Cobalt and copper-doped nickel ferrite nanoparticles as catalyst for direct methanol fuel cells

Abstract

Cobalt and copper-doped nickel Cu/CoNi-ferrite nanoparticles having a general formula Cu.sub.xCo.sub.xNi.sub.(1-x)Fe.sub.2O.sub.4 can be a catalyst for electrooxidation of methanol in direct methanol fuel cells (DMFC). The catalyst can be an efficient anode for DMFC in alkaline electrolytes. The Cu/CoNi-ferrite nanoparticles can have a sponge-like structure with irregular pores. A diameter of the Cu/CoNi-ferrite nanoparticles can range from about 8 nm to about 30 nm.

Claims

1. A method of preparing cobalt and copper-doped nickel ferrite nanoparticles, comprising: preparing a gel including iron nitrate, cobalt nitrate, nickel nitrate, copper nitrate, and a capping agent; drying the gel to provide a dried gel, wherein drying the gel comprises heating the gel to a temperature ranging from about 90 C. to about 110 C. for a period of time ranging from about 8 hours to about 12 hours; burning the dried gel to provide a brittle mass, wherein burning the dried gel includes heating the dried gel at a temperature ranging from about 165 C. to about 175 C. for a period of time ranging from about 30 minutes to about 2 hours; reducing the brittle mass to a powder; and calcining the powder to provide cobalt and copper-doped nickel ferrite nanoparticles, wherein the powder is calcined for about two hours to about five hours at a temperature ranging from about 400 C. to about 450 C.

2. The method of claim 1, wherein the gel is prepared by: dissolving iron nitrate in water to provide an iron nitrate solution; dissolving cobalt nitrate in water to provide a cobalt nitrate solution; dissolving nickel nitrate in water to provide a nickel nitrate solution; combining the iron nitrate solution, the cobalt nitrate solution, and the nickel nitrate solution to provide a first mixture; adding copper nitrate to the first mixture to provide a second mixture; adding a capping agent to the second mixture to provide a third mixture; adjusting a pH of the third mixture to provide an alkaline solution; heating the alkaline solution to provide a heated solution; and sealing the heated solution to provide a gel.

3. The method of claim 1, wherein the brittle mass is reduced to a powder by grinding.

4. The method of claim 1, wherein the powder is calcined for about three hours at about 420 C.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1A is a field emission scanning electron microscopy (FESEM) of the Cu.sub.xCo.sub.xNi.sub.(1-x)Fe.sub.2O.sub.4 material.

(2) FIG. 1B is a field emission scanning electron microscopy (FESEM) of the Cu.sub.xCo.sub.xNi.sub.(1-x)Fe.sub.2O.sub.4 material.

(3) FIG. 2A is a transmission electron microscopy (TEM) of the Cu.sub.xCo.sub.xNi.sub.(1-x)Fe.sub.2O.sub.4 material.

(4) FIG. 2B is a transmission electron microscopy (TEM) of the Cu.sub.xCo.sub.xNi.sub.(1-x)Fe.sub.2O.sub.4 material.

(5) FIG. 3 is a cyclic voltammogram of Cu/CoNi-ferrites electrodes in 0.5 M MeOH/1.0 M KOH medium at different scan rates at 25 C.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

(6) The following definitions are provided for the purpose of understanding the present subject matter and for construing the appended patent claims.

Definitions

(7) It should be understood that the drawings described above or below are for illustration purposes only. The drawings are not necessarily to scale, with emphasis generally being placed upon illustrating the principles of the present teachings. The drawings are not intended to limit the scope of the present teachings in any way.

(8) Throughout the application, where compositions are described as having, including, or comprising specific components, or where processes are described as having, including, or comprising specific process steps, it is contemplated that compositions of the present teachings can also consist essentially of, or consist of, the recited components, and that the processes of the present teachings can also consist essentially of, or consist of, the recited process steps.

(9) It is noted that, as used in this specification and the appended claims, the singular forms a, an, and the include plural references unless the context clearly dictates otherwise.

(10) In the application, where an element or component is said to be included in and/or selected from a list of recited elements or components, it should be understood that the element or component can be any one of the recited elements or components, or the element or component can be selected from a group consisting of two or more of the recited elements or components. Further, it should be understood that elements and/or features of a composition or a method described herein can be combined in a variety of ways without departing from the spirit and scope of the present teachings, whether explicit or implicit herein.

(11) The use of the terms include, includes, including, have, has, or having should be generally understood as open-ended and non-limiting unless specifically stated otherwise.

(12) The use of the singular herein includes the plural (and vice versa) unless specifically stated otherwise. In addition, where the use of the term about is before a quantitative value, the present teachings also include the specific quantitative value itself, unless specifically stated otherwise. As used herein, the term about refers to a 10% variation from the nominal value unless otherwise indicated or inferred.

(13) The term optional or optionally means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances in which it does not.

(14) Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which the presently described subject matter pertains.

(15) Where a range of values is provided, for example, concentration ranges, percentage ranges, or ratio ranges, it is understood that each intervening value, to the tenth of the unit of the lower limit, unless the context clearly dictates otherwise, between the upper and lower limit of that range and any other stated or intervening value in that stated range, is encompassed within the described subject matter. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges, and such embodiments are also encompassed within the described subject matter, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the described subject matter.

(16) Throughout the application, descriptions of various embodiments use comprising language. However, it will be understood by one of skill in the art, that in some specific instances, an embodiment can alternatively be described using the language consisting essentially of or consisting of.

(17) For purposes of better understanding the present teachings and in no way limiting the scope of the teachings, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, and other numerical values used in the specification and claims, are to be understood as being modified in all instances by the term about. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

(18) In an embodiment, the present subject matter relates to cobalt and copper-doped nickel ferrite (Cu.sub.xCo.sub.xNi.sub.(1-x)Fe.sub.2O.sub.4) nanoparticles or CuCoNiFNPs as a catalyst for electrooxidation of methanol in direct methanol fuel cells (DMFC). In an embodiment, the CuCoNiFNP catalyst can provide an efficient anode for DMFC in alkaline electrolytes. The CuCoNiFNPs can have a sponge-like structure with irregular pores. A diameter of the CuCoNiFNPs can range from about 8 nm to about 30 nm.

(19) In an embodiment, the CuCoNiFNPs can be prepared chemically by using a sol-gel auto-combustion method. In an embodiment, the method can include preparing a solution including iron nitrate, cobalt nitrate, nickel nitrate, copper nitrate, and a capping agent, adjusting a pH of the solution to provide an alkaline solution, heating the alkaline solution to provide a gel, subjecting the gel to a thermal treatment to provide a dry mass, reducing the dry mass to a powder, and calcining the dry mass to provide the CuCoNiFNPs. In an embodiment, the thermal treatment can include drying the gel and subjecting the dried gel to combustion.

(20) According to an embodiment, the gel can be prepared by first dissolving each of iron nitrate (0.01 M), cobalt nitrate (0.01 M), and nickel nitrate (0.01 M) separately in water to provide a nickel nitrate solution, a cobalt nitrate solution, and an iron nitrate solution. Then, the nickel nitrate solution, the cobalt nitrate solution, and the iron nitrate solution can be combined to provide a first mixture. Thereafter, copper nitrate can be added to the first mixture to provide a second mixture. In an embodiment, the capping agent can then be dissolved in water and then added to the second mixture and stirred for a period of time to provide a third mixture. In an embodiment, the capping agent is citric acid. The pH of the third mixture can then be adjusted to a value between pH 8 and pH 9 to provide an alkaline solution. In an embodiment, ammonia is added to the third mixture to adjust the pH. Then, the alkaline solution can be heated to a temperature ranging from about 60 C. to about 80 C. to provide a heated solution. For example, the alkaline solution can be heated to about 65 C., about 70 C., or about 75 C., to provide the heated solution. In an embodiment, the alkaline solution can be heated while stirring to provide the heated solution. The heated solution can then be sealed for about 12 hours to provide a gel. In an embodiment, the gel can then be subjected to a thermal treatment to provide a brittle mass. In an embodiment, the thermal treatment can include drying the gel and then subjecting the dried gel to combustion to provide the brittle mass. In an embodiment, the gel can be dried in an oven for about 8 hours to about 12 hours at a temperature ranging from about 90 C. to about 110 C. In an embodiment, the gel can be dried in an oven for about 10 hours at about 100 C. The combustion can include burning the resulting dried gel at a temperature ranging from about 165 C. to about 175 C. for a period of time ranging from about 30 minutes to about 2 hours. In an embodiment, the dried gel is burned at a temperature of 170 C. for about 1 hour. Combustion can transform the dried gel to a black, brittle mass. The brittle mass can then be ground to a powder. Then, the powder can be calcined to provide Cu.sub.xCo.sub.xNi.sub.(1-x)Fe.sub.2O.sub.4 nanoparticles. In an embodiment, the powder can be calcined for about two hours to about five hours at a temperature ranging from about 400 C. to about 500 C. In an embodiment, the powder can be calcined for about three hours at about 420 C.

(21) FIGS. 1A and 1B are FE-SEM images of the Cu.sub.xCo.sub.xNi.sub.(1-x)Fe.sub.2O.sub.4 material at two different magnifications. The morphology of the Cu.sub.xCo.sub.xNi.sub.(1-x)Fe.sub.2O.sub.4 nanoparticles is sponge-like with irregularly shaped pores. It is believed that the method of synthesizing the Cu.sub.xCo.sub.xNi.sub.(1-x)Fe.sub.2O.sub.4 nanoparticles, which involved combustion at 170 C. followed by calcination at 420 C., results in the development of the uneven porosity network. The morphological properties of Cu.sub.xCo.sub.xNi.sub.(1-x)Fe.sub.2O.sub.4 as seen in FIGS. 1A-1B were validated by TEM analysis. FIGS. 2A-2B show transmission electron microscopy (TEM) images of the Cu.sub.xCo.sub.xNi.sub.(1-x)Fe.sub.2O.sub.4 material at two different magnifications. As shown in FIGS. 2A-2B, the developed material includes random nanoscale and semi-spherical particles. The particles' diameter ranges from about 8 nm to about 30 nm.

(22) As described herein, the electrochemical effectiveness of the synthesized Cu.sub.xCo.sub.xNi.sub.(1-x)Fe.sub.2O.sub.4 nanoparticles as an electrode for electrocatalytic methanol oxidation was investigated. According to electrochemical investigations, the inclusion of Cu.sub.xCo.sub.xNi.sub.(1-x)Fe.sub.2O.sub.4 material significantly improved current values. The strong electrochemical stability of the produced electrode was shown by the calculated deactivation rate of the anodic current density for the Cu.sub.xCo.sub.xNi.sub.(1-x)Fe.sub.2O.sub.4 material. Accordingly, the Cu.sub.xCo.sub.xNi.sub.(1-x)Fe.sub.2O.sub.4 material can be used for the simple production of electrodes in direct methanol fuel cells (DMFC).

(23) In experiment, the Cu/CoNi-ferrites demonstrated satisfactory electrocatalytic performance as an electrocatalyst for methanol anodic processes. FIG. 3 is a cyclic voltammogram (CV) of Cu/CoNi-ferrites electrodes in 0.5 M MeOH/1.0 M KOH medium at different scan rates at 25 C. Oxidation and reduction peaks can be easily observed at 436 mV and 372 mV vs. Ag/AgCl in the oxidation and reduction plots, respectively. This characteristic, which can be caused by Ni, e.g., Ni.sup.(III)/Ni.sup.(II), is prevalent in the electrochemical investigation of Ni-composite electrodes. The Cu/CoNi-ferrites demonstrated satisfactory electrocatalytic performance, as evidenced by the obvious rise in the oxidation current that was seen. When compared to the current density produced when methanol was absent (around 0.75 mA/cm.sup.2), methanol oxidation started in the CV curve at 401 mV and continued until the anodic peak. The resulting current density then reached 73.9 mA/cm.sup.2. This difference in current density data shows that the Cu/CoNi-ferrite electrode successfully electrooxidized methanol. Also, the peaks and regions of the CV improved as the scan rate increased, indicating the strong electrocatalytic efficacy of the Cu/CoNi-ferrites electrode towards methanol electrooxidation.

(24) The inclusion of Cu.sub.xCo.sub.xNi.sub.(1-x)Fe.sub.2O.sub.4 significantly improved the obtained current values. The current value increased from 0.21 mA/cm.sup.2 at 0.425 V to 6.61 mA/cm.sup.2 at 0.612 V during methanol electrooxidation over Cu.sub.xCo.sub.xNi.sub.(1-x)Fe.sub.2O.sub.4, which is almost 308 times the current density value (0.0214 mA/cm.sup.2 at 0.61 V) reported in the absence of methanol Additionally, the improvement in anodic current density and charge transfer resistances suggests that the Cu.sub.xCo.sub.xNi.sub.(1-x)Fe.sub.2O.sub.4 catalyst has electro-oxidized methanol. Accordingly, the Cu.sub.xCo.sub.xNi.sub.(1-x)Fe.sub.2O.sub.4 catalyst is an efficient anode for DMFC at high pH.

(25) It is to be understood that the cobalt and copper-doped nickel Cu/CoNi-ferrite (Cu.sub.xCo.sub.xNi.sub.(1-x)Fe.sub.2O.sub.4) nanoparticles are not limited to the specific embodiments described above, but encompasses any and all embodiments within the scope of the generic language of the following claims enabled by the embodiments described herein, or otherwise shown in the drawings or described above in terms sufficient to enable one of ordinary skill in the art to make and use the claimed subject matter.