetravalent metal phosphates and pyrophosphates with composition M(IV)(O3P—H)2, M(IV)[O2P(OH)2]2[O2PO(OH)] and M(IV)P2O7(M=Zr, Hf, Ti). An important property of these solutions is that the said compounds are formed when the solvent is evaporated. This peculiarity allows an easy insertion of the compounds inside the pores of porous membranes, in polymeric membranes and in the electrodic interfaces of fuel cells. The acid properties of their surfaces, the high thermal stability and the insolubility in water make these particles extremely of interest for improving the efficiency of PEMFCs in the temperature range 90-130° C. The peculiar characteristics of non-water assisted proton conductivity of M(IV)[O2P(OH)2]2[O2PO(OH)] compounds open new prospects for their application in PEMFCs at low relative humidity.
摘要翻译：本发明基于四价金属磷酸盐和焦磷酸盐与前体有机溶液的制备，其组成为M（IV）（O 3 H 3 PH）2，M（IV）[O 2（OH）2 O 2（O 2）PO（OH）]和M（IV）P （M = Zr，Hf，Ti）。这些溶液的重要性质是当溶剂蒸发时形成所述化合物。这种特性允许化合物容易地插入多孔膜的孔中，在聚合物膜和燃料电池的电极界面中。其表面的酸性能，高热稳定性和水中的不溶性使得这些颗粒对于在90-130℃的温度范围内提高PEMFC的效率非常有意义.M的非水辅助质子传导性的特殊特性（Ⅳ）[O 2 P（OH）2]]> compounds compounds compounds compounds compounds compounds compounds compounds compounds compounds compounds compounds compounds compounds compounds compounds compounds compounds compounds compounds compounds compounds compounds compounds compounds compounds compounds compounds 在相对湿度较低的PEMFC中开辟新的应用前景。

6. 发明申请

US20060194702A1 Tetravalent metal acid triphosphates 失效
标题翻译：四价金属酸三磷酸盐
公开(公告)号：US20060194702A1
公开(公告)日：2006-08-31
申请号：US10545091
申请日：2004-02-18
申请人： Giulio Alberti , Riccardo Vivani , Silvia Masci
发明人： Giulio Alberti , Riccardo Vivani , Silvia Masci
IPC分类号： C10M143/02
CPC分类号： B01D67/0093 , B01D69/141 , B01D71/62 , B01J27/16 , C01B25/37 , H01G9/038 , H01G9/155 , H01G11/56 , H01M8/1007 , H01M8/1011 , H01M8/1016 , H01M8/103 , H01M8/1048 , Y02E60/13 , Y02E60/523 , Y02T10/7022
摘要： This invention is based on the preparation of new solid acid triphosphates with compositions of the general formula M(IV)(HPO4)(H2PO4)2, where M(IV) is a tetravalent metal or a mixture of tetravalent metals. These compounds are insoluble in water the greater part of most organic solvents. They show a high non-water assisted protonic conductivity (about 0.01-0.04 S/cm at 100° C. and a relative humidity lower than 1%). These compounds can be used as proton conduction separators in electrochemical devices, to operate at low relative humidity values, as for example in different fuel cells, protonic pumps for electrochemical hydrogenation and dehydrogenation of organic compounds, or for hydrogen production from hydrogenated organic compounds by electro-reforming, or also for removing hydrogen from equilibrium reactions. These compounds can also be used in electrochemical sensors, in super capacitors and as acid catalysts in non-aqueous or anhydrous gaseous phases.
摘要翻译：本发明基于具有通式M（IV）（HPO 4）（H 2 PO 4）2的组成的新的固体酸性三磷酸酯的制备，其中M（IV）是四价金属或四价金属的混合物。这些化合物在大部分有机溶剂中不溶于水。它们显示出非水辅助质子电导率高（在100℃约0.01-0.04S / cm，相对湿度低于1％）。这些化合物可用作电化学装置中的质子传导分离器，以低相对湿度值运行，例如在不同的燃料电池，用于电化学氢化的质子泵和有机化合物的脱氢，或通过电化学从氢化有机化合物产生氢气 - 还原，或从平衡反应中除去氢。这些化合物也可用于电化学传感器，超级电容器和非水或无水气相中的酸催化剂。

7. 发明授权

US07144652B2 Membrane-electrode assembly for polymeric membrane fuel cell 有权
标题翻译：用于聚合物膜燃料电池的膜 - 电极组件
公开(公告)号：US07144652B2
公开(公告)日：2006-12-05
申请号：US10011458
申请日：2001-10-22
申请人： Giulio Alberti , Mario Casciola , Enrico Ramunni , Rubén Ornelas Jacobo
发明人： Giulio Alberti , Mario Casciola , Enrico Ramunni , Rubén Ornelas Jacobo
IPC分类号： H01M4/86
CPC分类号： H01M8/1004 , H01M8/04089 , H01M8/04119 , H01M8/1039 , H01M8/1048 , H01M8/1051 , H01M2008/1095 , H01M2300/0082
摘要： The invention is relative to a membrane-electrode assembly for fuel cells, comprising a state of the art ion-exchange polymeric membrane and state of the art gas diffusion electrodes, whose electrochemical properties are modified through the addition of a hydrophilic component localized in correspondence to one or both the electrodic interfaces and/or one or both the external surfaces of the membrane. The modified membrane-electrode assembly is characterized by high protonic conductivity and high efficiency even in the presence of small quantities of carbon monoxide, or of other contaminants contained in the fuel, even at temperatures as low as 100° C., being also suitable for medium temperature (100–160° C.) operation at relative humidity level lower than saturation.
摘要翻译：本发明涉及用于燃料电池的膜 - 电极组件，其包括现有技术的离子交换聚合物膜和现有技术的气体扩散电极，其电化学性质通过添加相应于膜的一个或两个电极界面和/或一个或两个外表面。改进的膜 - 电极组件的特征在于即使在少量一氧化碳或燃料中包含的其它污染物的情况下，甚至在低至100℃的温度下也具有高质子传导性和高效率，也适用于中等温度（100-160°C），相对湿度低于饱和度。

8. 发明申请

US20050164092A1 Innovative method for the preparation of proton conducting nanopolymeric membranes for use in fuel cells or in catalytic membrane reactors 有权
标题翻译：用于制备用于燃料电池或催化膜反应器的质子传导纳米聚合物膜的创新方法
公开(公告)号：US20050164092A1
公开(公告)日：2005-07-28
申请号：US10508748
申请日：2003-03-20
申请人： Giulio Alberti , Mario Casciola , Monica Pica
发明人： Giulio Alberti , Mario Casciola , Monica Pica
IPC分类号： C08J9/40 , B01D69/14 , B01J19/24 , B01J27/16 , B01J31/02 , B01J31/18 , B01J35/06 , B01J37/02 , C07F7/00 , C07F9/38 , C07F19/00 , C08J5/22 , H01B1/06 , H01M8/02 , H01M8/10 , H01M10/40
CPC分类号： B01J31/185 , B01D69/141 , B01J19/2475 , B01J27/16 , B01J31/0258 , B01J31/0259 , B01J35/065 , B01J37/0201 , B01J2531/38 , B01J2531/42 , B01J2531/46 , B01J2531/48 , C07F9/3834 , C07F9/3843 , C08J5/2275 , C08J5/2287 , C08J2327/16 , H01M8/1044 , H01M8/1048 , H01M8/1062 , H01M8/1067
摘要： The invention is based on the preparation of an organic solution of preferably phosphonic acids and tetravalent metals salts, preferably of Zr, Ti, Sn and Ce, in organic solvents, which behaves as a solution of layered tetravalent metals salts, preferably phosphate-phosphonates, which are completely insoluble in the known solvents. This peculiarity allows an easy insertion of particles of the above compounds in the pores of porous membranes, in the matrices of those polymers, which are soluble in the same organic solvents, as well as in the membrane/electrode interfaces of fuel cells. The use of tetravalent metals salts, preferably zirconium phosphate-phosphonates, possessing high proton conductivity (in some cases higher than 10−1 S cm−1) allows the preparation of impregnated porous membranes and of nano-polymeric membranes combining good mechanical properties, and/or reduced permeability to gaseous species, with good proton conductivity. These membranes can therefore be employed in fuel cells even at temperatures higher than 80° C. These membranes also possess a high catalytic activity and can therefore be employed in catalytic membrane reactors.
摘要翻译：本发明基于在有机溶剂中制备优选膦酸和优选为Zr，Ti，Sn和Ce的四价金属盐的有机溶液，其作为层状四价金属盐，优选磷酸酯 - 膦酸盐的溶液，其完全不溶于已知溶剂。这种特性允许在可溶于相同有机溶剂的那些聚合物的基质以及燃料电池的膜/电极界面中容易地将上述化合物的颗粒插入多孔膜的孔中。使用具有高质子传导性（在某些情况下高于10℃-1cm -1 -1）的四价金属盐，优选磷酸锆磷酸盐，允许制备浸渍多孔膜和纳米聚合物膜结合良好的机械性能和/或降低气态物质的渗透性，具有良好的质子传导性。因此，这些膜即使在高于80℃的温度也可用于燃料电池中。这些膜也具有高催化活性，因此可用于催化膜反应器。

9. 发明授权

US5993768A Mesoporous crystalline composition with a high surface area of a tetravalent metal which can be used as catalyst 失效
标题翻译：介孔结晶组合物具有高表面积的四价金属，可用作催化剂
公开(公告)号：US5993768A
公开(公告)日：1999-11-30
申请号：US999263
申请日：1997-12-29
申请人： Piergiorgio Zappelli , Giulio Alberti , Mario Casciola , Fabio Marmottini , Riccardo Vivani
发明人： Piergiorgio Zappelli , Giulio Alberti , Mario Casciola , Fabio Marmottini , Riccardo Vivani
IPC分类号： B01J27/16 , B01J29/03 , B01J31/18 , C01B25/42 , C01B37/00 , C07F9/38 , C01B25/26
CPC分类号： C07F9/3843 , B01J27/16 , B01J35/1019 , B01J35/1061 , B01J35/108 , C01B25/42
摘要： Solid mesoporous crystalline composition of a pyrophosphate-phosphate of a tetravalent metal, with a high surface area and narrow distribution of the mesopores, having formula (I):M(P.sub.2 O.sub.7).sub.1-z (HPO.sub.4).sub.2z (I)wherein: M is a tetravalent metal and z varies from 0.05 to 0.25.The process for its production is described together with its uses.
摘要翻译：具有式（I）：M（P 2 O 7）1-z（HPO 4）2 z（I）的具有高表面积和中孔分布较窄的四价金属焦磷酸盐 - 磷酸盐的固体介孔结晶组合物其中：M为四价金属和z在0.05至0.25之间变化。描述其生产过程及其用途。

10. 发明授权

US5133857A Solid-state sensor for the determination of concentration of gases which can react with hydrogen 失效
标题翻译：用于确定可与氢反应的气体浓度的固态传感器
公开(公告)号：US5133857A
公开(公告)日：1992-07-28
申请号：US776863
申请日：1991-10-16
申请人： Giulio Alberti , Mario Casciola , Roberto Palombari
发明人： Giulio Alberti , Mario Casciola , Roberto Palombari
IPC分类号： G01N27/26 , G01N27/407 , G01N27/416
CPC分类号： G01N27/4073 , G01N27/4161
摘要： A solid-state sensor for determining the concentration of gases which can react with hydrogen, in particular, of oxygen, which includes a solid-state proton conductor into contact: on the one side, with a reference electrode, constituted in its turn by a metal hydride or a metal alloy, and on the other side with an electrode which catalyses the reaction of the gas to be detected, with said sensor being connected with a power feed system which supplies current or voltage impulses, and with a system which detects the value of potential after each impulse.
摘要翻译：一种固态传感器，用于确定能够与氢反应的气体的浓度，特别是与氧反应的气体的浓度，其包括固体质子导体，其与一个参比电极接触，该基准电极依次由金属氢化物或金属合金，另一侧具有催化待检测气体的反应的电极，所述传感器与供给电流或电压脉冲的供电系统连接，并且与检测每次冲动后的电位值。

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