Impregnation process using a bio-templating method for nano-catalyst incorporation into the electrodes of solid-state electrochemical cells

Abstract

A process for incorporating a nanocatalyst on the surface of and within the pores of an electrode comprising subjecting an electrode to a singular template impregnation to form a treated electrode having a bio-template layer; and then subjecting the treated electrode to a singular nano-catalyst impregnation for tethering the nano-catalyst to the treated electrode; and then removing the bio-template layer by performing thermolysis upon the treated electrode for forming a nano-catalyst bonded on the surface and within the pores of the electrode. A modified electrode or product made by this process is provided.

Claims

1. A process for incorporating at least one nanocatalyst on the surface of and within a plurality of pores of an electrode comprising: impregnating an electrode comprising pores with a plurality of catechol-based biomolecules to form a treated electrode having a bio-template layer; and then impregnating said treated electrode with at least one nano-catalyst; and then removing said bio-template layer by performing thermolysis upon the treated electrode for forming at least one nano-catalyst bonded on the surface and within the pores of said electrode.

2. The process of claim 1 wherein said electrode is impregnated with the plurality of catechol-based biomolecules by dipping said electrode into a solution comprising the plurality of catechol-based biomolecules.

3. The process of claim 1 wherein said electrode is impregnated with the plurality of catechol-based biomolecules by dripping a solution comprising the plurality of catechol-based biomolecules into said pores of said electrode.

4. The process of claim 1 wherein said treated electrode is rinsed with a solvent after said treated electrode is impregnated with the plurality of catechol-based biomolecules and before said treated electrode is impregnated with the at least one nano-catalyst.

5. The process of claim 1 wherein said treated electrode is impregnated with the at least one nano-catalyst by dipping said treated electrode into a salt solution comprising the at least one nano-catalyst.

6. The process of claim 1 wherein said treated electrode is impregnated with the at least one nano-catalyst by dripping a salt solution comprising the at least one nano-catalyst into said pores of said electrode.

7. The process of claim 1 wherein after said treated electrode is impregnated with the at least one nano-catalyst and before said bio-template layer is removed from said treated electrode, said treated electrode is dried.

8. The process of claim 1 wherein the thermolysis is performed at a temperature that is less than about 1000 degrees Centigrade.

9. The process of claim 1 comprising a plurality of impregnation steps, wherein the plurality of impregnation steps consist essentially of impregnating said electrode comprising pores with the plurality of catechol-based biomolecules to form said treated electrode having said bio-template layer; and then impregnating said treated electrode with the at least one nano-catalyst.

10. The process of claim 1 wherein the plurality of catechol-based biomolecules comprises poly-dopamine.

11. The process of claim 1 wherein the plurality of catechol-based biomolecules comprises poly-epinephrine.

12. The process of claim 1 wherein the plurality of catechol-based biomolecules comprises melanin.

13. The process of claim 1 wherein the plurality of catechol-based biomolecules comprises a compound that behaves like poly-dopamine and is selected from the group consisting of caffeic acid, DHC (d 3,4-dihydroxyhydrocinnamic acid), Tiron (4,5-dihydroxy-1,3 benzenedisulfonic acid disodium salt), gallic acid and celestine blue.

14. The process of claim 1, wherein said electrode is impregnated with from about 0.25 mg/ml to about 5 mg/ml loading of the plurality of catechol-based biomolecules.

15. The process of claim 1, wherein said electrode is impregnated with from about 0.5 mg/ml to about 2 mg/ml loading of the plurality of catechol-based biomolecules.

16. The process of claim 1, wherein said treated electrode is impregnated with from 0.2 mg to 10 mg loading of all of the at least one nano-catalyst.

17. The process of claim 1, wherein said treated electrode is impregnated with from 0.5 mg to 7 mg loading of all of the at least one nano-catalyst.

18. The process of claim 1, wherein the plurality of catechol-based biomolecules comprises at least one selected from the group consisting of poly-dopamine, poly-epinephrine, melanin, and a compound that behaves like poly-dopamine that is selected from the group consisting of caffeic acid, DHC (d 3,4-dihydroxyhydrocinnamic acid), Tiron (4,5-dihydroxy-1,3 benzenedisulfonic acid disodium salt), gallic acid and celestine blue.

Description

BRIEF SUMMARY OF THE DRAWINGS

(1) FIG. 1 shows the number of papers of recent impregnation/infiltration studies on SOFC electrodes.

(2) FIG. 2 shows an XPS characterization of twenty five (25) different poly-dopamine coated surfaces before and after coating by poly-dopamine.

(3) FIG. 3 shows the dependence of the poly-dopamine (PDA) and TiO.sub.2 film thickness (nm) on the time (in hours) of polymerization.

(4) FIG. 4 shows the influence of poly-dopamine concentration on the deposited CeO.sub.2 catalyst within a commercial anode-supported SOFC after bio-templated and dip-coated infiltration process of this invention.

(5) FIG. 5 shows a current-voltage plot of various concentrations of poly-dopamine (PDA) template and Ce infiltrated electrochemical cells using the process of this invention.

DETAILED DESCRIPTION OF THE INVENTION

(6) The present invention provides a process for incorporating (depositing) mono or multi-cation nano-catalyst into the electrodes of an electrochemical cell (such as solid-oxide fuel cells (SOFCs) or solid-oxide electrolysis cells (SOECs)).

(7) This method focuses on a facile wet impregnation deposition protocol (i.e. deposition process) to incorporate nano-catalyst homogenously throughout the porous three-dimensional electrodes. The method permits the deposition into a singular electrode or simultaneous deposition into both electrodes (anode and cathode). The deposition process is dependent upon a wet salt solution (where the medium may be water, alcohol, or organic liquid) being infiltrated into the solid porous electrode microstructure, where the solubility is altered and the inorganic catalyst is precipitated and deposited. The term impregnation (or sometime infiltration) is utilized to emphasize the point that the nano-catalyst must be deposited within the interior of the porous electrode (all the way to the electrolyte surface within the interior of the cell), and not to be only deposited at the outer surface of the electrode.

(8) An advantage of the process is that it lowers the processing time and labor needed to complete the impregnation task; the process requires only two deposition steps (with only one drying step), where previously demonstrated processes described in literature require greater than two steps (deposition and drying). The first step includes a single deposition step of the bio-template material; without drying, the electrochemical cell may be then exposed to the inorganic salt solution.

(9) A second advantage is that the impregnation process permits precise control of the nano-catalyst concentration level throughout the microstructure. This means that the deposition rate can be controlled to a predictable level, where then the nano-catalyst incorporation concentration would be dependent upon the exposure time to the solution and not due to the number of deposition steps.

(10) For a general description of the technology, the process includes the initial impregnation (infiltration) of a catechol-based molecules (for example, but not limited to, poly-dopamine and poly-norepinephrine. which is a biological chemical found in animals and humans) dissolved within an aqueous solution buffered to a constant pH. The catechol-based biomolecules are the key component of the technology, since this chemistry was found to adsorb and modify the chemistry of any surface (organic, metal, ceramic, and semiconductor). The chemical properties of this surface modifier also permit the controlled deposition (templating) of metal and metal oxide films over the bio-molecule; as we called bio-template layer.

(11) The electrochemical cell with the porous electrodes is dipped into the dopamine solution or, dopamine solution is dripped on to the porous electrodes surface and held for a specific time to control the deposition and adhesion of the poly-catechol on the electrode interior surface. The thickness of this surface modifying agent will depend upon the concentration of the monomer solution, pH, and deposition time. The electrochemical cell is then dipped into a separate salt solution (containing the inorganic salt that will dictate the nano-catalyst composition) or salt solution is dripped on to the porous electrodes and held within the solution for a given specific time. The hold processing time will dictate the thickness of the deposited polycrystalline film of the nano-catalyst material within the porous electrode microstructure. After drying, the electrochemical cell is thermally processed to oxidize, and drive any desired solid-state reaction of deposited material. The key is to thermally process at a temperature less than about 1000 C. (centigrade) to control the particle size of the nano-catalyst deposits (to restrict sintering and grain growth processes). Minimum firing temperature depends on the decomposition temperature of catalyst precursor solution but the key is to thermally process at a temperature of <1000 C. to control the particle size of the nano-catalyst deposits.

(12) The initial demonstrations of the technology utilized a dip-coating method to deposit both the bio-template and inorganic salt solution. A point deposition process (such as the use of a pipet or syringe) maybe used to deposit the poly-catechol and metal salt solutions at a specific location or across the whole electrode surface. This process is usually termed as a dripping method. The dip-coating protocol was initially adapted for the demonstrations since the entire electrode surface (both electrodes if desired) can be exposed to the solution at the same time; in addition, the porous structure may be exposed to a negative or positive pressure to remove gas within the porous structure and to drive the liquid into the microstructure, respectively. By permitting the electrode to be exposed to the entire homogenous solution at the same time, the desired amount of inorganic nano-catalyst may be controlled precisely due to the predictable deposition rate. Moreover, both electrodes could be infiltrated at the same time with the catalyst precursor, such that with the proper selection of the catalyst composition, the oxidation/reduction processes of the electrochemical cell may be modified and/or enhanced simultaneously.

(13) As described above, the advantages for using this bio-templating enhanced deposition process was to increase the amount of deposited/infiltrated/impregnated catalyst and secondly, to pin the catalyst to the pore walls by the spontaneous self-adhesive feature of catechol-based molecules; therefore, the migration of cations from deep microstructure region to the surface during drying was prevented. In published literature, these bio-adhesives have been used to only coat two-dimensional substrates, but never three-dimensional porous networks that are composed of more than one solid phase or chemistry (such is typical for solid-state electrochemical cells).

(14) The defined parameters could be modified using the provided working mechanism as a basis for selection of an adequate substitute. Alternative catechol-based bio adhesive such as melanin could also be used for templating. Initial bio-adhesive content and dispersant mixture (alcohol, water) and immersion time could be modified to change the aggregate size and the final thickness of the bio-template. Different nano-catalyst cation sources could be also used as the precursor. Moreover, precursor compositions or alcohol/water ratios could be modified in order to lower or elevate the wetting characteristics of precursor. Initial precursor molarity, and coating (immersion) time can be modified in order to aim various final catalyst loading. Pressure and vacuum assistance could be applied to enhance the deposition rate of nano-catalyst. Calcination temperature could be modified to control the final particle size of impregnated nano-catalysts. Finally, the chemistry and the stoichiometry of the catalysis can be modified for the utilization of different types of fuel candidates or depending on the target electrode (anode and/or cathode). Through the presented technology, the nano-catalyst can be multiple component metal (such as mono-, bi-, and tri-component composites or alloys) or oxide nano-particles.

(15) The technical descriptions and constraints of the process are as follows:

(16) 1. The porosity of the candidate electrode for infiltration should consist of a percolated open structure (can be as low as 25% porosity level);

(17) 2. If the candidate electrode is infiltrated by drip-coating method, the bio-template and catalyst precursor solutions must be dripped to completely cover the active electrode boundary which is typically the smallest electrode surface area;

(18) 3. If the candidate electrode is infiltrated by dip-coating method, the cell (or the whole cell) must be completely immersed and covered by the bio-template and catalyst precursor solutions stepwise;

(19) 4. The final poly-catechol aggregate size is very crucial for bio-template protocol of 3D porous architectures. Depending on the percolation and the percentage of the pore ratio, the final aggregate size must be lower than 150-250 nm (particle size). Final aggregate size can be tuned by solid concentration (varying 0.25 to 2 mg/ml), water/organic medium ratio (varying 100% water to 25% water/75% organic medium such as ethanol by volume);

(20) 5. Poly-catechol polymerization is very susceptible to pH drifts. A buffering agent, such as TRIS, tris(hydroxymethyl)aminomethane), should be used to fix the pH at a desired point;

(21) 6. After polymerization, the aggregate size of the poly-catechol species must not be equal or higher than the average pore size (such as in most commercial SOFCs, >100 nm). Above this range, few polymerized catechol based bio-molecule particles can clog the open pores and prevents the effective infiltration for both bio-templating and nano-catalyst solution impregnation steps;

(22) 7. When the whole cell or only one electrode is immersed to the solution, the system must be exposed to a vacuum to evacuate air imprisoned in the 3-D porous structure; otherwise, the air entrapped gas acts as a barrier layer for the infiltration. Depending on the thickness and the surface area of the cell, the amount needed for the vacuuming may change but it should be at least 5 minutes under 30 mm Hg;

(23) 8. Polymerized poly-catechol solution tends to sediment under stagnant conditions which cause local inhomogeneity inside the solution. To prevent this, the system should be tilted, strongly preferred on the rocker table. The frequency of the rocker table should be between 30-45 rpm;

(24) 9. After bio-templating, treated surface(s) should be rinsed with the clear solution of the same ethanol-water ratio of bio-template solution. The reason for doing this is to clean the surface for the loosely bonded bio-aggregates;

(25) 10. Nano-catalyst infiltration is followed by the drying step. The cell can be dried in a heated oven. The temperature of the oven must not exceed over the ignition temperature of solvent in the presence of the catalyst. For example, 150-180 C. for cerium based catalysis and ethanol; and

(26) 11. The calcination temperature must be higher than the decomposition temperature of the catalyst source.

(27) The present invention improves the electrode performance, and hence the overall performance, by infiltration/impregnation of nano-particles within the electrode microstructure, which increases the catalytic activity and redox reaction rates. By using the high surface area of the nano-particles, the triple phase boundary (TBP) length and activity may be enhanced, which is typically reflected in a decrease in the polarization resistance. In FIG. 1, recent impregnation/infiltration studies varying single to multi-cations, precious to conventional catalysis are tabulated. Current impregnation (infiltration) protocols often requires multiple steps to achieve adequate amount of nano-catalyst deposition within the electrochemical cells.

(28) Deposited catalyst loading is commonly measured by the weight difference and the amount is ranked in various units such as nano-catalyst amount over electrode surface area (mg/cm.sup.2), volume (mg/cm.sup.3, mmol/cm.sup.3) or weight percent (mg/g percentage). For example, one study was on the impregnation of samarium doped ceria (SDC) on NiO/SDC anode, optimum catalyst loading was reached after 7 infiltration cycles (20 mg/cm.sup.2). However, the performance of the 9th cycle infiltrated cell (25 mg/cm.sup.2) showed lower performance than the 5th cycle infiltrated cell (15 mg/cm.sup.2). Showing lower performance implied the thicker SDC coating on the nickel particles in the anode may block the gas diffusion to the TPB region. Similar profile can be seen in a study on impregnating SDC, Sm.sub.2O.sub.2, CeO.sub.2 and Al.sub.2O.sub.3 to Ni-based anodes (Liu et al., J. Solid State Electrochem, 2012). In all attempts, the maximum current density enhancement provided at the 4th cycle infiltrated cells which corresponds to 1.40-1.71 mmol/cm.sup.3 catalyst loading. Preferably a loading dose of from about 0.5 mg to about 4.5 mg of the nanocatalyst is employed. In a different perspective, one study was aimed to observe the effect of catalyst precursor molarity ranging from 0.5 M to 2.5 M on the performance by a single step infiltration (Timurkutluk et al., Int. J. Energy. Res., 2011). At the end, the final deposition amount was not mentioned, but the results showed that the performance of the cell enhanced by the deposited catalyst and reached 71% higher power density than the unimpregnated baseline cell, when high molarity precursor solution is used (1.5 M). The cells impregnated with 2 and 2.5 M monitored lower maximum power densities than the baseline due to the pore clogging and limiting the gas flow and electrical conductivity.

(29) In an embodiment of the process of the present invention, three-dimensional architecture of the electrode (or the whole cell) is templated by the bio-adhesive molecules in the first step (of a two-step process, which includes the singular organic template impregnation step and the singular nano-catalyst impregnation step). The process achieves a mono-layer adhesive coating over the pore walls of single/multi component electrodes homogenously. The catechol-based bio-molecules (such as for example, but not limited to, poly-dopamine, poly-norepinephrine) are bio-mimicked materials typically seen in marine mussels. These adhesive proteins undergo spontaneous polymerization in marine conditions (alkaline medium) by a facile and versatile process. FIG. 2 shows that the adhesive effect of poly-catechol film can bind to various substrates regardless of its chemistry (Lee et al., Science, 2007). As it is seen, dopamine deposited/bonded over the substrate after sometime that no substrate signal can be gained by XPS. To be more specific, the chemisorption between the bio-template and electrode, multi-metal oxide surface, is reported to initiate via the coordination interaction between the metal ion(s) and the catechol group. During the catalyst precursor dip-coating step, the deposited poly-dopamine template located on the pore walls binds with mono- or multi-metal ions via chelation. In one study, Cu.sup.+2 was stated to bind with either phenolic hydroxyl groups or nitrogen ligands depending on neutral to alkaline medium conditions (Liu et al, J. Am. Chem. Soc., 2014). By bio-templating of this invention, the nano-catalyst precursor infiltration can be performed efficiently since the dissolved catalyst cation(s) can attach to the bio-template layer and pin to that position. In that way, the drying process does not pull the nano-particle from the original deposited position to the surface during drying (by capillarity action). As an example, experiments were performed to form cerium dioxide (CeO2) nano-catalyst particles, which the performance enhancement effect has been proven for SOFC (Gorte et al., J. Power Sources, 2002). In that manner, cerium source raw materials, such as cerium nitrate hexahydrate, cerium chloride, etc., were used. As depicted above, the bio templating method of this invention can be applied to surfaces to different chemistries and coating nano-particles.

(30) The technology described here introduces a bio-template assisted dip-coating process for infiltration/impregnation of the nano-catalyst within the electrode microstructure. Bio-template method has been mostly utilized for 2D smooth surfaces. Only few studies have been assessed on coating of 3D architectures such as membranes or biomaterial scaffolds. The common structure of PDA coated 3D architecture is being single solid chemical phase with the high porosity values up to 40% (Ryou et al., Adv. Mater., 2011) to 85% with large pore size (300 m) (Wu et al., J. Mater. Chem, 2011). The success of bio-templating of 3-D architecture membranes owes not only to have highly open structure, large pore size, but also to the thin structure (typically 25 m-100 m) and infiltration to the two faces by dip-coating which decreases the infiltration depth by two times. After the application of polymerized poly-catechol adhesive, the surface can attract any type of dopant and/or coating regardless of its chemistry. With the present technology, the homogenous bio-templating layer, covering evenly over the multi-phase 3D pore network, leads to an homogenous nano-catalyst coating over the same pore surface, where the infiltrated nano-catalyst remains pinned during drying (without segregation to the surface). In the end, the bio-template is easily removed by thermolysis and the nano-catalyst is bonded to the pore wall through typical sintering processes.

(31) Conventional infiltration/impregnation protocols are basically performed in multiple repetitions of the same dripping method until the desired catalyst loading is achieved. The dripping method includes the simple process of dripping or pipetting a salt solution onto the surface of the electrode, where capillary action and gravity forces the salt solution into the porous electrode. The precipitation of the nano-catalyst typically occurs when the cell is permitted to dry; the change in the super-saturation level is altered during this drying process (leading to precipitation at the drying surface). This process takes multiple days and requires a significant number of sequential dripping and drying steps (typically 5-15 dripping and drying steps). In addition, due to the preferential drying at the surface of the electrode, the nano-catalyst is preferentially precipitated at the surface resulting in the blockage of the porosity in this location and the inhomogeneous deposition of the nano-catalyst (where there is a gradient identified from the surface to the electrolyte interface). Typically, rapid drying kinetics of the small amount (few milliliters) of liquid precursor also does not permit sufficient time for effective wicking of the catalyst through the surface blocked pores in following steps.

(32) In the present invention, the two-step process was originally utilized to deposit coatings onto two-dimensional, smooth surfaces. This process was modified for the impregnation of complex nano-catalyst into the three-dimensional porous network of an electrochemical electrode. The technology of the present invention solves the existing problems that are depicted above. By using the bio-template assisted dip-coating process of this invention, the impregnation efficiency can be increased in terms of catalyst loading in a single nano-catalyst deposition step (with only one drying step). In addition, the control of the overall nano-catalyst deposition concentration (or thickness) and drying segregation (inhomogeneity) is controlled using the present process/method.

(33) Bio-templating impregnation has three distinct advantages over other impregnation processes, as follows:

(34) 1. The method is not dependent upon the chemistry or wetting characteristics of the substrate or deposited material (nano-catalyst);

(35) 2. The adhesive effect of the bio-template surface modifier permits the pinning of the nano-catalyst after deposition and restricts migration during solvent drying; and

(36) 3. The deposition rate of the nano-catalyst is consistent (with control of temperature, pressure, and solution concentration) which leads to distinct control of the film thickness.

(37) By the implementation of bio-templating, substrates with various chemistries can be templated for different purposes. Secondly, after templating, again various materials ranging from proteins and DNA to various inorganic nano/macro particles can be deposited. More for the application side, the adaptation of this step to SOFC electrodes brings the pinning of nano-catalyst particles into the 3D architecture of the electrode(s) by weak attractive forces. These two functions have proven to be successful and versatile due to the catechol-based templating method. The fourth need for infiltration studies is controlling the deposition amount. FIG. 3 displays that bio-template and catalysis deposition rate is proportional to initial concentration and exponentially decreasing function of the reaction time. Hence, various architectures can be templated and infiltrated with desired amount of nano-catalyst (Zheng et al., Thin Solid Films, 2012).

(38) Data and Results

(39) For prior infiltration experiments, the technology of the present invention was applied to commercial anode-supported SOFCs. As set forth in FIG. 4, it is noted that by changing the poly-dopamine (PDA) concentration, the deposited catalyst amount changed and demonstrated a significantly higher deposition level over that without the bio-template surface modifier. A 0.5 mg/ml PDA solid loading was found to be the most optimal loading, where the final catalyst deposition level was 6.5 times higher than the infiltration process that used no poly-dopamine template. Below 0.5 mg/ml concentration, the effect of the poly-dopamine template was found not to have a significant effect on the overall deposition amount, where the deposition level of the nano-catalyst was in the similar range as the samples processed with no PDA. Catalyst deposition of 0.25 mg/ml PDA treated cell was 1.5 mg (0.5 mg/ml PDA had 6.5 mg catalyst loading). It is believed that the effect begins after 0.25 mg/ml PDA.

(40) The reason for getting a lower deposition rate at higher PDA concentrations was probably due to the spontaneous PDA aggregation, during continuous self-polymerization process. The PDA aggregates were found to block efficient infiltration of the catalyst precursor within the electrode structure during the dip-coating process.

(41) In FIG. 5, current-voltage plot of the 0.5 mg/ml PDA templated and Ce infiltrated electrochemical cells showed the lowest enhancement among the infiltrated cells, due to the overloaded catalyst level within the porosity which affected the gas diffusion rate. In the case of cells processed with a 1 mg/ml PDA template concentration, the Ce infiltrated cell showed a 51% higher performance over the baseline cell, where the total nano-catalyst loading with this templating concentration was 4.5 mg CeO.sub.2 (completed again, using the two-step process). These experiments showed that the adhesive property of bio-template had a very big influence on catalyst deposition in comparison to the conventional dip-coating method under the same conditions and parameters.

(42) The present invention's infiltration process on Solid Oxide Fuel Cells (SOFC's) can be applied to introduce nano-catalyst into the anode, cathode or both sides of SOFC electrodes. In that case, suitable metallic and metallic alloys (such as, but not limited to, Co, Mo, Pd, Pt, Ce, Ag, Ni, Cu, Ru, Rh) and metal oxide (such as, but not limited to, CeO.sub.2, Al.sub.2O.sub.3, CaO, La.sub.xSr.sub.yO.sub.3) nano-catalysts as oxidation/reduction enhancing catalyst, internal reforming catalyst, grain growth inhibitors, and contaminant catalyst can be infiltrated. This allows the flexibility of fuel choice such as, hydrogen, methane, and coal syngas; in addition, the long-term stability may be controlled with precise nano-catalyst selection, as well as, an increase in electrochemical performance. The key is that the process of this invention may be applied to existing commercial SOFCs without the manufacturing needing to alter their current product's microstructure (and thus, major processing methods and materials). The process set forth herein can be added to any existing products. Little to no limitations exist for controlling the agglomerate size of polymerized dopamine or similar bio-template chemistries using the processes of this invention.

(43) This process of this invention may be implemented for a variety of types of electrochemical cell applications, for example, but not limited to, the following:

(44) 1. Specific nano-catalysts for utilization of various fuel types such as for example, but not limited to, shale gas, and natural gas;

(45) 2. Sizes/geometry SOFC and solid oxide electrolysis cells (SOECs) such as for example, but not limited to, planar, and tubular cells; and

(46) 3. SOFC's types such as for example, but not limited to, electrolyte, cathode or metal supported SOFC's.

(47) All solid-oxide fuel cell (SOFC) commercial providers and/or manufacturers shall be interested in the process of this invention to enhance the performance of their existing technology without alteration to their current product.

(48) In the examples provided herein the following materials were employed: Dopamine hydrochloride (99%) and Cerium (HI) nitrate hexahydrate (REacton, 99.5% (REO) and TRIS buffer (Tris(hydroxymethyl)aminomethane, 99%) were purchased from Alfa Aesar. Epinephrine hydrochloride was purchased from Sigma Aldrich. Anode supported fuel cells (ASC-2.7, NexTech Materials, Ltd.) were purchased from Fuel Cell Materials. Reagent grade of nitric acid and ammonium hydroxide were used to shift the pH of dopamine or epinephrine solution. Nalgene polyethersulfone syringe filter with 0.2 m (Thermo Scientific) was used to filter polymerized poly-catechol solution.

(49) In one embodiment of the invention, a process incorporates at least one nanocatalyst on the surface of and within a plurality of pores of an electrode by impregnating an electrode comprising pores with a plurality of catechol-based biomolecules to form a treated electrode having a bio-template layer; and then impregnating the treated electrode with at least one nano-catalyst; and then removing the bio-template layer by performing thermolysis upon the treated electrode for forming at least one nano-catalyst bonded on the surface and within the pores of the electrode.

(50) In some embodiments, the electrode is impregnated with the plurality of catechol-based biomolecules by dipping the electrode into a solution comprising the plurality of catechol-based biomolecules.

(51) In some embodiments, the electrode is impregnated with the plurality of catechol-based biomolecules by dripping a solution comprising the plurality of catechol-based biomolecules into the pores of the electrode.

(52) In some embodiments, the treated electrode is rinsed with a solvent after the treated electrode is impregnated with the plurality of catechol-based biomolecules and before the treated electrode is impregnated with the at least one nano-catalyst.

(53) In some embodiments, the treated electrode is impregnated with the at least one nano-catalyst by dipping the treated electrode into a salt solution comprising the at least one nano-catalyst.

(54) In some embodiments, the treated electrode is impregnated with the at least one nano-catalyst by dripping a salt solution comprising the at least one nano-catalyst into the pores of the electrode.

(55) In some embodiments, the treated electrode is impregnated with the at least one nano-catalyst and before the bio-template layer is removed from the treated electrode, the treated electrode is dried.

(56) In some embodiments, the thermolysis is performed at a temperature that is less than 900 degrees Centigrade.

(57) In some embodiments, the only impregnation steps are impregnating the electrode comprising pores with the plurality of catechol-based biomolecules to form the treated electrode having the bio-template layer; and then impregnating the treated electrode with the at least one nano-catalyst.

(58) In some embodiments, the plurality of catechol-based biomolecules comprises poly-dopamine.

(59) In some embodiments, the plurality of catechol-based biomolecules comprises poly-epinephrine.

(60) In some embodiments, the plurality of catechol-based biomolecules comprises melanin.

(61) In some embodiments, the catechol-based biomolecule comprises a compound that behaves like poly-dopamine and is selected from the group consisting of caffeic acid, DHC (d 3,4-dihydroxyhydrocinnamic acid), Tiron (4,5-dihydroxy-1,3 benzenedisulfonic acid disodium salt), gallic acid and celestine blue.

(62) In some embodiments, the electrode is impregnated with from about 0.25 mg/ml to about 5 mg/ml loading of the plurality of catechol-based biomolecules, and preferably is from 0.50 mg/ml to about 2.0 mg/ml.

(63) In some embodiments, the electrode is impregnated with from about 0.5 mg/mL to about 1 mg/mL loading of the plurality of catechol-based biomolecules.

(64) In some embodiments, the electrode is impregnated with about 0.5 mg/mL loading of the plurality of catechol-based biomolecules.

(65) In some embodiments, the treated electrode is impregnated with from 0.2 mg to 10 mg loading of all of the at least one nano-catalyst.

(66) In some embodiments, the treated electrode is impregnated with from 0.5 mg to 7.0 mg loading of all of the at least one nano-catalyst.

(67) In another embodiment of the invention, an electrode comprises a plurality of pores and at least one nanocatalyst, wherein the at least one nanocatalyst is bonded on the surface and within the pores of the electrode by impregnating the electrode with a plurality of catechol-based biomolecules to form a treated electrode having a bio-template layer; and then impregnating the treated electrode with the at least one nano-catalyst; and then removing the bio-template layer by performing thermolysis upon the treated electrode.

(68) In some embodiments, the electrode is loaded with from 0.2 mg to 10 mg of all of the at least one nano-catalyst.

(69) In some embodiments, the plurality of catechol-based biomolecules comprises at least one selected from the group consisting of poly-dopamine, poly-epinephrine, and melanin. Other embodiments include wherein the catechol-based molecule comprises a compound that behaves like poly-dopamine and is selected from the group consisting of caffeic acid, DHC (d 3,4-dihydroxyhydrocinnamic acid), Tiron (4,5-dihydroxy-1,3 benzenedisulfonic acid disodium salt), gallic acid and celestine blue.

(70) It will be appreciated by those persons skilled in the art that changes could be made to the embodiments described herein without departing from the broad inventive concept thereof. It is understood, therefore, that this invention is not limited to the particular embodiments disclosed, but is intended to cover modifications that are within the spirit and scope of the invention, as defined by the appended claims.