3D reduced graphene oxide foams embedded with nanocatalysts, synthesizing methods and applications of same

Abstract

A method of synthesizing three-dimensional (3D) reduced graphene oxide (RGO) foams embedded with water splitting nanocatalysts includes providing a first solution containing nickel (II) nitrate, a second solution containing iron (III) nitrate, and a graphene oxide (GO) aqueous suspension; mixing the GO aqueous suspension with the first solution and the second solution to form a GO-NiFe mixture; adjusting a pH value of the GO-NiFe mixture to be about 3.5; and performing hydrothermal reaction in the GO-NiFe mixture to form RGO-NiFe foams, wherein nanocatalysts containing Ni-Fi oxide particles are embedded in porous structures of the 3D RGO foams.

Claims

1. A method of synthesizing a three-dimensional (3D) reduced graphene oxide (RGO) foam embedded with nanocatalysts, comprising: providing a first solution containing nickel (II) nitrate, a second solution containing iron (III) nitrate, and a graphene oxide (GO) aqueous suspension; mixing the GO aqueous suspension with the first solution and the second solution to form a GO-NiFe mixture suspension; adjusting a pH value of the GO-NiFe mixture suspension to be about 3.5; and performing hydrothermal reaction in the GO-NiFe mixture suspension to form a RGO-NiFe foam, wherein nanocatalysts containing Ni-Fi oxide particles are embedded in a porous structure of the 3D RGO foam.

2. The method of claim 1, wherein the GO-NiFe mixture suspension is characterized with a molar ratio of C:Ni:Fe=14:1:0.33.

3. The method of claim 1, wherein the first and second solutions are provided by dissolving Ni(NO.sub.3).sub.2.6H.sub.2O and Fe(NO.sub.3).sub.3.9H.sub.2O into deionized water, respectfully.

4. The method of claim 1, wherein the pH value of the GO-NiFe mixture suspension is adjusted by adding a NaOH solution therein.

5. The method of claim 1, wherein the hydrothermal reaction in the GO-NiFe mixture suspension is performed in a sealed autoclave for hydrothermal reaction at a predetermined temperature for a period of time.

6. The method of claim 5, wherein the predetermined temperature is in a ranges of about 160-200 C., and the period of time is in a range of about 7-11 h.

7. The method of claim 1, further comprising washing the RGO-NiFe foam with deionized water.

8. The method of claim 7, further comprising freeze-drying the RGO-NiFe foam under about 0.05 mbar vacuum at about 50 C. to obtain the RGO-NiFe solid foam.

9. The method of claim 1, further comprising, prior to performing hydrothermal reaction in the GO-NiFe mixture suspension, ultrasonicateing the GO-NiFe mixture suspension to remove air bubbles that are trapped in the GO-NiFe mixture suspension.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The accompanying drawings illustrate one or more embodiments of the invention and, together with the written description, serve to explain the principles of the invention. The same reference numbers may be used throughout the drawings to refer to the same or like elements in the embodiments.

(2) FIG. 1A shows schematically preparation of a RGO-NiFe foam through a one-pot hydrothermal process, according to one embodiment of the invention.

(3) FIG. 1B shows appearance of the RGO-NiFe product in autoclave after the reaction, according to one embodiment of the invention.

(4) FIG. 1C shows a RGO-MoS.sub.2 foam produced from a one-pot hydrothermal growth, according to one embodiment of the invention.

(5) FIG. 2A shows C 1s XPS spectra of three RGO foam samples, according to embodiments of the invention. The insert in FIG. 2A shows the bond assignment of the C 1s spectrum of the RGO foam sample.

(6) FIG. 2B shows Ni 2p XPS spectra of two RGO-NiFe foam samples, according to embodiments of the invention.

(7) FIG. 2C shows Fe 2p XPS spectra of two RGO-NiFe foam samples, according to embodiments of the invention.

(8) FIG. 3 shows XRD patterns of (a) GO-NiFe gel-like mixture before hydrothermal reaction; (b) RGO-NiFe foam from hydrothermal reaction; and (c) RGO-NiFe foam further annealed at about 500 C., according to embodiments of the invention.

(9) FIG. 4 shows Raman spectra of RGO-NiFe hybrid materials: (a) a GO-NiFe gel-like mixture before hydrothermal reduction; (b) a RGO-NiFe foam from hydrothermal reduction; and (c) a RGO-NiFe foam further annealed at about 500 C., according to embodiments of the invention. The lines marked with the asterisk near 520 cm.sup.1 is from Si substrate.

(10) FIGS. 5A-5C show SEM images of a RGO foam through a hydrothermal process, RGO-NiFe foam fabricated from hydrothermal reaction, and a RGO-NiFe foam further annealed at about 500 C., respectively, according to embodiments of the invention.

(11) FIGS. 6A-6B show TEM images of a hydrothermally fabricated RGO-NiFe foam in different scales, according to one embodiment of the invention.

(12) FIGS. 6C-6D show TEM images of a RGO-NiFe foam annealed at about 500 C. in different scales, according to one embodiments of the invention.

(13) FIG. 7 shows polarization curves of (a) a RGO-NiFe foam prepared by hydrothermal reduction, (b) a RGO-NiFe foam annealed at about 500 C. and (c) a RGO-NiFe membrane annealed at about 500 C., respectively, according to embodiments of the invention. The insert is the CV of the RGO-NiFe foam sample, showing the peak around 1.48 V for the Ni(II)/Ni(III or IV) redox process.

(14) FIG. 8 shows Tafel plots of (a) a RGO-NiFe foam produced by hydrothermal reduction, (b) a RGO-NiFe foam annealed at about 500 C., and (c) a RGO-NiFe membrane annealed at about 500 C., respectively, according to embodiments of the invention.

DETAILED DESCRIPTION OF THE INVENTION

(15) The invention will now be described more fully hereinafter with reference to the accompanying drawings, in which exemplary embodiments of the invention are shown. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this invention will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Like reference numerals refer to like elements throughout.

(16) The terms used in this specification generally have their ordinary meanings in the art, within the context of the invention, and in the specific context where each term is used. Certain terms that are used to describe the invention are discussed below, or elsewhere in the specification, to provide additional guidance to the practitioner regarding the description of the invention. For convenience, certain terms may be highlighted, for example using italics and/or quotation marks. The use of highlighting has no influence on the scope and meaning of a term; the scope and meaning of a term is the same, in the same context, whether or not it is highlighted. It will be appreciated that same thing can be said in more than one way. Consequently, alternative language and synonyms may be used for any one or more of the terms discussed herein, nor is any special significance to be placed upon whether or not a term is elaborated or discussed herein. Synonyms for certain terms are provided. A recital of one or more synonyms does not exclude the use of other synonyms. The use of examples anywhere in this specification including examples of any terms discussed herein is illustrative only, and in no way limits the scope and meaning of the invention or of any exemplified term. Likewise, the invention is not limited to various embodiments given in this specification.

(17) It will be understood that, as used in the description herein and throughout the claims that follow, the meaning of a, an, and the includes plural reference unless the context clearly dictates otherwise. Also, it will be understood that when an element is referred to as being on another element, it can be directly on the other element or intervening elements may be present therebetween. In contrast, when an element is referred to as being directly on another element, there are no intervening elements present. As used herein, the term and/or includes any and all combinations of one or more of the associated listed items.

(18) It will be understood that, although the terms first, second, third etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer or section from another element, component, region, layer or section. Thus, a first element, component, region, layer or section discussed below could be termed a second element, component, region, layer or section without departing from the teachings of the invention.

(19) Furthermore, relative terms, such as lower or bottom and upper or top, may be used herein to describe one element's relationship to another element as illustrated in the figures. It will be understood that relative terms are intended to encompass different orientations of the device in addition to the orientation depicted in the figures. For example, if the device in one of the figures is turned over, elements described as being on the lower side of other elements would then be oriented on upper sides of the other elements. The exemplary term lower, can therefore, encompasses both an orientation of lower and upper, depending of the particular orientation of the figure. Similarly, if the device in one of the figures is turned over, elements described as below or beneath other elements would then be oriented above the other elements. The exemplary terms below or beneath can, therefore, encompass both an orientation of above and below.

(20) It will be further understood that the terms comprises and/or comprising, or includes and/or including or has and/or having, or carry and/or carrying, or contain and/or containing, or involve and/or involving, and the like are to be open-ended, i.e., to mean including but not limited to. When used in this invention, they specify the presence of stated features, regions, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and/or groups thereof.

(21) Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present invention, and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

(22) As used herein, around, about or approximately shall generally mean within 20 percent, preferably within 10 percent, and more preferably within 5 percent of a given value or range. Numerical quantities given herein are approximate, meaning that the term around, about or approximately can be inferred if not expressly stated.

(23) As used herein, the phrase at least one of A, B, and C should be construed to mean a logical (A or B or C), using a non-exclusive logical OR.

(24) As used herein, the term Hummers method refers to a chemical process that can be used to generate graphite oxide through the addition of potassium permanganate to a solution of graphite, sodium nitrate, and sulfuric acid. It is commonly used by engineering and lab technicians as a reliable method of producing quantities of graphite oxide. It is also able to be revised in the creation of a one-molecule-thick version of the substance known as graphene oxide. In 1958, Hummers and Offeman reacted graphite with a mixture of KMnO.sub.4 and concentrated H.sub.2SO.sub.4 and achieved similar levels of oxidation to Brodie's method (Cite ref26: Hummers, W. S.; Offeman, R. E. Preparation of Graphitic Oxide. Journal of the American Chemical Society 1958, 80, 1339-1339). Ever since then, the Hummers method has been widely studied and modified in many ways. Typically, the modified Hummers method involves a pre-expansion step of graphite to increase the interlayer spacing and to achieve higher degree of oxidation. For pre-expansion, graphite is first treated with a mixture of concentrated sulfuric acid (H.sub.2SO.sub.4), potassium persulfate (K.sub.2S.sub.2O.sub.8) and phosphorus pentoxide (P.sub.2O.sub.5) at 80 C. for several hours. The pre-treated graphite is then diluted, filtered, washed, dried, and oxidized using a mixture of concentrated sulfuric acid, sodium nitrate (NaNO.sub.3) and potassium permanganate (KMnO.sub.4) at 45 C. for 2 h. The GO produced by this method contains up to 26 wt % oxygen. The oxidation degree and product yield have been greatly improved. In 2010, Tour and coworkers developed a more convenient and effective method, known as improved Hummers method (Cite ref31: Marcano, D. C.; Kosynkin, D. V.; Berlin, J. M.; Sinitskii, A.; Sun, Z.; Slesarev, A.; Alemany, L. B.; Lu, W.; Tour, J. M. Improved Synthesis of Graphene Oxide. ACS Nano 2010, 4, 4806-4814) to improve the degree of oxidation of GO, minimize the evolution of toxic gases during oxidation, and to get large-area GO sheets. In this synthesis protocol, sodium nitrate (NaNO.sub.3) is replaced by six equivalents of potassium permanganate (KMnO.sub.4). Additionally, the reaction mixture consists of a 9:1 mixture of concentrated sulfuric acid (H.sub.2SO.sub.4) and phosphoric acid (H.sub.3PO.sub.4). One of the advantages of this invention is the absence of NaNO.sub.3, thus no generation of toxic gases such as NO.sub.2, and N.sub.2O.sub.4 in the reaction, and making it more environmentally friendly.

(25) The description below is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. The broad teachings of the invention can be implemented in a variety of forms. Therefore, while this invention includes particular examples, the true scope of the invention should not be so limited since other modifications will become apparent upon a study of the drawings, the specification, and the following claims. For purposes of clarity, the same reference numbers will be used in the drawings to identify similar elements. It should be understood that one or more steps within a method may be executed in different order (or concurrently) without altering the principles of the invention.

(26) The world demands sustainable and renewable energy to counteract the climate change related to the CO.sub.2 emission from fossil fuels [1, 2]. Hydrogen production from water splitting with renewable power sources, considered as one of the most efficient ways to produce such energy at low cost and high purity, has attracted increasing attention [3-9]. In the water splitting process, water molecules are reacted to form molecular hydrogen and molecular oxygen. The splitting of water can be written as two half reactions. At the cathode, protons are reduced to hydrogen (hydrogen evolution reaction, HER), in acidic solution 2H.sup.++2 e.sup..fwdarw.H.sub.2, and 2H.sub.2O+2e.sup..fwdarw.2OH.sup.+H.sub.2 in basic solution. At the anode, water is oxidized to oxygen (oxygen evolution reaction, OER). In acidic solution, OER involves four proton-coupled electron transfers and oxygen-oxygen bond formation, 2H.sub.2O.fwdarw.O.sub.2+4H.sup.++4e.sup., and in alkaline solution, four hydroxyl groups (OH.sup.) were transformed into H.sub.2O molecules and O.sub.2 molecule with four electrons involved, 4OH.sup..fwdarw.O.sub.2+2H.sub.2O+4e.sup.[4, 8-10]. OER usually requires an overpotential in substantial excess of its thermodynamic potential (1.23 V vs the reversible hydrogen electrode (RHE), at standard temperature and pressure) to deliver an acceptable current density [4, 11]. Currently best known catalysts for water splitting contain precious metals such as Pt for HER and Ir for OER [4, 12-14]. However, these materials are rare and expensive. Therefore, search for low-cost, highly stable, low-overpotential, and high earth abundant electrocatalysts for water splitting is of keen interest [4].

(27) OER, as an important half-reaction for water splitting, has been intensely studied for many decades [4]. Among OER electrocatalysts, NiFe-based compounds have been used as active OER catalysts [4, 8, 16]. More recently, NiFe-based nanostructural materials have attracted great attention for being promising OER electrocatalysts in alkaline conditions for better activity and stability [6, 12-14, 16, 17]. Ni and Fe mixed oxides (NiFe oxides) have one of the lowest reported overpotentials for OER of about 0.20 V to obtain a current density of about 10 mA/cm.sup.2 [13, 14]. More interestingly, these electrocatalytic Ni and Fe oxide-based nanomaterials possess high performance for hydrogen and oxygen evolution when synthesized on carbon nanostructures as demonstrated recently [12-14]. It has been observed that nanoscale nickel oxide/nickel heterostructures formed on carbon nanotube (CNT) sidewalls are highly effective HER electrocatalysts with activity similar to platinum by Dai's group [12]. It was noticed that the formation of NiO/Ni heterostructure relied on the oxidized CNT growth substrate. Without any CNT as support, the same reaction steps produced aggregated Ni particles in a plate-like morphology with lower HER activity than NiO/Ni-CNT, in strong contrast to the small nanoparticle structure of NiO/Ni on CNT. These results suggested that on oxidized CNTs, the reduction of oxidized Ni species during thermal decomposition was impeded or retarded likely due to pinning or interactions of Ni species with oxidized CNTs through oxygen functional groups, delaying the reduction of Ni into larger aggregates via Ostwald ripening. It was concluded that substrate-precursor interaction could profoundly affect the morphology, structure and catalytic activity of materials [12]. With the same approach, Dai's group developed nanoscale NiFe-CNT electrocatalyst that presented superior OER performance over iridium catalyst [13].

(28) In agreement with Dai's work, it was further demonstrated by Cui's group that the catalytic activity can be dramatically improved, when transition metal oxide (iron, cobalt, nickel oxides and their mixed oxides) nanoparticles (about 20 nm) grown on carbon fiber paper (CFP) substrates are electrochemically transformed into ultra-small diameter (2-5 nm) nanoparticles through lithium-induced conversion reactions. Different from most traditional chemical syntheses, this method maintains excellent electrical interconnection among nanoparticles and results in large surface areas and many catalytically active sites. More interestingly, it was found that lithium-induced ultra-small NiFeO.sub.x nanoparticles are active bifunctional catalysts exhibiting high activity and stability for overall water splitting in base, better than the combination of benchmark catalysts iridium and platinum [14].

(29) In certain aspects, this invention focuses on a facile one-pot hydrothermal assembly of 3D RGO-nanocatalyst hybrid foams as effective catalysts for OER and HER, which produces low-cost, highly stable, low-overpotential, and high earth abundant electrocatalysts NiFe oxide and MoS.sub.2 for water splitting.

(30) According to the invention, NiFe oxide electro-nanocatalysts can be grown in 3D porous RGO foams that have presented a number of interesting applications [18-23]. The 3D RGO foam structure fabricated from flexible RGO sheets forms an effective network for electron transfer, provides massive pore structures for ion transport, and results in large surface areas for reaction [19, 20]. However, previous research work for NiFe oxide catalyst synthesis on carbon-based substrates involved multi-steps [12-14, 16], which increases the complexity for the synthesis. To solve the problems, this invention invents a facile, one-step process to synthesize RGO foam embedded with NiFe oxide nanoparticles. In certain embodiments, RGO-NiFe is used to represent RGO-NiFeO.sub.x, where NiFeO.sub.x could be a mixture of NiO and Fe.sub.2O.sub.3, depending on the thermal annealing conditions [14]. First, 3D RGO foams are fabricated using graphene oxide (GO) suspensions made from the modified Hummers method (the modified Hummers GO) [24]. Then the facile one-pot hydrothermal assembly of RGO-NiFe hybrid foams is obtained. The 3D RGO foams embedded with NiFe oxide nanoparticles (<5 nm) were successfully prepared in one-step hydrothermal process in a narrow pH range around 3.5. One embodiment of the preparation process of RGO-NiFe foams is illustrated in FIG. 1A. The RGO-NiFe foams were characterized using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The electrochemical properties of the RGO-NiFe foams were investigated by using a three-electrode system under alkaline conditions. It was observed that the OER onset potential of the RGO-NiFe sample was about 1.46 V vs. RHE, and the Tafel slope of about 57 mV/decade in 1 M KOH, comparable to those of iridium catalyst [14] and NiFe nanocompounds synthesized by other groups [13, 14, 16]. As a comparison with the RGO-NiFe porous foam, a RGO-NiFe membrane was also prepared via vacuum filtration and annealed at about 500 C. for OER studies, which has a tightly packed layered structure [25], in contrast with the 3D porous structure of the foam.

(31) In one aspect of the invention, a method of synthesizing 3D RGO foams embedded with water splitting nanocatalysts includes providing a first solution containing nickel (II) nitrate, a second solution containing iron (III) nitrate, and a graphene oxide (GO) aqueous suspension; mixing the GO aqueous suspension with the first solution and the second solution to form a GO-NiFe mixture; adjusting a pH value of the GO-NiFe mixture to be about 3.5; and performing hydrothermal reaction in the GO-NiFe mixture to form RGO-NiFe foams, wherein nanocatalysts containing Ni-Fi oxide particles are embedded in porous structures of the 3D RGO foams.

(32) In one embodiment, the GO-NiFe mixture is characterized with pH=3.5 and C:Ni:Fe=14:1:0.33.

(33) In one embodiment, the pH value of the GO-NiFe mixture is adjusted by adding a NaOH solution therein.

(34) In one embodiment, the first and second solutions are provided by dissolving Ni(NO.sub.3).sub.2.6H.sub.2O and Fe(NO.sub.3).sub.3.9H.sub.2O into deionized water, respectfully.

(35) In one embodiment, the hydrothermal reaction in the GO-NiFe mixture is performed in a sealed autoclave for hydrothermal reaction at a predetermined temperature for a period of time. In one embodiment, the predetermined temperature is in a ranges of about 160-200 C., and the period of time is in a range of about 7-11 h.

(36) In one embodiment, the method further includes washing the RGO-NiFe foam with deionized water.

(37) In one embodiment, the method further includes freeze-drying the RGO-NiFe foam under about 0.05 mbar vacuum at about 50 C. to obtain the RGO-NiFe solid foam.

(38) In one embodiment, the method further includes, prior to performing hydrothermal reaction in the GO-NiFe mixture, ultrasonicateing the GO-NiFe mixture to remove air bubbles that are trapped in the GO-NiFe mixture.

(39) In another aspect of the invention, a method of synthesizing 3D RGO foams embedded with water splitting nanocatalysts includes providing at least one solution containing at least one precursor of nanocatalysts, and a graphene oxide (GO) aqueous suspension; mixing the GO aqueous suspension with the at least one solution to form a mixture; and performing hydrothermal reaction in the mixture to form a 3D RGO foam embedded with the nanocatalysts.

(40) In one embodiment, the at least one precursor comprises Na.sub.2MoO.sub.4 and L-cysteine. In one embodiment, the 3D RGO foam embedded with the nanocatalysts is a 3D RGO-MoS.sub.2 foam.

(41) In one embodiment, the mixture is characterized with pH=5.8.

(42) In one embodiment, the at least one solution comprises a first solution containing nickel (II) nitrate, and a second solution containing iron (III) nitrate. In one embodiment, the first and second solutions are formed by dissolving Ni(NO.sub.3).sub.2.6H.sub.2O and Fe(NO.sub.3).sub.3.9H.sub.2O into deionized water, respectfully.

(43) In one embodiment, the mixture is characterized with pH=3.5 and C:Ni:Fe=14:1:0.33.

(44) In one embodiment, the hydrothermal reaction in the mixture is performed in a sealed autoclave for hydrothermal reaction at a predetermined temperature for a period of time. In one embodiment, the predetermined temperature is in a ranges of about 160-200 C., and the period of time is in a range of about 7-11 h.

(45) In one embodiment, the 3D RGO foam embedded with the nanocatalysts is the RGO-NiFe foam.

(46) In one embodiment, the method further includes freeze-drying the RGO-NiFe foam under about 0.05 mbar vacuum at about 50 C.

(47) In one embodiment, the method further includes, prior to performing hydrothermal reaction in the mixture, ultrasonicateing the mixture to remove air bubbles that are trapped in the mixture.

(48) In yet another aspect, the invention relates to 3D RGO foams embedded with nanocatalysts, synthesized the above disclosed methods.

(49) In a further aspect, the invention relates to a device for water splitting including a working electrode containing 3D RGO foams embedded with nanocatalysts, where the 3D RGO foams embedded with nanocatalysts are synthesized the above disclosed methods.

(50) A facile one-pot hydrothermal assembly of 3D RGO-nanocatalyst hybrid foams as effective catalysts for oxygen evolution reaction and hydrogen evolution reaction, can find applications related to hydrogen fuel clean energy, space applications, biomedical applications, and tissue engineering.

(51) These and other aspects of the present invention are further described below. Without intent to limit the scope of the invention, exemplary instruments, apparatus, methods and their related results according to the embodiments of the present invention are given below. Note that titles or subtitles may be used in the examples for convenience of a reader, which in no way should limit the scope of the invention. Moreover, certain theories are proposed and disclosed herein; however, in no way they, whether they are right or wrong, should limit the scope of the invention so long as the invention is practiced according to the invention without regard for any particular theory or scheme of action.

Fabrication of RGO Foams

(52) In this exemplary example, GO was synthesized from natural graphite using modified Hummers method [24, 26]. The concentration of prepared GO suspension solution was determined to be about 2 mg/mL. About 63 atomic % was C, as estimated by XPS. The 3D RGO foam was fabricated via a hydrothermal process [13, 18, 20, 27]. Different pH levels were systematically studied and the sturdy RGO foam was formed in a wide pH range of about 1.5-11.5 when using the GO suspension from the modified Hummers method. To be consistent with the condition for the RGO-NiFe foam synthesis, the pH of the GO suspension was adjusted to about 3.5. About 10 mL of the GO suspension were transferred to a 23 mL Teflon-lined autoclave (Model No. 4749, Parr) and went through a hydrothermal reduction process at about 180 C. for about 9 h. The as-prepared RGO foam was carefully taken out of the autoclave and washed with DI water for several times. Finally, it was freeze-dried under about 0.05 mbar vacuum at about 50 C. using a freeze dryer (Labconco FreeZone 2.5).

Fabrication of RGO-NiFe Foams

(53) In this exemplary embodiment, the one-pot production of the RGO-NiFe foam was very sensitive to the pH of the GO-NiFe mixture. Only in a narrow pH range, one-pot assembled sturdy RGO-NiFe foam can be produced. Factors including different pH levels and the starting stoichiometric ratios of GO and NiFe (Ni/Fe=3:1) [14, 16] were systematically studied. The one-pot RGO-NiFe foam can only be formed under a narrow pH range around 3.5 and the optimal condition was determined as pH=3.5 and C:Ni:Fe=14:1:0.33. In other conditions, the reactions resulted in a mixture of RGO and NiFe oxide-related products, and a stable 3D RGO-NiFe foam structure cannot be produced. To grow the RGO-NiFe foam, the solutions of about 0.10 M nickel (II) nitrate and about 0.10 M Iron (III) nitrate were first prepared by dissolving Ni(NO.sub.3).sub.2.6H.sub.2O and Fe(NO.sub.3).sub.3.9H.sub.2O into deionized water (MilliQ water 18.2 M.Math.cm), respectfully. About 10 mL of the homogeneous graphene oxide aqueous suspension was mixed under stirring with about 0.75 mL of Ni(NO.sub.3).sub.2 solution and about 0.25 mL of Fe(NO.sub.3).sub.3 solution to form a GO-NiFe mixture. The pH of the GO-NiFe mixture was then adjusted to around 3.5 by carefully adding a NaOH solution. Afterwards, the mixture was lightly ultrasonicated for several minutes to get rid of air bubbles that were trapped in the gel-like mixture. The mixture was then sealed in the autoclave for hydrothermal reaction at about 180 C. for about 9 h. After the reaction, a cylindrical foam sitting in a colorless solution was observed in the autoclave (FIG. 1B), suggesting successful one-pot growth of the RGO-NiFe foam, where all nickel-iron oxide particles were embedded in the porous structure of the 3D RGO foam. The resulting RGO-NiFe foam was taken out of the autoclave and washed with deionized water for several times. The RGO-NiFe foam was then freeze-dried under about 0.05 mbar vacuum at about 50 C. to obtain the RGO-NiFe solid foam (also termed as RGO-NiFe foam in the disclosure). The foam has a cylindrical shape with an approximate diameter of about 1.5 cm and the height of about 1.5 cm. The fabrication process of the exemplary embodiment is shown in FIG. 1A.

Thermal Treatment of RGO-NiFe Foams

(54) In this exemplary embodiment, the RGO-NiFe foam was annealed in a tube furnace at about 500 C. under the protection of N.sub.2 for about one hour. Then the RGO-NiFe sample was cooled down to room temperature and ready for use (also termed as RGO-NiFe foam 500 C. in the disclosure).

Preparation of a RGO-NiFe Membrane

(55) In one embodiment, as a comparison to the RGO-NiFe foam, a RGO-NiFe membrane was also prepared via vacuum filtration. Specifically, about 20 mL of the GO suspension solution was mixed under stirring with about 1.5 mL of 1.0 M Ni(NO.sub.3).sub.2 and about 0.5 mL of 1.0 M Fe(NO.sub.3).sub.3 solutions based on the ratio C:Ni:Fe=1.4:1:0.33, with the amount of Ni and Fe about 10 times more than that in the foam samples. Then, about 4.5 mL of 1.0 M NaOH solution was slowly added to the mixture and stirred for about 30 min at about 70 C. After that, the gel-like mixture was filtered through a 0.8 m pore-size ATTP filter membrane via vacuum filtration. The resulting GO-NiFe membrane was then thermally annealed at about 500 C. for about 1 h under the protection of N.sub.2 (also termed as RGO-NiFe film 500 C. in the disclosure).

Materials Characterizations

(56) The RGO-NiFe samples were characterized by XPS, XRD, Raman spectroscopy, SEM, and TEM. XPS samples were drop-dried onto silicon substrates and measured on a K-Alpha X-ray XPS System equipped with monochromatic Al K (h =1486.6 eV). XRD data were collected using a Rigaku MiniFlex 600 XRD system for a step size of about 0.02 and dwell time of about 5/min in the 2 range of 3-80 at standard potential and current settings of about 40 kV and about 15 mA, employing a monochromatic Cu K target radiation source (=1.5418 ). Raman spectroscopy was performed using an EZ Raman-N microscope (excitation wavelength 532 nm) at about 50% power, room temperature, solid samples on silicon wafer. The morphology and microstructure of the samples were analyzed using a JEOL 7000F SEM with energy-dispersive X-ray (EDX) analysis of the composition. TEM imaging was performed using JEOL 2100F TEM, operated at 60 kV.

Sample Preparation for Electrochemical Measurements

(57) In one embodiment, to prepare the RGO-NiFe catalyst samples on glassy carbon disk electrodes (MF-2012, BASi), about 1 mg of the RGO-NiFe foam sample was mixed with about 100 l of DI water, about 100 l of ethanol, and about 5 l of about 5 wt % Nafion solution (Sigma-Aldrich) by at least 15 min ultrasonication to form a homogeneous catalyst ink. Afterwards, about 5 l of the ink was drop-casted and dried on to a glassy carbon electrode of about 3 mm in diameter, with loading of about 0.35 mg/cm.sup.2 including RGO, which about 70% of the loading, about 0.24 mg/cm.sup.2, is on the active area of the electrode. The RGO-NiFe membrane sample was also prepared on a glassy carbon working electrode using the same method.

Electrochemical Measurements

(58) In one embodiment, to examine the electrochemical OER catalytic activities, a standard three-electrode electrochemical system was investigated using a BASi Epsilon electrochemical workstation. The catalyst ink-loaded glassy carbon disk electrode was used as a working electrode. A Pt wire electrode (MW-1032, BASi) mounted in a CTFE cylinder was used as a counter electrode. A saturated calomel electrode (SCE, Thermo Scientific) was selected as the reference electrode with a potential of about 1.043 V versus RHE in 1 M KOH (prepared from KOH pellets/certified ACS, Fischer Chemical), calibrated against a HydroFlex hydrogen reference electrode (ET070, EQAD). No contributions for the OER from 1 M KOH were observed. The electrochemistry workstation was used to measure the cyclic voltammetry (CV) and the linear sweep voltammetry (LSV). The CV measurements were conducted in a voltage window from about 0.8 to about 0.8 V (vs. SCE) with scan rates typically of about 50-100 mV/s. The LSV measurements were performed in a potential window of about 0-0.8V (vs. SCE) under a constant sweep rate of about 5 mV/s. The potentials were referred to RHE and were iR-corrected, unless noted. All of the electrochemical measurements were performed under 1 atmosphere in air and at room temperature.

Growth of RGO and RGO-NiFe Foams

(59) In one embodiment, the hydrothermal method is chosen to fabricate 3D porous RGO foams because of its unique features. In general, hydrothermal reduction is a chemical reduction method for GO, usually performed in a sealed container, so the solvent can be brought to a temperature well above its boiling point by the increase of pressure resulting from heating. In a typical hydrothermal process, overheated supercritical water can play the role of reducing agent and offers a green chemistry alternative to organic solvents [27-29]. However, in the experimental condition, the temperature used is about 180 C., below 374 C., the critical temperature of water. Therefore, the supercritical water does not exist. The water may play an important role as discussed by West [30]. The water serves as the pressure transmitting agent in the forms of liquid and vapor. It enables reactions to happen with possible enhanced solubility under pressure and with the aid of liquid and vapor phases. In addition, its physiochemical properties can be widely changed with changes in pressures and temperatures, which allows the catalysis of a variety of ionic bond cleavage reactions in water [29]. So a stable and homogeneous dispersion of reduced nanosheets, RGO, can be produced. Most of reported results regarding RGO foam formation [18, 20] are based on GO from the modified Hummers method [24]. In certain embodiments, the modified Hummers GO can be used to grow a relatively sturdy cylindrical GO foam at a wide pH range tested, from 1.5 to 11.5. On the other hand, the improved Tour GO [31] can form stable 3D porous foams in a relatively narrow pH range and the foam formation is sensitive to the autoclave inner surface cleanness. As shown in FIG. 1C, 3D RGO-MoS.sub.2 foam was synthesized using Tour GO at pH=5.8, with starting materials of Na.sub.2MoO.sub.4 and L-cysteine [32]. For one-step hydrothermal production of RGO-NiFe foams, the requirement for pH levels is even more stringent. After trials and errors, it was found that only in a narrow pH range around 3.5, one-pot assembled 3D RGO-NiFe foam can be successfully produced by using the modified Hummers GO, with the ratio C:Ni:Fe=14:1:0.33.

RGO Foam and RGO-NiFe Foam Characterizations

(60) As discussed in the previous work [20], under the hydrothermal synthesis conditions, reactions are expected between/among the hydroxyl, carboxyl, and epoxy functional groups of adjacent GO sheets to generate aromatic ether and ester bonds between the sheets, mainly at the edges [20, 27]. C1s XPS analysis reveals that the RGO foams made via the hydrothermal process contained the dominant CC bonds (about 284.8 eV), hydroxyl COH (about 286 eV), ether CO (about 287 eV), and ester C(O)O (about 289 eV) bonds (FIG. 2A). The -* shake-up satellite peak was observed for the GO foam around about 292 eV [33]. This indicated that the delocalized conjugation, a characteristic of aromatic C structure, was partially restored in RGO foam samples [34, 35]. Similarly, for the C1s XPS spectra of the RGO-NiFe foam sample and the RGO-NiFe foam 500 C. sample shown in FIG. 2A, in addition to the dominant CC bonds (about 284.8 eV), the peaks of the ether CO (about 287 eV) and ester C(O)O (about 289 eV) bonds were also observed. XPS spectra (FIGS. 2B-2C) also corroborated the existence of both Ni and Fe in the two hybrid foam materials. The Ni species was mostly in the +2 oxidation state from the Ni 2p spectra (FIG. 2B), with Ni 2p.sub.3/2 binding energies close to 855.6 eV. The Fe species was mostly in the +3 oxidation state from the Fe 2p spectra (FIG. 2C) [13].

(61) The phase structures of RGO-NiFe samples were measured by XRD, as shown in FIG. 3. Almost no peaks were observed for the GO-NiFe gel-like mixture sample, as shown in curve (a) of FIG. 3, and the RGO-NiFe foam sample, as shown in curve (b) of FIG. 3, indicating that either the sample was poorly crystallized (the GO-NiFe gel-like mixture sample) or the crystalline size of the sample (the RGO-NiFe foam sample) was too small to be detected in XRD (<5 nm), as observed by other groups previously [14, 36]. When annealing at about 500 C., as shown in curve (c) of FIG. 3, a few peaks were observed. The peaks centered at around 37.5 and 43.2 corresponded to NiO (111) and NiO (200), respectively. The diffraction peak centered at around 2=29.3 corresponded to the (220) plane of Fe.sub.3O.sub.4, and the 63.0 peak corresponded to the (220) plane of NiO or the (440) plane of Fe.sub.3O.sub.4 [14]. The observed Fe.sub.3O.sub.4 peaks suggested the further reduction of Fe.sub.2O.sub.3.fwdarw.Fe.sub.3O.sub.4 when annealing at about 500 C. The XRD data were further corroborated with Raman spectra and TEM images.

(62) Raman spectra shown in FIG. 4 further revealed the structural information of the samples. Initially, the GO-NiFe gel-like mixture shows no observable D band (1350 cm.sup.1) and G band (1590 cm.sup.1) of GO, but a broad peak at about 510 cm.sup.1 coming from the M-O (mainly NiO) vibrational band of the disordered NiFe hydroxides in the GO-NiFe gel-like mixture [17]. When the sample was hydrothermally treated at about 180 C., GO was reduced to better crystallized RGO foam with enhanced Raman intensity at about 1350 cm.sup.1 and about 1590 cm.sup.1. The disordered NiFe hydroxides became crystallized with the NiO band peak position shifting to the red at about 450 cm.sup.1. When annealed at about 500 C., an additional band at about 560-670 cm.sup.1 appeared, which could be related to Fe.sub.2O.sub.3 and Fe.sub.3O.sub.4 [17]. The D and G bands almost disappeared, suggesting a dramatic decrease in the amount of RGO.

(63) SEM image in FIG. 5A shows the porous 3D structures of RGO foam. The functional groups, such as hydroxyl, carboxyl, and epoxy groups that are mainly located on GO sheets edges, were covalently interconnected and cross-linked with each other during the hydrothermal process, thereby forming a monolithic 3D chemically linked RGO network [18, 20]. This unique 3D structure can accommodate the active sites of NiFe oxide nanoparticles, facilitate their electron transfer at electrode surfaces, and maintain their electrochemical activities. The RGO-NiFe foam sample has a well-defined and interconnected 3D porous network as imaged by SEM in FIG. 5B. The NiFe oxide nanoparticles were grown on the 3D RGO backbones. The pore sizes of the network are in the range of sub-micrometers to several micrometers and the pore walls include thin layers of stacked graphene sheets. This 3D porous structure provides a good support for the NiFe oxide nanoparticles, greatly increases the electron transport and results in a larger surface area. In comparison, the foam after annealed at about 500 C., lost some of the RGO, with an increase of NiFe nanoparticle concentration in the sample, as shown in FIG. 5C.

(64) TEM images showed distinct differences between the RGO-NiFe foam sample and its 500 C. annealed sample. As shown in FIGS. 6A-6B, NiFe oxide nanoparticles are roughly spherical with an average diameter of less than about 5 nm. However, after 500 C. annealing, in addition to the small NiFe oxide nanoparticles of about 2-5 nm in diameter, large particles of about 20-30 nm in diameter were observed, accompanying with the decomposition of RGO support, as shown in FIGS. 6C-6D. As a result, the sample annealed at about 500 C. might suggest an increased amount and size of NiFe nanoparticles, a poorer electron transport due to loss of RGO, and a decreased surface area of RGO network.

RGO-NiFe Samples on OER

(65) Shown in the insert of FIG. 7 is the CV of the RGO-NiFe foam sample. The peak around 1.48 V is assigned to the Ni(II)/Ni(III or IV) redox process [13]. The polarization curves in FIG. 7 clearly show that all three RGO-NiFe samples were able to produce oxygen when used as an electrocatalyst. The RGO-NiFe foam sample achieved a current density of about 24.5 mA/cm.sup.2 at about 1.7 V, indicating the highest electrocatalytic ability among the three samples. Its onset of oxygen evolution took place at about 1.46 V. In addition, the sample achieved a current density of about 10 mA/cm.sup.2 at the potential of about 1.62 V, while the RGO-NiO/Ni foam 500 C. sample had an about 10 mA/cm.sup.2 current density at a higher potential of about 1.71 V. In comparison, the 500 C. annealed RGO-NiO/Ni membrane sample had an about 10 mA/cm.sup.2 current density at about 1.68 V (Table 1). The result indicates that the RGO-NiFe foam had the better electrocatalytic performance than the other two RGO-NiFe samples annealed at 500 C. Since the onset potentials are almost the same for the three samples, as listed in Table 1, the intrinsic OER activities for the three samples are similar. The difference in OER current densities at a given OER potential, for example, at about 1.6 V vs. RHE in FIG. 7, could be caused by the difference in a few factors, including the number of active sites, the conductivity of RGO, and the surface area needed for electron transfer and ion transport in the samples. The result suggests that further improvement of OER activities for RGO-NiFe foam is possible, by optimizing these factors.

(66) TABLE-US-00001 TABLE 1 Comparison of OER properties of NiFe oxide and Ir/C electrocatalysts in 1M KOH solution. Onset Potential at Tafel potential 10 mA/cm.sup.2 slope Sample (V) (V) (mV/dec) Reference RGO-NiFe Foam 1.46 1.62 57 This invention RGO-NiFe Foam 1.47 1.71 75 This 500 C. invention RGO-NiFe Film 1.46 1.68 87 This 500 C. invention NiFe-CNT 1.45 1.47 31 [13] Pristine NiFe-CFP 1.50 1.57 44.0 [14] 2-cycle NiFe-CFP 1.43 1.48 31.5 [14] NiFe-NGF 1.49 1.57 45 [16] (0.1M KOH) Ir/C 1.47 1.52 39.2 [14] Ir/C (0.1M KOH) 1.48 1.64 54 [16]

(67) It is worthwhile to discuss the use of carbon materials on the anode because of the concern of electrochemical oxidation of carbon [37]. Recently, there have been an increasing number of reports that carbon materials are used in the anode side as a support or scaffold for nanostructural catalysts in alkaline solution. The graphene-based carbon materials include carbon nanotubes [13], carbon fibers [14, 38], reduced graphene oxide [16, 39], and graphene shells [40]. The anodes show excellent stability under the water splitting tests. The contributions of the carbon support for OER are usually negligible below about 1.65 V vs RHE [9]. However, recent experimental data indicate that with the carbon support, NiFe oxide-based water splitting can be run at about 1.8 V for a long period of time without degradation [14], suggesting the stability of the anode with the carbon support. In contrast, carbon supported Pt and Ir benchmark catalysts showed an unstable water splitting performance, which decayed over time [14]. In addition, the NiFe nanocatalysts on the carbon supports were bifunctional and lowered the HER and OER overpotentials, so water splitting reaction can be effectively and stably run at about 1.51 V [14]. These results open the opportunities for the use of carbon supported nanocatalysts for OER in alkaline solution. Furthermore, reactive oxygen species (ROS) generated in the water oxidation progress contribute to the instability of catalytic materials [41]. The stability the carbon-supported NiFe catalysts could be related to ROS scavenging properties of graphene-based materials [42]. These graphene-based materials like carbon nanotubes also present self-recovery capability from oxidation in alkaline conditions [43-48].

(68) In one embodiment, the polarization curves are fitted to the Tafel equation =b log(j/j.sub.0), where is the overpotential, b is the Tafel slope, j is the current density, and j.sub.0 is the exchange current density [49]. The Tafel slope indicated the increase of the overpotential required in order to raise the current density by 10-fold [12, 50, 51]. A smaller increase in overpotential, as represented by a smaller Tafel slope value, would mean a more efficient OER. The Tafel slope, along with the slope values, was displayed in FIG. 8. The RGO-NiFe foam sample exhibited a Tafel slope of about 57 mV/decade in 1 M KOH. This value was the closest one to that of the Ir/C reference (about 40 mV/decade) [13, 14, 49]. The RGO-NiFe foam 500 C. sample had a Tafel slope of about 75 mV/decade, weaker than that of as-prepared 3D RGO-NiFe foam sample. This might be explained by the fact that the further heat annealing processes had a negative impact to the 3D porous structure of the RGO foam by increasing the sizes of NiFe nanoparticles and decreasing the surface area of RGO, which resulted in a weaker electron transport and poorer catalytic ability. It is worth noting that the RGO-NiFe membrane sample, made through vacuum filtration then followed by annealing at about 500 C. (the amount of Ni and Fe was 10 times more than that in the foam samples), exhibited the largest value of Tafel slope of about 87 mV/decade. This might be partly caused by the insufficient surface area of the catalyst in the membrane, for which, further study is underway. The electrochemical performances of RGO-NiFe samples were summarized in Table 1, together with a few benchmark NiFe oxide electrocatalysts synthesized from other research groups. The OER properties of the RGO-NiFe foam sample are close to those of pristine NiFeCFP [14] and approach those of other listed superior samples [13, 14, 16]. The OER performance of the RGO-NiFe foams could be further improved by tuning other synthesis factors such as temperatures and solvents etc., in addition to pH.

(69) In brief, according to the invention, nanoscale Ni and Fe mixed oxide OER nanoparticles embedded in 3D reduced graphene oxide foam network (RGO-NiFe foam) and 3D RGO-MoS.sub.2 HER foam were successfully synthesized through the simple one-pot hydrothermal process according to embodiments of the invention. With a focus on the RGO-NiFe foam, the as-prepared RGO-NiFe foam sample, together with the foam sample annealed at about 500 C. and a RGO-NiFe membrane sample were evaluated for their OER properties. The highest OER activity of the electrocatalysts was observed for the RGO-NiFe foam sample, and the Tafel slope of about 57 mV per decade was achieved and comparable to those of iridium catalyst [14] and NiFe nanocompounds synthesized by other groups [13, 14, 16]. The relatively high catalytic activity of the sample was possibly attributed to the nanoscopic NiO/FeO.sub.x interfaces in the graphene 3D structure with an enhanced surface area that was ideally suited for electron transfer and ion transport. The highly active RGO-NiFe hybrid foam catalyst with low cost, earth abundance and environmental friendliness is promising for future water-splitting devices. Further development of self-assembling 2D graphene sheets into complex 3D macrostructures is being carried out for further understanding their assembly behaviors and producing graphene-based materials with industrial interests. Among other things, the approach can be applied to develop other viable, environmentally friendly, and earth-abundant OER and HER catalysts for water splitting, and other applications related to hydrogen fuel, space applications, biomedical applications, and tissue engineering. The approach can be efficiently used at room-temperature, in contrast with current high temperature methods.

(70) The foregoing description of the exemplary embodiments of the invention has been presented only for the purposes of illustration and description and is not intended to be exhaustive or to limit the invention to the precise forms disclosed. Many modifications and variations are possible in light of the above teaching.

(71) The embodiments were chosen and described in order to explain the principles of the invention and their practical application so as to enable others skilled in the art to utilize the invention and various embodiments and with various modifications as are suited to the particular use contemplated. Alternative embodiments will become apparent to those skilled in the art to which the invention pertains without departing from its spirit and scope. Accordingly, the scope of the invention is defined by the appended claims rather than the foregoing description and the exemplary embodiments described therein.

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