CN114927706A - Catalyst and preparation method and application thereof - Google Patents

Catalyst and preparation method and application thereof Download PDF

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CN114927706A
CN114927706A CN202210484549.7A CN202210484549A CN114927706A CN 114927706 A CN114927706 A CN 114927706A CN 202210484549 A CN202210484549 A CN 202210484549A CN 114927706 A CN114927706 A CN 114927706A
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catalyst
equal
ceramic
source
anode
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赵凯
陈旻
陈东初
徐庆
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Foshan University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H01M4/9025—Oxides specially used in fuel cell operating at high temperature, e.g. SOFC
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9041—Metals or alloys
    • H01M4/905—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC
    • H01M4/9066—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC of metal-ceramic composites or mixtures, e.g. cermets
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Ceramic Engineering (AREA)
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Abstract

The invention discloses a catalyst, which is a metal-ceramic catalyst with a molecular formula of Ni 1‑m Mo m /Ce 1‑x‑ y Gd x Ca y O 2‑δ Wherein m is more than or equal to 0.001 and less than or equal to 0.5, x is more than or equal to 0.005 and less than or equal to 0.20, y is more than or equal to 0.01 and less than or equal to 0.15, and delta is more than or equal to 1.75 and less than or equal to 1.99. The catalyst prepared according to the technical scheme of the invention not only can realize high-efficiency catalysis on complex hydrocarbon fuel at a lower temperature (700 ℃), but also can realize in-situ regeneration of the catalyst, and is beneficial to improving the comprehensive stability of the battery.

Description

Catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of solid oxide fuel cells, and particularly relates to a catalyst of a solid oxide fuel cell, and a preparation method and application thereof.
Background
The Solid Oxide Fuel Cell (SOFC) is a novel energy conversion device, can directly convert chemical energy in Fuel into electric energy, and has the characteristics of high energy conversion efficiency, environmental friendliness and the like. The SOFC adopts all-solid-state ceramics as a cell component, the operation temperature is 500-900 ℃, hydrogen can be used as fuel, natural gas, shale gas and natural gas hydrate can be used for power generation, and the SOFC has the characteristic of fuel diversity.
The solid oxide fuel cell mostly adopts a metal Ni-based anode as a cell support body so as to be beneficial to high electronic conductivity and high-efficiency catalytic activity of the solid oxide fuel cell. When using hydrocarbon fuels (e.g., methane fuel), the metallic Ni-based anode will catalyze methane cracking, causing anode fouling problems. On one hand, the carbon deposition of the anode reduces the active catalytic reaction area on the surface of the electrode, blocks the electrode and is not beneficial to gas diffusion, so that the performance of the anode is degraded; on the other hand, at the operating temperature of the SOFC, the carbon deposits will react with the metallic Ni-based anode, causing the anode to expand in volume, cracking the cell, and causing the cell to fail.
In order to solve the problem, researchers at home and abroad develop structural design research on the catalytic unit of the fuel cell and provide two cell configurations, namely an external reforming catalytic SOFC and an internal reforming catalytic SOFC. Among them, the internal reforming SOFC has received attention from researchers due to its advantages such as high degree of modularity and small cell system size. The internal reforming SOFC is formed by applying a reforming catalyst layer on the surface of the anode of a single cell of the traditional SOFC to realize the catalytic conversion of hydrocarbon fuel. During cell operation, the complex hydrocarbon fuel is first converted to simple H via a reforming catalyst layer 2 And fuel gas such as CO, newly generated H 2 And CO will diffuse to the fuel cell anode functional layer and participate in the electrochemical oxidation reaction. The fuel catalyst layer can avoid the cracking of complex hydrocarbon fuel in the anode of the battery, reduce the risk of carbon deposition of the anode of the battery and improve the operation stability of the battery.
In the early research, researchers mainly take an SOFC single cell as a support body, prepare a catalytic layer on the surface of an anode, and construct an anode catalytic layer/anode electrochemical layer double-layer anode structure to improve the electrochemical performance of the cell in hydrocarbon fuel. For example, CN103165903A (201110422373.4) prepared a layer of Cu-LSCM-CeO on the surface of the anode of a traditional SOFC single cell 2 A catalyst layer to improve fuel catalytic performance. However, the catalytic activity of Cu-based catalysts for complex hydrocarbon fuels is not yet ideal. CN110600775A (201910936331.9) discloses an in-situ reforming solid oxide fuel cell, which is prepared by preparing metallic Ni-based catalyst on the surface of SOFC anode,to improve the catalytic activity of the catalytic layer. Using Ni-LaMnO 3 The catalyst can improve the chemical catalytic performance of the SOFC single cell, but the stability of the catalyst does not meet the application requirements of the SOFC. Earlier researches also find that the NiMo-zirconia doped cerium oxide catalyst has excellent catalytic performance on isooctane and is applied to an anode catalytic layer of an SOFC single cell for isooctane fuel. However, in the course of the catalytic reaction, the cerium oxide-based catalytic layer undergoes oxidation and reduction processes, causing a change in volume of the catalytic layer, resulting in cracking of the catalytic layer. At the moment, the complex hydrocarbon gas which is not subjected to catalytic conversion can diffuse to the anode electrochemical functional layer through cracks to induce anode carbon deposition, so that the performance of the battery is degraded. Therefore, improving the structural stability of the catalytic layer is the focus of the current research.
In recent years, researchers have proposed a porous YSZ supported SOFC single cell configuration based on the chemical and structural stability of Yttria Stabilized Zirconia (YSZ) materials, with dual functions of mechanical support and chemical catalysis achieved by preparing the catalyst in a porous YSZ support. However, porous YSZ is a catalytically inert material, and using YSZ as a support does not help to optimize the catalytic performance of the cell. On the other hand, the preparation of the YSZ supported SOFC has the problem of high-temperature co-firing of the cell catalyst layer support and the cell electrochemical function layer, which increases the complexity of cell preparation.
Therefore, the development of a catalyst with high catalytic efficiency and wide fuel adaptability is of great significance to the commercial application of the SOFC system.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a catalyst which is used for catalytically converting hydrocarbon fuel into H by applying a catalyst layer on the surface of an SOFC single cell anode 2 And CO to improve the electrochemical performance and stability of the battery. The catalyst of the invention is used at a temperature of 600-750 ℃. On the other hand, the invention adopts the design of the independent anode catalyst layer battery, and the contact mode between the catalyst layer and the battery function layer is physical contact, so that the internal stress caused by structure mismatching can be reduced, and the stability of the battery is improved.
Specifically, the invention is realized by the following method:
in one aspect, the present invention provides a catalyst that is a metal-ceramic type catalyst having the molecular formula Ni 1-m Mo m /Ce 1-x-y Gd x Ca y O 2-δ Wherein m is more than or equal to 0.001 and less than or equal to 0.5, x is more than or equal to 0.005 and less than or equal to 0.20, y is more than or equal to 0.01 and less than or equal to 0.15, and delta is more than or equal to 1.75 and less than or equal to 1.99.
In the invention, Gd and Ca are adopted for composite doping, which is beneficial to improving the catalytic performance of the catalyst. The catalyst in the prior art can effectively catalyze the conversion of hydrocarbon fuel at 750 ℃, when the temperature is reduced to 700 ℃, the catalytic activity is obviously declined, and in order to ensure the catalytic performance, noble metal materials such as Ru and the like are required to be added into a catalyst metal phase, but even under the condition of not using noble metals, the catalytic reaction temperature of the catalyst can not exceed 700 ℃, for example 600-700 ℃, and the catalytic activity is high.
The catalytic process of the catalyst of the invention for hydrocarbon fuels involves the following basic steps: adsorption of hydrocarbon on the surface of a catalyst; secondly, decomposing hydrocarbon on the surface of the catalyst; partial oxidation of hydrocarbon on the surface of catalyst and reduction of catalyst; desorption of newly generated small molecular fuel gas on the surface of the catalyst; catalyst captures oxygen source (e.g. H) 2 O or CO 2 ) But oxidized to an initial state. Wherein, the steps of (i) and (ii) are mainly determined by the influence of the binding energy of the NiMo metal in the catalyst relative to different gas molecules, and the steps of (iii) and (iv) are mainly influenced by the ceramic phase (namely Ce) in the catalyst 1-x- y Gd x Ca y O 2-δ ) Oxygen storage capacity and redox cycle performance.
The ceramic phase of the metal-ceramic catalyst of the present invention is a composite ceramic oxide having a fluorite structure, which has a large amount of oxygen ions and a certain concentration of oxygen vacancies, which represent the absence of oxygen in the crystal structure, forming vacancies. Ce 1-x- y Gd x Ca y O 2-δ Where δ reflects the oxygen vacancy concentration in the material. During the catalytic process, the hydrocarbon fuel may be oxidized at the catalyst surface (corresponding to the transfer of oxygen from the catalyst to the hydrocarbon,catalyst is partially reduced), partial oxidation of the hydrocarbon fuel occurs to produce H 2 And CO.
Meanwhile, in hydrocarbon fuel, carbon on the surface of the catalyst is a main cause of the performance degradation (deactivation) of the catalyst, and in this case, the catalyst is regenerated by introducing a certain oxygen source (for example, air) into the SOFC anode to oxidize the carbon. Therefore, in the catalytic reaction, the catalyst undergoes repeated oxidation-reduction processes, and the oxygen ions and oxygen vacancies in the porous ceramic phase promote the oxidation-reduction processes of the catalyst.
Conventional internal reforming catalytic SOFCs have a monolithic structure with a catalyst layer and a cell anode prepared by a sintering process (which is equivalent to the catalyst layer and the anode layer being tightly bonded together). When the catalyst layer is regenerated in situ, the catalyst is partially oxidized (for example, an oxide layer may be formed on the surface of the metal phase, and the ceramic phase Ce 1-x-y Gd x Ca y O 2-δ And may also be partially oxidized, as a change in delta value), causing the catalytic layer to expand, and because the catalytic layer and the anode layer are tightly bonded together, expansion of a single layer will induce stress, causing cracking of the catalytic layer.
Further, the molecular formula of the catalyst is Ni 0.999 Mo 0.001 /Ce 0.845 Gd 0.005 Ca 0.15 O 1.8475 、Ni 0.85 Mo 0.15 /Ce 0.855 Gd 0.095 Ca 0.05 O 1.9025 Or Ni 0.5 Mo 0.5 /Ce 0.79 Gd 0.2 Ca 0.01 O 1.89 。
Further, Ni in the catalyst 1-m Mo m The content is 2-12 wt%. The proportion of Ni and Mo in the catalyst mainly influences the performance stability of the catalyst, in the process of catalyzing hydrocarbon fuel conversion by the catalyst, the carbon deposition phenomenon can be caused by the cracking of the hydrocarbon fuel on the surface of the catalyst, so that the catalyst is inactivated, and the addition of Mo in the Ni-based metal is beneficial to inhibiting the adsorption of carbon on the surface of the catalyst, so that the carbon deposition inactivation on the surface of the catalyst is relieved.
In particular, Ni in the catalyst 1-m Mo m In an amount of3-11 wt%, 4-10 wt%, 5-9 wt%, 6-8 wt%; preferably, Ni is present in the catalyst 1-m Mo m Is present in an amount of about 2 wt%, about 3 wt%, about 4 wt%, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, about 10 wt%, about 11 wt%, or about 12 wt%.
Further, the catalyst has a porous structure and the pore diameter is 1-20 μm. The porous structure increases the specific surface area of the catalyst, and is more favorable for the diffusion and adsorption of hydrocarbons in the catalyst.
The present invention optimizes the catalytic performance of the catalyst by improving the composition of the ceramic phase thereof, so that it can exhibit catalytic performance equivalent to that of a noble metal-containing catalyst when the reaction temperature is lowered to 700 ℃.
In one aspect, the present invention provides a method for preparing the above catalyst, comprising the steps of:
preparing a ceramic material:
weighing a cerium source, a gadolinium source and a calcium source, and mixing with a solvent to obtain a mixture;
heating, ball milling and calcining the mixture to obtain Ce 1-x-y Gd x Ca y O 2-δ A ceramic material;
preparing a ceramic support body:
ce is mixed 1-x-y Gd x Ca y O 2-δ Ball milling and calcining the ceramic material and the pore-forming agent to obtain porous Ce 1-x-y Gd x Ca y O 2-δ A ceramic support;
Ni 1-m Mo m /Ce 1-x-y Gd x Ca y O 2-δ preparing a catalyst:
preparing Ni source and Mo source into Ni-containing material 2+ And a solution containing Mo 6+ The solution of (1);
mix Ni 2+ Solution and Mo 6+ Solution immersion Ce 1-x-y Gd x Ca y O 2-δ The catalyst is obtained by calcining the ceramic support.
Specifically, the preparation method of the catalyst comprises the following steps:
preparing a ceramic material:
preparing 5-8 wt% polyvinyl alcohol aqueous solution by using polyvinyl alcohol as a raw material;
according to Ce 1-x-y Gd x Ca y O 2-δ Weighing cerium source, gadolinium source and calcium source according to the element metering ratio, dissolving the cerium source, the gadolinium source and the calcium source in a polyvinyl alcohol aqueous solution to obtain a mixture, heating the mixture to 100-300 ℃, evaporating the water to dryness, carrying out a combustion reaction to obtain a product, ball-milling and drying the product by using absolute ethyl alcohol as a medium, calcining the dried product in an air atmosphere at the temperature of 700-1000 ℃ for 1-3h to obtain Ce 1-x-y Gd x Ca y O 2-δ A ceramic material;
preparing a ceramic support:
adding Ce 1-x-y Gd x Ca y O 2-δ Ball milling the ceramic material and pore-forming agent, pressing the mixed powder into a ceramic substrate (with the thickness of 0.1-1.5mm) by adopting a dry pressing method, and calcining at 1300-1500 ℃ for 3-5h to obtain porous Ce 1-x-y Gd x Ca y O 2-δ A ceramic support;
Ni 1-m Mo m /Ce 1-x-y Gd x Ca y O 2-δ preparing a catalyst:
preparing the Ni source and the Mo source into a solution with the concentration of 0.25-1.5 mol L according to the element metering ratio -1 Ni of (2) 2+ An aqueous solution and 0.001 to 0.24mol L of -1 Mo 6+ Aqueous solution, and then Ni is added under pressure of 0.02-0.1atm 2+ Aqueous solution and Mo 6+ Impregnating porous Ce with an aqueous solution 1-x-y Gd x Ca y O 2-δ The ceramic support body is calcined for 0.5 to 2 hours at the temperature of 500 ℃ and 700 ℃ in the air atmosphere to obtain Ni 1-m Mo m /Ce 1-x-y Gd x Ca y O 2-δ A catalyst.
Most of traditional internal reforming catalytic SOFC (solid oxide fuel cell) anode catalyst layers take a cell anode (or a single cell) as a support body, the catalyst layers do not have self-supporting property, the catalyst layers and the cell anode are prepared into a whole through a sintering process, and a multi-layer anode structure (such as an anode catalyst layer and an anode electrochemical functional layer) needs to meet a strict thermal expansion coefficient matching condition so as to ensure the structural stability of the cell in the temperature rising and falling processes (if the thermal expansion coefficients of the cell anode catalyst layer and the anode electrochemical functional layer are not matched, the cell may crack the functional layer due to internal stress in the temperature rising and falling processes, so that the structural stability of the cell is reduced). The catalyst material prepared in the invention is composed of a ceramic substrate and has self-supporting property. The method is not required to be attached to a single SOFC cell, namely, the problem of thermal expansion coefficient matching is not considered. In the process of assembling the battery, the anode catalyst layer is only needed to be placed on the surface of the battery anode, and the catalyst layer and the battery anode are not needed to be sintered into a whole by adopting a sintering process, so that the expansion and the contraction of the catalyst and the anode are relatively independent in the processes of temperature rise and temperature reduction, and the stability of the whole structure of the battery is further improved.
Further, in the preparation process of the ceramic material, the cerium source is selected from cerium nitrate or cerium acetate, the gadolinium source is selected from gadolinium nitrate or gadolinium acetate, and the calcium source is selected from calcium nitrate or calcium acetate; the solvent is 5-8 wt% polyvinyl alcohol water solution.
Further, in the preparation process of the ceramic material, the heating temperature of the mixture is 100-.
Specifically, in the preparation process of the ceramic material, the heating temperature of the mixture is 150-250 ℃; preferably, the mixture is heated at a temperature of about 100 ℃, about 150 ℃, about 200 ℃, about 250 ℃ or about 300 ℃.
Specifically, in the preparation process of the ceramic material, the calcination temperature is 750-950 ℃, 800-900 ℃ or 850-900 ℃; preferably, the calcination temperature is about 700 ℃, about 750 ℃, about 800 ℃, about 850 ℃, about 900 ℃, about 950 ℃ or about 1000 ℃.
Specifically, in the preparation process of the ceramic material, the calcination time is 1.5-2.5h or 1.5-2 h; preferably, the calcination time is about 1h, about 1.5h, about 2h, about 2.5h, or about 3 h.
Further, in the preparation process of the ceramic support, the pore-forming agent is selected from polymethyl methacrylate, carbon powder or starch, the calcination temperature is 1300-1500 ℃, and the calcination time is 3-5 h. During the calcination, the pore-forming agent is ablated, thereby obtaining the porous ceramic substrate.
Specifically, in the preparation process of the ceramic support, the calcination temperature is 1350-; preferably, the calcination temperature is about 1300 ℃, about 1350 ℃, about 1400 ℃, about 1450 ℃, or about 1500 ℃.
Specifically, in the preparation process of the ceramic support body, the calcination time is 3.5-4.5h or 3.5-4 h; preferably, the calcination temperature is about 3 hours, about 3.5 hours, about 4 hours, about 4.5 hours, or about 5 hours.
Further, Ni 1-m Mo m /Ce 1-x-y Gd x Ca y O 2-δ During the preparation of the catalyst, the Ni source is selected from Ni (NO) 3 ) 2 ·6H 2 O or nickel acetate, Mo source is selected from (NH) 4 ) 6 Mo 7 O 24 ·6H 2 O；Ni 2+ Solution and Mo 6+ The solution is impregnated with Ce by vacuum impregnation 1-x- y Gd x Ca y O 2-δ A ceramic support; the calcination temperature is 500-700 ℃, and the calcination time is 0.2-5 h.
Further, Ni is added under a pressure of 0.02 to 0.1atm 2+ Solution and Mo 6+ Solution impregnation in porous Ce 1-x- y Gd x Ca y O 2-δ A ceramic support.
Preferably, Ni 2+ The solution is Ni 2+ Aqueous solution of Mo 6+ The solution is Mo 6+ An aqueous solution.
In another aspect, the present invention provides a battery anode comprising an anode layer and the above-described catalyst.
Further, the cell anode is preferably a SOFC single cell anode.
In yet another aspect, the invention provides a cell comprising a cell anode as described above.
Further, the single cell is preferably an SOFC single cell.
According to the technical scheme of the invention, the method has the following beneficial effects: high efficiency of complex hydrocarbon fuel (methanol, ethanol, isooctane and the like) can be realized at lower temperature (for example, 600-700℃)And the catalyst can be catalyzed, and the in-situ regeneration of the catalyst can be realized, so that the comprehensive stability of the battery is improved. On the other hand, the invention adopts the independent design of the anode catalyst layer, can reduce the internal stress caused by the structure mismatching in the integral design of the anode catalyst layer/the anode electrochemical function layer, and improves the stability of the battery. The anode catalyst of the present invention is composed of porous Ce 1-x-y Gd x Ca y O 2-δ The ceramic support body can not only provide reactive active sites for the conversion of hydrocarbon fuel, but also inhibit oxygen source (O) in the hydrocarbon fuel 2 ，H 2 O) and the like are directly contacted with an anode electrochemical functional layer, so that local oxidation of the metal-based anode is avoided; meanwhile, excessive oxidant (such as air) can be input into the anode to oxidize carbon deposition in the catalyst layer, so that the inactivation and regeneration of the catalyst are realized, and the catalytic stability is further improved.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description.
Drawings
The invention is further described with reference to the following figures and examples, in which:
FIG. 1 shows the results of three-point bending strength tests of the metal-ceramic catalyst layer according to the present invention;
FIG. 2 is Ce prepared by the embodiment of the invention 1-x-y Gd x Ca y O 2-δ XRD test results of the ceramic phase;
FIG. 3 shows Ni prepared according to an example of the present invention 1-m Mo m /Ce 1-x-y Gd x Ca y O 2-δ XRD test results of the metal-ceramic type catalyst;
FIG. 4 shows Ni prepared in example 2 of the present invention 1-m Mo m /Ce 1-x-y Gd x Ca y O 2-δ SEM test results of metal-ceramic type catalysts;
fig. 5 is a schematic structural diagram of a SOFC single cell with a separate catalytic layer prepared by an embodiment of the present invention;
fig. 6 is an SEM photograph of a SOFC single cell with a separate catalytic layer prepared by an example of the present invention;
FIG. 7 shows Ni prepared by an example of the present invention 1-m Mo m /Ce 1-x-y Gd x Ca y O 2-δ A test device map of the layer versus the catalytic performance of the hydrocarbon fuel;
FIG. 8 is a high temperature fuel cell test setup to study the electrochemical performance of a SOFC single cell;
FIG. 9 shows Ni prepared in example 2 of the present invention 1-m Mo m /Ce 1-x-y Gd x Ca y O 2-δ Catalytic layer pair CH 4 The catalytic performance test result of the partial oxidation reforming reaction;
FIG. 10 shows Ni prepared according to example 1 of the present invention at different test temperatures 1-m Mo m /Ce 1-x-y Gd x Ca y O 2-δ Catalytic layer pair CH 4 The result of the catalytic performance stability test of (2);
FIG. 11 shows the results of the catalyst prepared in example 2 of the present invention catalyzing complex liquid hydrocarbon fuel conversion;
FIG. 12 shows Ni prepared in example 3 of the present invention 1-m Mo m /Ce 1-x-y Gd x Ca y O 2-δ Catalyst layer pair C 2 H 5 The catalytic performance test result of the OH fuel;
FIG. 13 shows Ni prepared in example 2 of the present invention 1-m Mo m /Ce 1-x-y Gd x Ca y O 2-δ Catalyst layer pair C 8 H 18 The catalytic performance test results of the fuel;
FIG. 14 shows Ni prepared in example 1 of the present invention 1-m Mo m /Ce 1-x-y Gd x Ca y O 2-δ The influence of the catalytic layer on the electrochemical performance of the SOFC single cell is obtained;
fig. 15 shows the performance stability test results of the SOFC single cell prepared in example 1 of the present invention in methane fuel at 700 ℃.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative, and is not to be construed as limiting the invention.
Wherein the materials are commercially available unless otherwise specified, and the methods are conventional unless otherwise specified.
Example 1
Preparing a ceramic material:
preparing 5 wt% polyvinyl alcohol aqueous solution from polyvinyl alcohol as raw material according to Ce 0.845 Gd 0.005 Ca 0.15 O 1.8475 Weighing 7.338g of cerium nitrate, 0.045g of gadolinium nitrate and 0.708g of calcium nitrate according to the stoichiometric ratio of metal elements, dissolving the cerium nitrate, the gadolinium nitrate and the calcium nitrate in a polyvinyl alcohol aqueous solution, obtaining a mixture after the raw materials are completely dissolved, moving the mixture on a heating plate, heating the mixture to 200 ℃, evaporating water to dryness until combustion reaction occurs to obtain a combustion product, ball-milling the product on a spheroidal graphite machine for 24 hours by taking absolute ethyl alcohol as a medium, drying the product at 80 ℃ after ball-milling, and calcining the product at 850 ℃ in an air atmosphere for 2 hours to obtain Ce 0.845 Gd 0.005 Ca 0.15 O 1.8475 And (3) powder.
Preparing a ceramic support body:
adding Ce 0.845 Gd 0.005 Ca 0.15 O 1.8475 Ball-milling and mixing with polymethyl methacrylate, pressing the mixed powder into a disc-shaped ceramic substrate with the diameter of 30mm and the thickness of 1mm by a dry pressing method, and calcining the ceramic substrate at 1400 ℃ for 4h in air atmosphere to obtain Ce 0.845 Gd 0.005 Ca 0.15 O 1.8475 A ceramic matrix.
Ni 1-m Mo m /Ce 1-x-y Gd x Ca y O 2-δ Preparing a catalyst:
with Ni (NO) 3 ) 2 ·6H 2 O and (NH) 4 ) 6 Mo 7 O 24 ·6H 2 O as a raw material, based on Ni 0.999 Mo 0.001 The preparation concentration of the medium metal element is 0.999mol L -1 Ni 2+ And 0.001mol L -1 Mo 6+ Aqueous solution of Ni under a pressure of 0.1atm 2+ And Mo 6+ Ion impregnation into porous Ce 0.845 Gd 0.005 Ca 0.15 O 1.8475 Ceramic matrixCalcining in air atmosphere at 600 ℃ for 1h in pores to obtain Ni 0.999 Mo 0.001 /Ce 0.845 Gd 0.005 Ca 0.15 O 1.8475 Catalyst, the impregnation process was repeated 6 times to obtain a metal-ceramic type catalyst layer.
Example 2
Preparing a ceramic material:
preparing 5 wt% polyvinyl alcohol aqueous solution from polyvinyl alcohol as raw material according to Ce 0.855 Gd 0.095 Ca 0.05 O 1.9025 7.425g of cerium nitrate, 0.858g of gadolinium nitrate and 0.236g of calcium nitrate are weighed according to the stoichiometric ratio of metal elements, the cerium nitrate, the gadolinium nitrate and the calcium nitrate are dissolved in a polyvinyl alcohol aqueous solution to obtain a mixture after the raw materials are completely dissolved, the mixture is moved to a heating plate to be heated to 200 ℃, the moisture is evaporated to dryness until a combustion reaction occurs to obtain a combustion product, the product is ball-milled for 24 hours on a spheroidal graphite machine by taking absolute ethyl alcohol as a medium, the product is dried at 80 ℃ after ball milling, and is calcined for 2 hours at 850 ℃ in an air atmosphere to obtain Ce 0.855 Gd 0.095 Ca 0.05 O 1.9025 And (3) powder.
Preparing a ceramic support body:
adding Ce 0.855 Gd 0.095 Ca 0.05 O 1.9025 Ball-milling and mixing with polymethyl methacrylate, pressing the mixed powder into a disc-shaped ceramic substrate with the diameter of 30mm and the thickness of 1mm by a dry pressing method, and calcining the ceramic substrate at 1400 ℃ for 4h in air atmosphere to obtain Ce 0.855 Gd 0.095 Ca 0.05 O 1.9025 A ceramic matrix.
Ni 1-m Mo m /Ce 1-x-y Gd x Ca y O 2-δ Preparing a catalyst:
with Ni (NO) 3 ) 2 ·6H 2 O and (NH) 4 ) 6 Mo 7 O 24 ·6H 2 O as a raw material, based on Ni 0.85 Mo 0.15 The preparation concentration of the medium metal elements is 0.85mol L -1 Ni 2+ And 0.15mol L -1 Mo 6+ Aqueous solution of Ni under a pressure of 0.1atm 2+ And Mo 6+ Ion impregnation into porous Ce 0.855 Gd 0.095 Ca 0.05 O 1.9025 Calcining the ceramic matrix in the pores for 1h at 600 ℃ in an air atmosphere to obtain Ni 0.85 Mo 0.15 /Ce 0.855 Gd 0.095 Ca 0.05 O 1.9025 Catalyst, the impregnation process was repeated 6 times to obtain a metal-ceramic type catalyst layer.
Example 3
Preparing a ceramic material:
preparing 5 wt% polyvinyl alcohol aqueous solution from polyvinyl alcohol as raw material according to Ce 0.79 Gd 0.2 Ca 0.01 O 1.89 Weighing 6.861g of cerium nitrate, 1.805g of gadolinium nitrate and 0.047g of calcium nitrate according to the stoichiometric ratio of metal elements, dissolving the cerium nitrate, the gadolinium nitrate and the calcium nitrate in a polyvinyl alcohol aqueous solution, obtaining a mixture after the raw materials are completely dissolved, moving the mixture on a heating plate, heating the mixture to 200 ℃, evaporating water to dryness until combustion reaction occurs to obtain a combustion product, ball-milling the product on a spheroidal graphite machine for 24 hours by taking absolute ethyl alcohol as a medium, drying the product at 80 ℃ after ball-milling, and calcining the product at 850 ℃ in an air atmosphere for 2 hours to obtain Ce 0.79 Gd 0.2 Ca 0.01 O 1.89 And (3) powder.
Preparing a ceramic support:
ce is mixed 0.79 Gd 0.2 Ca 0.01 O 1.89 Ball-milling and mixing with polymethyl methacrylate, pressing the mixed powder into a disc-shaped ceramic substrate with the diameter of 30mm and the thickness of 1mm by a dry pressing method, and calcining the ceramic substrate at 1400 ℃ for 4h in air atmosphere to obtain Ce 0.79 Gd 0.2 Ca 0.01 O 1.89 A ceramic matrix.
Ni 0.5 Mo 0.5 /Ce 0.79 Gd 0.2 Ca 0.01 O 1.89 Preparing a catalyst:
with Ni (NO) 3 ) 2 ·6H 2 O and (NH) 4 ) 6 Mo 7 O 24 ·6H 2 O as a raw material, based on Ni 0.5 Mo 0.5 The preparation concentration of the medium metal element is 0.5mol L -1 Ni 2+ And 0.5mol L -1 Mo 6+ Aqueous solution at a pressure of 0.1atmMix Ni 2+ And Mo 6+ Ion impregnation into porous Ce 0.79 Gd 0.2 Ca 0.01 O 1.89 Calcining the ceramic matrix in the pores for 1h at 600 ℃ in an air atmosphere to obtain Ni 0.5 Mo 0.5 /Ce 0.79 Gd 0.2 Ca 0.01 O 1.89 Catalyst, the impregnation process was repeated 6 times to obtain a metal-ceramic type catalyst layer.
And (3) performance testing:
the metal-ceramic type catalyst layer prepared in example 1 was subjected to a three-point bending strength test, and the results are shown in fig. 1. It can be seen that the fracture strength of the prepared metal-ceramic catalyst layer is 23MPa, and the SOFC support meets the requirement on mechanical performance (SOFC requires that the fracture strength of a matrix is more than 20 MPa).
XRD test of the ceramic phases prepared in examples 1 to 3, wherein (a) is the ceramic phase prepared in example 1, (b) is the ceramic phase prepared in example 2, and (c) is the ceramic phase prepared in example 3, showed that the Ce having fluorite structure can be obtained by the combustion method of polyvinyl alcohol, and the test results are shown in FIG. 2 1-x-y Gd x Ca y O 2-δ A ceramic material.
XRD test results of the metal-ceramic type catalysts prepared in examples 1 to 3, in which (a) is the catalytic layer prepared in example 1, (b) is the catalytic layer prepared in example 2, and (c) is the catalytic layer prepared in example 3, are shown in fig. 3, show that: ni was observed in the range of 40-55 ° 2 θ 1-m Mo m The corresponding XRD diffraction peak shows that Ni can be prepared by the preparation process of the invention 1-m Mo m /Ce 1-x-y Gd x Ca y O 2-δ Metal-ceramic type catalysts.
The SEM test results of the metal-ceramic type catalyst prepared in example 2 are shown in fig. 4, and the results show that the porosity of the porous catalytic layer is 35 to 40%, which meets the application requirements of the fuel cell. FIG. 4(b) is a photograph showing a high magnification structure of the catalytic layer in porous Ce 0.855 Gd 0.095 Ca 0.05 O 1.9025 Uniformly distributed nano-scale Ni can be observed on the surface of the ceramic framework 0.85 Mo 0.15 The results of SEM tests show that Ni with uniformly distributed metal phase can be obtained by the preparation method of the invention 0.85 Mo 0.15 /Ce 0.855 Gd 0.095 Ca 0.05 O 1.9025 A catalytic layer.
FIG. 5 is a schematic diagram of a single cell SOFC with a separate catalytic layer, made of Ni 1-m Mo m /Ce 1-x-y Gd x Ca y O 2-δ The catalytic layer and the SOFC electrochemical functional layer (the functional layer comprises NiO-YSZ anode layer/(ZrO) 2 ) 0.92 (Y 2 O 3 ) 0.08 /Ce 0.8 Sm 0.2 O 1.9 Double layer electrolyte layer/La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ A cathode layer). Ni 1-m Mo m -Ce 1-x-y Gd x Ca y O 2-δ The thickness of the catalytic layer is 0.1-1.5mm, the thickness of the NiO-YSZ anode layer is 0.1-1.5mm, and the thickness of other battery functional layers is 5-100 mu m.
FIG. 6 is an SEM photograph of an SOFC single cell with a separate catalytic layer prepared in example 2, and it can be seen that the anode and the cathode of the cell have a porous microstructure characteristic of YSZ/Ce 0.8 Sm 0.2 O 1.9 The electrolyte is relatively compact, the contact among different functional layers of the battery is good, the anode supporting type single battery can be prepared by adopting the process of the invention, and independent Ni is used 0.85 Mo 0.15 /Ce 0.855 Gd 0.095 Ca 0.05 O 1.9025 The anode catalyst layer is applied to the anode surface of the single cell to obtain the hydrocarbon fuel SOFC single cell with reforming catalysis function.
FIG. 7 shows Ni of the present invention 1-m Mo m /Ce 1-x-y Gd x Ca y O 2-δ The performance of the catalytic layer was investigated using a quartz tube reactor with an internal diameter of 7 mm. Firstly, crushing a catalyst layer supporting body, weighing 0.3g of crushed powder, placing the crushed powder in a quartz tube reactor, fixing the crushed powder in the middle of the quartz tube by adopting quartz cotton, monitoring the catalytic reaction temperature by adopting a K-type thermocouple, and respectively carrying out O reaction at the temperature of 700 ℃ and 750 DEG C 2 The reforming catalytic performance of the catalyst on hydrocarbon fuel was investigated by gas chromatography at a/C ratio of 0.5.
(1) When methane (CH) is used 4 ) When the fuel is used, the flow rate of methane is 50mL/min, the air flow rate is 125mL/min, and the fuel conversion rate and H are calculated by the following formula 2 And yield of CO:
methane conversion rate (CO and CO) 2 The sum of moles of (a)/(the moles of input methane);
H 2 yield ═ H 2 Moles/(2 x moles of input methane);
CO yield is moles CO/moles input methane.
(2) When methanol (CH) is used 3 OH) as fuel, the flow rate of liquid methanol was 0.09mL/min and the flow rate of nitrogen was 100mL/min, and the fuel conversion and H were calculated using the following formulas 2 And CO yield:
methanol conversion (CO and CO) 2 The sum of moles of (c)/(moles of methanol input);
H 2 yield ═ H 2 (2 x input moles of methanol);
CO yield-moles of CO/moles of methanol input.
(3) When ethanol (C) is used 2 H 5 OH) is the fuel. The flow rate of the liquid ethanol was 0.065mL/min, the air flow rate was 62.5mL/min, and the fuel conversion and H were calculated by the following formulas 2 And CO yield:
conversion rate of ethanol (CO, CO) 2 And the sum of the moles of methane)/(2 x moles of ethanol input);
H 2 yield ═ H 2 (3 x moles of ethanol input);
CO yield-moles of CO/(moles of ethanol input 2).
(4) When isooctane (C) is used 8 H 18 ) When the fuel is used, the flow rate of liquid isooctane is 0.046mL/min, the air flow rate is 125mL/min, and the fuel conversion rate and H are calculated by adopting the following formulas 2 And CO yield:
isooctane conversion rate (CO, CO) 2 And the sum of the moles of methane)/(moles of 8 × input isooctane);
H 2 yield ═ H 2 (iv) moles/(9 x moles of iso-octane input);
CO yield-moles of CO/(moles of 8 × input isooctane).
FIG. 8 shows a high temperature fuel cell testing device for studying electrochemical performance of SOFC single cells, in which Al is adopted in the present invention 2 O 3 And sealing the battery sample by using the ceramic sealant, and raising the temperature of the battery to 700 ℃ for electrochemical performance test. When hydrogen is used as a fuel, the hydrogen is directly input into the anode port of the cell; when hydrocarbon is used as fuel, the mixed gas of hydrocarbon and air is introduced into the anode port of the fuel cell, and the flow rate of the hydrocarbon and the air is controlled to regulate and control O in the anode fuel 2 The ratio of/C.
FIG. 9 shows O at 700 ℃ 2 Ni prepared in example 2 with a C ratio of 0.5 0.85 Mo 0.15 /Ce 0.855 Gd 0.095 Ca 0.05 O 1.9025 Catalytic layer pair CH 4 Catalytic performance of partial oxidation reforming reactions. When Ni is in the catalyst 1-m Mo m When the mass fraction of (2) is increased to 8 wt%, the methane conversion rate is gradually increased from 40% to 82%, and simultaneously, H 2 The yield is increased from 29% to 75%, and the CO yield is increased from 22% to 36%, indicating that the increase of Ni 1-m Mo m The content is favorable for promoting the conversion of methane in the catalytic layer, and Ni is further increased 1-m Mo m When the content is 12 wt%, the catalytic performance of the catalyst is not obviously changed. On the one hand, with porous Ce 1-x-y Gd x Ca y O 2-δ In Ni 1-m Mo m Increased content of catalytically active centers (Ni) 1-m Mo m /Ce 1-x-y Gd x Ca y O 2-δ Metal/ceramic interface) is close to saturation, resulting in no significant improvement in catalytic performance; on the other hand, too high Ni incorporation into the catalyst 1-m Mo m The metal phase content will induce high temperature sintering of the catalyst,reducing the catalytic performance. Thus, when Ni is present in the catalyst 1-m Mo m When the content is increased from 8 wt% to 12 wt%, the performance of the catalyst has no obvious change.
FIG. 10 is O 2 Ni prepared in example 1at different test temperatures (700 ℃ and 750 ℃) at a C of 0.5 0.999 Mo 0.001 /Ce 0.845 Gd 0.005 Ca 0.15 O 1.8475 Catalytic layer pair CH 4 The stability of the catalytic performance of (2) was investigated. The results show that: ni at 700-750 deg.C 1-m Mo m /Ce 1-x-y Gd x Ca y O 2-δ The catalyst can realize stable catalysis on methane. When the reaction temperature is 700 ℃, the conversion rate of methane is 80 percent, and H 2 And CO yields of 70% and 36%, respectively; when the reaction temperature was increased to 750 ℃, the methane conversion increased to 94%, H 2 And CO yields of 80% and 42%, respectively.
FIG. 11 is a graph of the results of the catalyst of the present invention catalyzing complex liquid hydrocarbon fuel conversions. FIG. 11 compares Ni prepared in example 2 0.85 Mo 0.15 /Ce 0.855 Gd 0.095 Ca 0.05 O 1.9025 Catalytic layer partial oxidation reforming performance on methanol at 700 ℃ and 750 ℃. At O 2 Under the catalytic reaction condition that the ratio of C to C is 0.5, the conversion rate of the methanol fuel is 80-90 percent, and the H content is 2 And CO yields of 70-80% and 35-40%, respectively.
FIGS. 12-13 show Ni prepared in example 3 1-m Mo m /Ce 1-x-y Gd x Ca y O 2-δ Catalyst layer pair C 2 H 5 OH and Ni prepared in example 2 0.85 Mo 0.15 /Ce 0.855 Gd 0.095 Ca 0.05 O 1.9025 Catalyst layer C 8 H 18 And (4) testing the catalytic performance of the fuel. As shown in FIGS. 12-13, at O 2 The ratio of Ni to C is 0.5, the catalytic reaction temperature is 700-750 DEG, Ni 1-m Mo m -Ce 1-x-y Gd x Ca y O 2-δ The catalyst layer can realize high-efficiency catalysis on the hydrocarbon fuel. For SOFC, the reduction of the working temperature is beneficial to inhibiting the high-temperature aging of materials, reducing the complexity of the system and improving the battery systemThe system stability is of great significance to SOFC commercialization.
FIG. 14 shows Ni prepared in investigation example 1 0.999 Mo 0.001 /Ce 0.845 Gd 0.005 Ca 0.15 O 1.8475 The effect of the catalytic layer on the electrochemical performance of the SOFC single cell. The results show that: application of Ni 1-m Mo m /Ce 1-x-y Gd x Ca y O 2-δ After the catalytic layer (see fig. 14(a)), the maximum output power density of the cell in standard hydrogen fuel was 509mW/cm 2 When the fuel is converted into isooctane, the maximum output power density is 303mW/cm 2 The cell can maintain 60% of its original performance (that of a standard hydrogen fuel). Whereas the prior art fuel cell without a catalytic layer (see FIG. 14(b)) had a maximum output power density of 552mW/cm in a standard hydrogen fuel at 700 deg.C 2 When the fuel is converted into isooctane, the maximum output power density is 250mW/cm 2 The performance is reduced by 54.7%. The maximum output power density in isooctane of the cell using the catalytic layer compared with the cell without the catalytic layer is 250mW/cm 2 Increased to 303mW/cm 2 The performance is improved by 20 percent, and the high-efficiency catalytic function of the catalyst in the fuel cell is proved.
Fig. 15 shows the performance stability of SOFC single cells in methane fuel at 700 ℃. As shown in FIG. 15(a), at 300mA/cm 2 Under the discharge current density of the battery, the voltage decay rate of a single cell without a catalyst layer in the first 9 hours is 11.3mV/h, and the performance of the battery is degraded after the carbon deposition of the anode is activated by adopting the in-situ activation of the anode (oxidation reduction: the carbon deposition in the catalyst is eliminated by introducing 15mL/min into the anode of the battery for 5 minutes). For cells without a free standing catalytic layer, this reactivation process may lead to anodic oxidation, reducing the electrochemical performance and stability of the cell. Application of Ni prepared in example 1 to the surface of SOFC Single cell Anode 0.999 Mo 0.001 /Ce 0.845 Gd 0.005 Ca 0.15 O 1.8475 After the catalyzed layer, the cell showed excellent performance stability during the first 16 hours of operation at 300mA/cm as shown in FIG. 15(b) 2 At a current density of only the voltage decay rate of1.8mV/h, after the catalyst is added and the in-situ activation treatment is carried out (oxidation reduction: 15mL/min is introduced into the anode of the battery for 5 minutes), the comprehensive voltage decay is reduced to 1.1mV/h, and the voltage decay rate of the battery is reduced by 39%. This result demonstrates the promotion of catalyst in situ activation on cell stability.
The embodiments of the present invention have been described in detail with reference to the drawings, but the present invention is not limited to the embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.

Claims (11)

1. A catalyst, characterized in that the catalyst is a metal-ceramic type catalyst with a molecular formula of Ni 1-m Mo m /Ce 1-x-y Gd x Ca y O 2-δ Wherein m is more than or equal to 0.001 and less than or equal to 0.5, x is more than or equal to 0.005 and less than or equal to 0.20, y is more than or equal to 0.01 and less than or equal to 0.15, and delta is more than or equal to 1.75 and less than or equal to 1.99.
2. The catalyst of claim 1 wherein the catalyst has the formula Ni 0.999 Mo 0.001 /Ce 0.845 Gd 0.005 Ca 0.15 O 1.8475 、Ni 0.85 Mo 0.15 /Ce 0.855 Gd 0.095 Ca 0.05 O 1.9025 Or Ni 0.5 Mo 0.5 /Ce 0.79 Gd 0.2 Ca 0.01 O 1.89 。
3. Catalyst according to claim 1 or 2, characterized in that Ni in the catalyst 1-m Mo m The content is 2-12 wt%.
4. A catalyst according to any one of claims 1 to 3, characterized in that the catalyst has a porous structure with pore sizes in the range of 1 to 20 μm.
5. A process for preparing a catalyst as claimed in any one of claims 1 to 4, characterized by comprising the steps of:
preparing a ceramic material:
weighing a cerium source, a gadolinium source and a calcium source, and mixing with a solvent to obtain a mixture;
heating, ball milling and calcining the mixture to obtain Ce 1-x-y Gd x Ca y O 2-δ A ceramic material;
preparing a ceramic support body:
adding Ce 1-x-y Gd x Ca y O 2-δ Ball milling and calcining the ceramic material and the pore-forming agent to obtain porous Ce 1-x-y Gd x Ca y O 2-δ A ceramic support;
Ni 1-m Mo m /Ce 1-x-y Gd x Ca y O 2-δ preparing a catalyst:
preparing Ni source and Mo source into Ni-containing material 2+ And a solution containing Mo 6+ The solution of (1);
mix Ni 2+ Solution and Mo 6+ Solution immersion Ce 1-x-y Gd x Ca y O 2-δ And calcining the ceramic support to obtain the catalyst.
6. The preparation method according to claim 5, wherein during the preparation of the ceramic material, the cerium source is selected from cerium nitrate or cerium acetate, the gadolinium source is selected from gadolinium nitrate or gadolinium acetate, and the calcium source is selected from calcium nitrate or calcium acetate; the solvent is 5-8 wt% polyvinyl alcohol water solution.
7. The method as claimed in claim 5, wherein the heating temperature of the mixture is 300 ℃ and the ball milling medium is absolute ethanol, the ball milling time is 12-48h, the calcining temperature is 1000 ℃ and the calcining time is 1-3 h.
8. The preparation method as claimed in claim 5, wherein in the preparation process of the ceramic support, the pore-forming agent is selected from polymethyl methacrylate, carbon powder or starch, the calcination temperature is 1300-1500 ℃, and the calcination time is 3-5 h.
9. The method of claim 5, wherein Ni is 1-m Mo m /Ce 1-x-y Gd x Ca y O 2-δ The Ni source is selected from Ni (NO) during the preparation of the catalyst 3 ) 2 ·6H 2 O or nickel acetate, Mo source is selected from (NH) 4 ) 6 Mo 7 O 24 ·6H 2 O；Ni 2+ Solution and Mo 6+ The solution is impregnated with Ce by vacuum impregnation 1-x-y Gd x Ca y O 2-δ A ceramic support; the calcination temperature is 500-700 ℃, and the calcination time is 0.2-5 h.
10. A battery anode, comprising an anode layer and the catalyst of any of claims 1-4.
11. A cell comprising the battery anode of claim 10.
CN202210484549.7A 2022-05-06 2022-05-06 Catalyst and preparation method and application thereof Pending CN114927706A (en)

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