CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit of and priority to co-pending U.S. Provisional Patent Application No. 62/234,157, filed on September 29, 2015, entitled "SCALABLE PHOTOREACTOR FOR HYDROGEN PRODUCTION," the contents of which is incorporated by reference herein in its entirety.

BACKGROUND

Hydrogen fuel is a zero-emission fuel that can be used to power vehicles, machinery, and other electric devices. As there is very little free hydrogen gas, hydrogen is only an energy carrier and not an energy resource like fossil fuels. However, hydrogen can be produced by steam reforming of hydrocarbons, eiectroiysis, and thermolysis. Today, fossil fuels are the dominant source for hydrogen and can be processed to produce hydrogen via steam reforming. However, these current methods do not represent a sustainable source for free hydrogen and the steam reforming process generates substantial amounts of carbon dioxide, which requires expensive and often impractical solutions and unused to prevent the carbon dioxide release into the atmosphere.

Hydrogen can also be obtained from water via water splitting that can occur by techniques such as electrolysis, chemically assisted electrolysis, radiolysis, photocatalysis, and thermolysis. However the inefficiencies, expensive materials and input energy required for hydrogen production from water an industrial scale has limited their implementation on a large scale. Current methods for splitting water via eiectroiysis typically require a membrane to separate the hydrogen protons during the wafer splitting reaction and to specifically allow them to combine with electrons to produce H ₂ gas. The need of a membrane significantly increases the cost and scalability of the water splitting reactor also referred to herein as an electrolyzer. The electrolyzer should enable to separately produce hydrogen and oxygen in such configuration with avoiding cross-over of product each other. As such, there exists an urgent unmet need to develop improved methods and systems of water splitting for the production of hydrogen gas for hydrogen fuel production.

SUMMARY

Provided herein are various embodiments of devices, systems and methods of water splitting for the improved production of hydrogen gas for hydrogen fuel production . Various embodiments of a membrane-free water-splitting electrolyzer are described herein, in one or more embodiments the membrane-free water-splitting electrolyzer can contain a power source configured to generate about 1 .4 V to about 2.2 V, a rail reactor, where the rail reactor can be operatively coupled to the power source, and where the rail reactor can have a first "U" shaped channel and a second "U" shaped channel; and an eiectrocatalysi element, where the eiectrocatalysi element can have a first eiectrocatalyst and a second electrocatalyst, where the first eiectrocatalyst and the second eiectrocatalyst can be electrically coupled to the power source, where the first electrocatalyst can be positioned within the first "U" shaped channel and , where the second electrocatalyst can be positioned within the second "U" shaped channel. Embodiments of the membrane-free water-splitting electrolyzer can have a solar ceil as the power source, in some embodiments of the membrane-free water splitting electrolyzer, the first and the second "U" shaped channel can each be composed of an alkaline resistant polymer or co-polymer. In some embodiments of the membrane-free water-splitting electrolyzer, the first and the second electrocatalyst each can contain a transition metal, a noble metal, or a transition metal and a noble metal. In some embodiments, at least one component of the membrane-free water-splitting electrolyzer can be in fluidic contact with an electrolyte solution, in some embodiments of the membrane-free water-splitting electrolyzer, the electrolyte solution can be a densely buffered electrolyte solution. In some embodiments of the membrane-free water-splitting electrolyzer the electrolyte solution can be an acidic buffered electrolyte solution, an alkali buffered electrolyte solution, or a neutral buffered electrolyte solution.

Also described herein are embodiments of a system that can have a plurality of membrane-free water splitting electrolyzers. In one or more embodiments the system can have a plurality of rows, where each row of the plurality of rows can include a plurality of membrane-free water-splitting electrolyzers, where each membrane free water-splitting eiectrolyzer of the plurality of membrane-free water splitting electrolyzers can have a rail reactor, wherein the rail reactor can be operatively coupled to a power source configured to generate about 1 .4 V to about 2.2 V, and where the rail reactor can include a first and a second "U" shaped channel; and an electrocataiyst element, where the electrocatalyst element can include a first and a second electrocataiyst, where the first and the second electrocatalyst can be electrically coupled to the power source, where the first electrocataiyst can be positioned within the first "U" shaped channel, and where the second electrocatalyst can be positioned within the second "IT shaped channel. In some embodiments of the system, each row can be coupled to at least one other row via the channels of the membrane-free water-splitting eiectrolyzer. in some embodiments of the system, at least one component of at least one membrane-free water-splitting eiectrolyzer of the plurality of membrane-free water-splitting electrolyzers can be in fiuidic contact with an electrolyte solution . In some embodiments, the electrolyte solution can be a densely buffered electrolyte solution , in some embodiments, the electrolyte solution can be an acidic buffered electrolyte solution , an alkali buffered electrolyte solution , or a neutral buffered electrolyte solution .

Also described herein are methods of water-splitting. In one or more embodiments the methods of water-splitting can include applying a voltage to a membrane-free rail reactor, where the rail reactor can have a first and a second "U" shaped channel; and an electrocataiyst element, where the electrocatalysts element can have a first and a second electrocatalyst, where the first electrocataiyst can be positioned within the first "U" shaped channel, and where the second electrocataiyst can be positioned within the second "U" shaped channel. In some embodiments of the method, the voltage is about 1 .4 V to about 2.2 V. In some embodiments of the method, the electrocatalyst element can be in fluidic contact with an electrolyte solution, in some embodiments of the method, the electrolyte solution can be a densely buffered electrolyte solution, in some embodiments of the method, the electrolyte solution can be an acidic buffered electrolyte solution, an alkali buffered electrolyte solution, or a neutral buffered electrolyte solution, in some embodiments of the method, the method can further include generating the voltage, wherein the voltage can be generated by a solar ceil. In some embodiments of the method, the first and the second "U" shaped channel each be composed of an alkaline resistant polymer or co-polymer. In some embodiments of the method, the electrocatalyst can contain a transition metal, a noble metal, or a transition metal and a noble metal.

Other systems, methods, features, and advantages of the present disclosure will be or become apparent to one with skill in the art upon examination of the following drawings and detailed description . It is intended that all such additional systems, methods, features, and advantages be included within this description , be within the scope of the present disclosure, and be protected by the accompanying claims.

BRIEF DESCRIPTION OF THE DRAWINGS

Further aspects of the present disclosure will be readily appreciated upon review of the detailed description of its various embodiments, described below, when taken in conjunction with the accompanying drawings. The components in the drawings are not necessarily to scale, emphasis instead being placed upon dearly illustrating the principles of the present disclosure. Moreover, in the drawings, like reference numerals designate corresponding parts throughout the several views.

Fig. 1 shows one embodiment of a membrane-free water splitting eiectroiyzer.

Fig. 2 shows another embodiment of a membrane-free water splitting eiectroiyzer.

Fig. 3 shows another embodiment of a membrane-free water splitting eiectroiyzer. Fig. 4 shows another embodiment of a membrane-fee water splitting electrolyzer.

Fig. 5 shows a system containing coupled membrane-free water splitting electrolyzers as substantially described herein.

Figs. 6A-6C show graphs demonstrating experimentally observed potentials reaching -10 rnA cm^ over a polycrystailine Pt disk electrode in 1 .5 mol L ^"1 phosphate solutions with various (Fig. 6A) K ^÷ or (Fig. 6B) Na ^÷ concentration, and (Fig. 6C) in 1 .5 mol L ^""1 MH ₂ P0 (M: Li, Na and K) electrolyte solutions with bubbling H ₂ (conditions: -50 mV s ^"1 , 3600 rpm, 298 K).

Fig. 7 shows a graph demonstrating experimentally observed potentials reaching -10 mA cm ^"2 in various electrolyte solutions over a polycrystailine Pt disk electrode with bubbling H ₂ (conditions: -50 mV s ^" \ 3600 rpm, 298 K).

Figs. 8A-8B show graphs demonstrating experimentally observed potentials reaching -10 mA cm ^"2 over a polycrystailine Ni disk electrode in (Fig, 8A) 1 .5 mol L ^"1 phosphate solutions with various K ⁺ concentration, and (Fig. 8B) in various simple electrolyte solutions (conditions: H ₂ bubbling, -50 mV s ^~ \ 3600 rpm, 298 K).

Figs. 9A-9B show graphs demonstrating experimentally observed potentials reaching -10 mA cm ^"2 over a Ni o electrode in (Fig. 9A) 1 .5 mol L ^"1 phosphate solutions with various K ⁺ concentration, and (Fig. 9B) in various concentrations of K _{1 2} H _{1 8} P0 ₄ (conditions: H ₂ bubbling, -50 mV s ^~ \ 3600 rpm, 298 K).

Figs. 10A-10D show graphs demonstrating 0 ₂ solubility in various electrolyte solutions of (Fig. 1 QA) Na* with H ₂ P0 ₄ ^" , ΗΡ0 ₄ ^2" , Ρθ ' ^" , HC0 ₃ ^" or C0 ₃ ^2" , and (Fig. 10B) Lf, Na*, K ⁺ , Rb ⁺ or Cs ⁺ with H ₂ P0 ₄ ^" , calculated using the Sechenov equation, (Fig. 10C) kinematic viscosity of alkali metal (Na ⁺ or K ⁺ ) with various anion (H ₂ P0 ₄ ^" , HP0 ^2" or HC0 ₃ ^" ) electrolyte solutions taken from the data book, ⁵ '' and (Fig. 10D) calculated limiting diffusion current for the oxygen reduction reaction in various electrolyte solutions.

Figs. 1 1A-1 1 B show graphs demonstrating experimentally observed electric current densities at 400 mV vs. RHE in various electrolyte solutions over a polycrystailine Pt disk electrode with (Fig. 1 1 A) C½ and (Fig. 1 1 B) H ₂ bubbling (conditions: -50 mV s ^" \ 3600 rpm, 298 K).

Fig. 12 shows a graph demonstrating a comparison between electric current densities with 0 ₂ bubbling at -50 mV vs. RHE (y-axis) and with 0 ₂ bubbling at 400 mV vs. RHE + with H ₂ bubbling at -50 mV vs. RHE (x-axis), recorded in various electrolyte solutions over a polycrystalline Pt disk electrode (conditions: -50 mV s ^-1 , 3600 rpm, 298 K).

Fig. 13 shows a graph demonstrating calculated faradaic efficiency to the hydrogen evolution reaction in various electrolyte solutions over a polycrystalline Pt disk electrode.

Figs. 14A-14D show graphs demonstrating linear-sweep voitammograms over a polycrystalline Pt disk electrode with various bubbling gases (Ar, H ₂ or 0 ₂ ) in (Fig. 14A) 2.1 mo I L ^{" 1} K ⁺ and 1 .5 mol L ^"1 phosphate, (Fig. 14B) 3.0 mol L ^"1 K ₂ HP0 ₄ , (Fig. 14C) 1 .0 mol L ^"1 HCI0 ₄ and (Fig. 14D) 1 .0 mol L ^"1 KOH (conditions: -50 mV s ^"1 , 3800 rpm, 298 K).

Fig. 15 shows a graph demonstrating the solution resistance as a function of solute concentration.

Figs. 16A-16C show photographs demonstrating one embodiment of a scalable rail reactor in use. Fig. 16A shows a side view, Fig. 16B demonstrates the oxygen production, and Fig. 16C demonstrates the hydrogen production from the embodiment of the scalable rail reactor.

Fig. 17 shows a graph demonstrating hydrogen and oxygen evolution from one embodiment of the scalable rail reactor.

DETAILED DESCRIPTION

Before the present disclosure is described in greater detail, it is to be understood that this disclosure is not limited to particular embodiments described, and as such may, of course, vary, it is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting. Although particular embodiments are described, those embodiments are mere exemplary implementations of the system and method. One skilled in the art will recognize other embodiments are possible. Ail such embodiments are intended to fall within the scope of this disclosure.

Where a range of values is provided , 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 disclosure. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges and are also encompassed within the disclosure, 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 disclosure.

it should be noted that ratios, concentrations, amounts, and other numerical data can be expressed herein in a range format, it is to be understood that such a range format is used for convenience and brevity, and thus, should be interpreted in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. To illustrate, a concentration range of "about 0.1 % to about 5%" should be interpreted to include not only the explicitly recited concentration of about 0.1 wt% to about 5 wt% , but also include individual concentrations (e.g ., 1 %, 2%, 3%, and 4%) and the sub-ranges (e.g. , 0.5%, 1 .1 %, 2.2% , 3.3% , and 4.4%) within the indicated 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 disclosure, e.g. the phrase "x to y" includes the range from 'x' to y as well as the range greater than 'x' and less than y. The range can also be expressed as an upper limit, e.g. 'about x, y, z, or less' and should be interpreted to include the specific ranges of 'about x', 'about y', and 'about z' as well as the ranges of less than x', less than y', and 'less than z'. Likewise, the phrase 'about x, y, z, or greater' should be interpreted to include the specific ranges of 'about x', 'about y', and 'about as well as the ranges oi 'greater than x', greater than y', and 'greater than . In some embodiments, the term "about" can include traditional rounding according to significant figures of the numerical value. In addition, the phrase "about 'x' to y" includes "about 'x' to about y".

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present disclosure, the preferred methods and materials are now described.

Ail publications and patents cited in this specification are herein incorporated by reference as if each individual publication or patent were specifically and individually indicated to be incorporated by reference and are incorporated herein by reference to disclose and describe the methods and/or materials in connection with which the publications are cited . The citation of any publication is for its disclosure prior to the filing date and should not be construed as an admission that the present disclosure is not entitled to antedate such publication by virtue of prior disclosure. Further, the dates of publication provided could be different from the actual publication dates that may need to be independently confirmed .

As will be apparent to those of skill in the art upon reading this disclosure, each of the individual embodiments described and illustrated herein has discrete components and features which may be readily separated from or combined with the features of any of the other several embodiments without departing from the scope or spirit of the present disclosure. Any recited method can be carried out in the order of events recited or in any other order that is logically possible.

Embodiments of the present disclosure will employ, unless otherwise indicated, techniques of nanotechnology, organic chemistry, biochemistry, material science, chemical engineering, engineering and the like, which are within the skill of the art. Such techniques are explained fully in the literature.

Discussion

Described herein in various aspects are scalable, membrane-free water-splitting electroiyzers that can contain a power source to provide energy to drive the water-splitting reaction. Other compositions, compounds, methods, features, and advantages of the present disclosure will be or become apparent to one having ordinary skill in the art upon examination of the following drawings, detailed description, and examples, it is intended that all such additional compositions, compounds, methods, features, and advantages be included within this description, and be within the scope of the present disclosure.

With a general description of the membrane-free water-splitting electroiyzers in mind, attention is directed to Figs. 1 -2, which show embodiments of a membrane-free water- splitting electrolyzer 100 of the present disclosure. The membrane-free eiectrolyzer can contain a power source 1 10, such as a solar cell. The energy source can be configured to generate about 1 .4 to about 2.2 V, which can be used directly for electrocatalysis of water. As used herein "about," "approximately," and the like, when used in connection with a numerical variable, generally refers to the value of the variable and to all values of the variable that are within the experimental error (e.g., within the 95% confidence interval for the mean) or within ±10% of the indicated value, whichever is greater. In this way, the need for additional voltage converters or amplifiers can be eliminated.

In embodiments where the power source is a solar cell, the solar cell can contain three sets of silicon cells 1 1 1 a, b, and c. Each set of silicon ceils can be connected to shared electrodes. For example, as shown in Fig. 1 , the each set of silicon cells 1 1 1 a, b, and c contains 15 silicon cells. In this configuration, each set of silicon cells can be configured to deliver about 0.45 to about 0.75 V each. When the energy generated by each set of the silicon cells is combined, the total energy generated by the solar cell can be about 1 .4 to about 2.2 V. The variation of the voltage can be achieved with combining sets of different numbers of soiar ceils, such as combining 2 sets of 3 cells (1 .35 V) and 1 set of 4 cells (1 .8 V) to achieve 1 .5 V.

The membrane-free electrolyzer can further contain a rail reactor 120, where the rail reactor can be directly or indirectly coupled to the power source 1 10. Figs, 1 -2 show the portions separated from one another for clarity. The rail reactor can be configured to collect gases generated during electrocataiysis. The rail reactors can contain or be made from a polymer or co-polymer. In some embodiments, the polymer or co-polymer can contain an alkaline tolerant polymer. An alkaline tolerant polymer (co-polymer), as the term is used herein, refers to a polymer (co-polymer) that is not broken down or remains functional and substantially intact when in an environment having an alkaline pH. Suitable polymers include, but are not limited to, poiyisobutylene, polypropylene, polyethylene, and fluoroplastics, polyamides, polyvinyl chloride, polystyrene, and polyvinylidene fluoride.

The rail reactor can be configured to have two channels 121 , 122 that can optionally be conjoined along one side. The height of the rail reactor can be between 1 and 10 cm. The width of the rail reactor can be between 0.2 and 15 cm, and the length of the rail reactor can be 15 cm up to meter scale. The rail reactor can be extended and/or connected to other rail reactors if needed. Each channel 121 , 122 can be open along the length of one side of the channel, such as the bottom, in some embodiments, each channel can form a "U" shape. These are also referred to herein as "U" shaped channels. The exact shape of the channel can vary. For example, in some embodiments, the U shape can contain that are about 90 degrees (see e.g. Fig. 1 , 121 and 122) or can be more curved (see e.g. Fig. 2, 121 and 122). The power source 1 10 can be coupled to the closed side of the U shape of the rail reactor 120 and/or channel(s) 121 (122). in some embodiments, the power source 130 can extend the length of the rail reactor 120 or channel 121 , 122,

The membrane-free electrolyzer can further contain an electrocatalyst element 130, which can contain electrocataiysis 131 , 132. In various aspects, the electrocatalyst element can have a height of between about 0.2 and 30 cm and anywhere in between, a depth of between about Q.4 and 2 cm and anywhere in between, and a length up to 1 meter or more, and can extended or connected to one or more other membrane-free elctroylyzers or components thereof. Any electrocatalysts capable of driving the water-splitting reaction can be used, in some embodiments, the electrocatalysts can contain one or more abundant elements, including but not limited to, nickel (Ni), iron (Fe), cobalt (Co), manganese (Mn), copper (Cu), titanium (Ti), vanadium (V), niobium (Nb), chromium (Cr), molybdenum (Mo), and/or tungsten (W). In some embodiments, the electrocatalysts can include one or more metals such as a noble metal (e.g. ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), osmium (Os), iridium (ir), platinum (Pt), and gold (Au)), aluminum (Al), zinc (Zn), cadmium (Cd), gallium (Ga), indium (in), tin (Sn), and bismuth (Bi) and/or other transition metal. In some embodiments, the electrocatalysts can contain one or more nonmetals, such as boron (B), carbon (C), nitrogen (N), oxygen (O), phosphine (P), and sulfur (S), which may form metal oxides, metal carbides, metal nitrides, metal sulfides and/or metal phosphides. The exact composition of the electrocatalyst can be selected based on the needed overvoltage provided by the solar ceils. One of ordinary skill in the art will appreciate such compositions and methods of testing such compositions, which are ail within the scope of this disclosure.

The electrocatalysts 131 , 132 can be operativeiy coupled to the rail reactor 120. in some embodiments, each electrocatalyst 131 , 132 can fit inside the "U" formed by each channel 121 , 122 of the rail reactor. The electrocatalysts 131 , 132 can be positioned at a distance of about 1 cm to about 10 cm (and anywher, in between) away from each other within the membrane-free eiectrolyzer. In some embodiments, the electrocatalysts 131 , 132 can be positioned at a distance of about 2 cm from each other.

The electrocatalyst element can be electrically coupled to the power source 1 10 and can be fluidically coupled to the rail reactor 120. in some embodiments, a first electrocatalyst 131 can act as a cathode and a second electrocatalyst can act as an anode 132 (see e.g. Fig, 3). The hydrogen molecules can collect at the cathode side and the oxygen molecules can collect at the anode side. In some embodiments, each electrocatalyst 131 , 132, can share a cathode side or an anode side with the neighboring set of solar ceils. The neighboring rail reactor can be, depending on the required distance between electrodes, used to separate hydrogen and oxygen molecules as shown in Fig. S. Similarly, in this configuration, electrolyte can be shared with neighboring components. An example of this embodiment is shown in Fig. 4, which is discussed in greater detail below.

With the general description of the various components in mind, attention is directed to Fig. 3, which shows another view of one embodiment of a membrane-free electrolyzer 100 of the present disclosure, in operation, the power source 1 10 can provide an amount of energy to the electrocataiysts, which then can facilitate the splitting of water to form hydrogen and oxygen molecules. The amount of energy can be about as much as needed to drive the water-splitting reaction. In these embodiments, the amount of energy can range from about 1 .4 V to about 2.2V. As discussed above, the power source 1 10 can be a solar cell. When the hydrogen and oxygen atoms are formed they can be captured by the rail reactor as shown in Fig. 3, where each gas can be collected in a separate channel of the rail reactor.

The various embodiments demonstrated in Figs. 1 -3 can have a single solar ceil with 3 sets of silicon cells. However, the number of solar cells used can vary. For example, as shown in Fig. 4, the membrane-free electrolyzer 400 can be configured to incorporate at least two solar ceils 410, 440, where each solar ceil has three sets of silicon ceils 41 1 a, b, c and 441 a, b, c. Each solar cell 410, 440 can be operatively coupled to one channel of the rail reactor 420, 450. The shape and dimensions of the rail reactor and its channels can be as previously described in relation to Figs. 1 -3. The composition of the rail reactor can be as previously described in relation to Figs. 1 -3.

An electrocatalyst 430, 460 can be positioned within the "U" of each channel of the rail reactor 420, 450. Each electrocatalyst 430, 460 can have an anode side and a cathode side. The electrocataiysts 430, 460 can be positioned within the membrane-free electrolyzer 400 such that the anode sides of the electrocataiysts 430, 460 face inward towards each other as depicted in Fig. 4. The spacing and positioning of the eiectroctaiysis relative to one another can be as otherwise described in relation to Figs. 1 -3. The composition of the electrocatalysts can be as previously described in relation to Figs. 1 -3.

As in the previous embodiments, when voltage is supplied to the electrocatalysts 430, 460 by the power sources 410, 440, water can be split into hydrogen and oxygen molecules. Each solar cell can provide 0.4-0.6 V, which can be added up to provide adequate voltage 1 .4-2.2 V for water electrolysis. These product molecules can be separately collected in each channel of the rail reactor 420, 450 as depicted in Fig. 4 and as previously described. Another set of solar cell 440 can be situated next to a set of solar cell 410, where the cathode 460 can be shared to produce hydrogen gases. The rail reactor, electrode and electrolyte can be continued to expand by repeating this entire unit (410,440,420,450,430,460).

As previously discussed, a limitation of currently available water-splitting electrolyzers is that they are not particularly scalable. An advantage of the membrane-free water-splitting electrolyzers described herein is that they can be combined to form a larger system containing multiple electrolyzers that can work together to scale up the production of hydrogen and oxygen atoms from water. With this in mind, attention is turned to Fig. 5, which demonstrates one embodiment of a membrane-free water-splitting electrolyzer system 500 containing a plurality of membrane-free water-splitting electrolyzers described in association with any of Figs. 1 -4. The system 500 can contain a plurality of sets 510 a, b, c of membrane-free, water-splitting electrolyzers 400 a-l. The sets 510 a, b, c can be arranged as rows with the individual membrane-free, water splitting electrolyzers 400 a-l being aligned within the system such that the individual channels within each electrolyzer aligns with the next, row such that a larger channel that extends between the sets 510 a, b, c is formed. In short, each individual electrolyzer 400 in the system 500 can be thought of as a modular component of the whole system. While only 3 sets are depicted in the system 500 of Fig. S, it will be instantly appreciated that the system can be scalable to any desired size by adding any desired number of additional sets of elecirolyzers. Likewise, although only 12 individual electrolyzers 400 a-l are shown in each set 510 a, b, c, it will be appreciated that because of the modular nature of the individual electrolyzers that the system 500 can be scaled to any desired size by adding additional electrolyzers to each set 510 a, b, c. This modular scalability of the system 500 can be at least partially attributed to the self-contained modular design of the individual membrane-free water-splitting electrolyzers described in relation to Figs, 1 -4. Although the system 500 is depicted using the embodiments of the of membrane- free water-splitting electrolyzers described in relation to Fig, 4, it will be appreciated that any of the individual electrolyzers described herein or combination thereof can be combined in a similar fashion to generate a scalable system as described in relation to Fig. 5.

The membrane-free water-splitting electrolyzer can be operated upon applying voltage provided by the solar cells, to the anode and the cathode.

in some embodiments an electrolyte solution (i.e. a solution containing an electrolyte) can be used with any of the membrane-free water splitting electrolyzers described herein, in some embodiments, the electrolyte solution can be a densely buffered electrolyte solution, where the concentration of solute is greater than 1 mol L ^"1 . The electrolyte solution can contain an alkali cation (e.g. Li ⁺ , Rb ⁺ , Na ⁺ , K ⁺ , and Cs ⁺ ), an anion (e.g. H ₂ PG ^" , HP0 ₄ ^2" , P0 ₄ ³ , B(GH) ^4" , B ₄ 0 ₇ ^2" , citrate, acetate, HC0 ³ \ and C0 ₃ ^2~ ). in some embodiments, the electrolyte solution can be a neutral-buffered electrolyte solution (e.g. KH ₂ P0 ₄ , K HP0 ₄ , K ₃ P0 ₄ , LiH PG , NaH ₂ P0 ₄ , NaBQ ₃ , and NaHC0 ₃ ). in some embodiments, the electrolyte solution can be an alkali solution (e.g. NaOH and KOH). In other embodiments, the electrolyte solution can be an acidic solution (e.g. H ₂ S0 ₄ and HCi0 ₄ ). The solute concentration of the electrolyte solution can range from about Q.01 to about 4.0 mol L ^"1 ). In some embodiments, the solute concentration of the electrolyte solution can be about 1 .5 M. In some embodiments, the solute concentration of the electrolyte solution can be about 2.0 mol L ^"1 . EXAMPLES

Now having described the embodiments of the present disclosure, in general, the following Examples describe some additional embodiments of the present disclosure. While embodiments of the present disclosure are described in connection with the following examples and the corresponding text and figures, there is no intent to limit embodiments of the present disclosure to this description. On the contrary, the intent is to cover all alternatives, modifications, and equivalents included within the spirit and scope of embodiments of the present disclosure.

Example 1 : Electrolyte engineering toward igh hydrogen production performance and oxygen to!eranee under buffered-neutraf conditions

introduction: Utilization of the renewable energy as energy sources is one of the most promising concepts for the construction of a sustainable society. These decades witnessed a drastic progress in the solar fuei production: photovoltaic ceils generate electricity from the sunlight, ^1"4 whereas photoelectrochemical ⁵ and photocata lytic ^6"11 wafer splitting directly produce hydrogen and oxygen by harvesting the sunlight. An electroiyser can electrochemically split water molecules, ^12,13 that can be conjugated with the photovoltaic cells. ^14,15 During the photoeiectrochemical and photocataiytic water splitting, what takes place on the surface is simply eiectrocataiysis. ¹¹ The eiectrocatalysis will thus play a role in the solar fuel production process in the future.

Most of the studies regarding the electrochemical hydrogen evolution reaction (HER) have been carried out under both extremely acidic ^16"21 and alkaline conditions. ^20"27 Recently, some studies have been dedicated to the HER under neutral pH conditions. ^28"33 in typical supporting electrolytes, e.g., Na ₂ S0 or NaCI0 ₄ , ^30,31 the reactant for the HER at neutral pH has to be the water molecule to obtain a substantial H ₂ production rate (for example, around -10 mA cm ^"2 , corresponding to -10 % solar to hydrogen efficiency): ^30"32 Under such conditions, its mass-transport flux becomes slower than the surface hydronium ion reduction rate due to smaller hydronium ion activities. In unbuffered-neutral pH electrolyte solutions, therefore, a huge additional overpotential is required to obtain higher electric currents compared with those at acidic or alkaline pH levels. ³² In buffered electrolyte solutions, however, this two-step HER (hydronium ion reduction followed by water molecule reduction) is not practically observed and instead only a monotonic increase in a reduction current is obtained. ^28,29 The resultant onset potential is reported to be ~0 V vs. RHE using Pt as an electrode, which is comparable to those in acidic and alkaline solutions. ^28,23,34 Some claim that the reactant under such condition is likely the weak acid itself, e.g., phosphate species (H ₂ PQ ₄ ^~ and HP0 ₄ ^2" ). ^35"39

Previously, we reported that HER performances show a volcano-shaped trend with the solute concentration under buffered-neutral conditions, exhibiting the highest performance at around 2 mol L ^"1 (in the case of sodium phosphate solution at pH 5). ^¾ It is revealed that the HER under densely-buffered conditions over Pt electrocataiysts is predominantly governed by a mass-transport of weak acid. The concentration overpotential in denser solution than 1 .0 mol L ^~1 is calculated to be as high as 50 % among kinetic overpotential, concentration overpotential and potential drop induced by the solution resistance. This finding suggests that a fine electrolyte tuning will lead to much higher mass- transport and result in higher HER performances under neutral pH conditions.

On the other hand, oxygen gases are evolved at the anode (oxygen evolution reaction, OER) during water splitting. Typically, active catalysts for the HER also show good oxygen reduction reaction (ORR) performances, as intensively studied, such as pt ^40~43 and multi-metal catalysts. ^44"49 Therefore, the evolved oxygen, which can be transported from the anode to the cathode, is reduced back to the water molecule. In typical water splitting cell (both electrochemical and photocatalytic water splitting), the cross-over of the product significantly lowers the total efficiency major!y by the undesired competitive reaction. The concept of the oxygen-tolerant HER is, thus, of great significance. ⁶⁰

Recently, some novel ways have been proposed to avoid this efficiency loss: core- shell structured materials that selectively suppresses the oxygen molecule mass-transport to the reduction site, ^{10,1 1 ,51 ,62} and more selective catalyst toward the HER (high HER activity and poor ORR activity). ⁶³ Previously, we carried out an ORR study under densely-buffered conditions over a Pt electrocatalyst, showing that electrolyte properties (gas solubility, the kinematic viscosity and the diffusion coefficient) solely governs the oxygen mass-transport in the densely-buffered electrolyte solution. The study implies that a careful choice of electrolyte leads to a significantly lowered oxygen mass-transport within the ceil. The small oxygen mass-transport will result in the reduced gas cross-over, which in turn increase the cell efficiency.

A high hydrogen production with high oxygen tolerance can result in efficient water splitting, which can be primarily achieved by utilization of buffered solution, irrespective of catalyst nature. Herein, we investigate the HER and ORR, including the HER in the presence of oxygen, under densely-buffered conditions. Various kinds of electrolyte solutions (KH2PO4, K2HPO4, K3PO4, UH2PO4, NaH ₂ P0 ₄ , NaHC0 ₃ , HCIO4, KOH and mixture of them) were used with a variety of solute concentrations (0.01 - 3.0 mol L ^~1 ). Observed HER performances under buffered-neutral conditions were well reproduced by the diffusion coefficient of weak acids (H ₂ P0 ₄ ^"" , HPQ ₄ ^2~ etc.) and mean activity coefficient. Also, the gas mass-transport flux was found to be universally described by the solution viscosity, the gas solubility and the diffusion coefficient. Our benchmarking study disclosed that all the HER and ORR performances over Pt electrocatalysts were predictable, which allowed us to pin down the optimal conditions. Under such conditions (1 .5 M NaH PQ ₄ or 1 .5 M 40 % K ₂ HP0 + 60 % KH ₂ PO ₄ ), overpotential required to achieve -10 mA cm ^"2 , equivalent to approximately 10 % solar to hydrogen efficiency, was found to be less than 40 mV, where the selectivity to the HER in the presence of oxygen was as high as 90 %.

Experimental: A rotating disk electrode (RDE) configuration was applied to our study for controlling the mass-transport phenomena. A poly-crystalline Pt disk electrode with a 3.0 mm diameter (0.071 cm ² geometric surface area) was purchased from BAS, inc. Before each measurement, the Pt disk-electrode was polished first with 1 μηι diamond and then with 0.05 μιη alumina (both purchased from BAS, Inc.). The disk rotation speed was controlled at 1600-4900 rpm. A three-electrode system was employed, in which a KCI- saturated Ag/AgCi electrode and a Pt wire were used as reference and counter electrodes, respectively. Various electrolyte solutions purchased from Sigma-Aidricb were used: Na ₂ S0 ₄ (>99.99 %), H ₂ S0 ₄ (99.999 %), HCIO ₄ (99.999 %), NaOH (99.99 %), KOH (99.99 %), Na ₂ HP0 ₄ (99.5 %), H3PO4 (99.9 %), NaHC0 ₃ (>99.95 %), KH ₂ P0 ₄ (>98 %), K ₂ HP0 ₄ (>99 %) and K ₃ P0 ₄ (>95 %). Before and during all of the measurements, Ar (99.999 %), H ₂ (produced using a N H ₂ 300 Hydrogen Generator, D. B. S. Strumenti Scientific! S.p.A.) or 0 ₂ (99.9995 %) was continuously supplied. Cyclic and linear-sweep voltammogram measurements were performed at room temperature (297 K) with a scan rate of 50 mV s ^~1 using a 16-channel, research-grade potentiosiat system (VIV1P3) purchased from BioLogic Science Instruments. Ail of the current densities described in this report are expressed in terms of the geometric electrode surface area, and ail of the current-potential relationships have been iR-corrected using measured impedance values (100 kHz, amplitude 10 mV and 298 K) unless otherwise specified.

Results: Demonstrated herein is the concept that a fine tuning of electrolyte can lead to a controlled electrochemical hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) under buffered-neutrai conditions. First the HER in various electrolyte solution will be discussed, showing how apparent HER performances are altered by electrolyte solutions. Then, the ORR will be examined to evaluate gas mass-transportation in the cell. Finally, the HER and ORR will be combined to describe the HER in the presence of oxygen.

Hydrogen production: The HER was investigated using a polycrystalline Pt disk- electrode as a model catalyst in various electrolyte solutions under buffered conditions. Our previous study revealed that, in densely buffered solutions, the HER performances are shown to increase with the solute concentration at lower concentration, whereas further denser solution lowers mass-transport resulting in poorer performances. ³² The highest HER performance was obtained at around 2.0 mol L ^{" 1} in sodium phosphate solution at pH 5, where the concentration overpotential is calculated to be significantly huge (accounting for more than half of the required overpotential). ³⁵ If such is the case, then tuning electrolyte properties toward improved mass-transport is anticipated to enhance the HER at neutral pH. The factors governing the apparent HER performance in the buffered solution are (1 ) diffusion coefficient and (2) mean activity coefficient of the electrolyte solution. ³⁵ The former of the diffusion coefficient D is theoretically obtained by the Stokes-Einstein equation: ⁵⁴

_D = JL.

^6πα >* Equation (1 )

where k is the Boltzmann's constant; T is the absolute temperature; a defines the effective size of ion and μ denotes the solution viscosity. The equation fells that the diffusion coefficient is described by the effective sizes of ion in the solution (-hydrated size) and the solution viscosity at a given temperature. Among typical alkali cation, the following order was obtained as their sizes in aqueous liquid phase: ^55,56

Li ⁺ > Na ⁺ > K ^* > Cs ⁺ Equation (2)

For the anion in the buffered solution, e.g., phosphate, the following were found: ^55,56

H ₂ P0 ₄ ^" > HPO4 ^2" Equation (3)

The viscosity of such electrolyte solution was available in the data book, which was as follows:"

Li ⁺ > Na ⁺ > > Cs ⁺ Equation (4)

HP0 ₄ ^2~ > H ₂ P0 ₄ ^~ Equation (5)

(2)-(5) gave the order of the diffusion coefficient among simple alkali metal phosphate solutions:

Li ⁺ -A > Na ^÷ -A > K ⁺ -A > Cs ⁺ -A (A = H ₂ PQ ₄ ^~ and HPG ₄ ^2~ ) Equation (6) l¥]-H ₂ P0 ₄ ^~ > -H ₂ P0 ₄ ^~ (M = Li ⁺ , Na ⁺ , K ⁺ and Cs ⁺ ) Equation (7)

On the other hand, quantitative description of the mean activity coefficient is still under debate. ^58"64 Nevertheless, existing literature allows us to discuss it qualitatively. Based on "like sees like" ⁶⁹ or "matching water affinity" ⁶⁰ concept, ⁵⁸ the following order of the mean activity coefficient ywas obtained for the alkali metal phosphate solution:

LiH ₂ P0 ₄ > NaH ₂ P0 ₄ > KH ₂ P0 ₄ > CsH ₂ P0 ₄ Equation (8)

Cs ₂ HP0 ₄ > K ₂ HP0 ₄ > Na ₂ HP0 ₄ > Li ₂ HP0 ₄ Equation (9) and

-H ₂ P0 ₄ ^~ > -H ₂ P0 ₄ ^~ (M = Li ⁺ and Na ⁺ ) Equation (10) -H ₂ PO,f > -H ₂ P0 ₄ ^~ (M = K ⁺ and Cs ⁺ ) Equation (1 1)

Because higher diffusion coefficients and mean activity coefficients are anticipated to result in apparently higher HER performances, the optimal conditions can be theoretically found at (a) Na- or K- H ₂ P0 ₄ , (b) K _x H ₃ - _x P0 ₄ (1 < x < 2) and (c) Cs _x H ₃ ~ _x PQ ₄ (1 < x < 2). This rationale was experimentally examined.

in Figs. 6A-6C, experimentally observed potentials reaching -10 mA cm ^"2 are compiled for various electrolyte solutions. Fig. 6A shows the potential as a function of K ⁺ in the solution with 1 .5 mol L ^~! of phosphate, where 1 ,5 and 3.0 mo I L ^"1 K ⁺ correspond to KH ₂ P0 ₄ and K ₂ HP0 ₄ , respectively. The required overpotentia! first decreased with increasing the K ⁺ composition from 1 .5 mol L ^~ \ reaching the smallest (35.0 ± 1 .3 mV) at around 1 .8 mol L ^"1 , and then monotonically decreased. On the other hand, in Fig. 6B, where the potential is compiled against Na ⁺ concentration, a slight increase in the overpotential with the Na ⁺ concentration was observed: -37.8 ± 1 .0 mV (1 .5 mol L ^"1 Na ⁺ ) and -38.7 ± Q.2 mV (1 .8 mol L ^"1 Na ⁺ ). Note that from now on the mixed solutions of MH ₂ P0 ₄ and M ₂ HP0 ₄ are referred as Ivl-phosphate. Also, 1 .5 mol L ^{" 1} H ₂ P0 ₄ (M = Li, Na and K) solutions were investigated for the HER as shown in Fig, 6C. A volcano-shaped dependence was observed, e.g., NaH ₂ P0 ₄ showed the smallest overpotential among them. Notably, as will be discussed later in F g. 7, at all the concentration (0.1 - 1 .5 mol L ^~! ) the highest HER performance was obtained in NaH ₂ P0 ₄ than those in LiH ₂ P0 ₄ and KH ₂ P0 . All the observations described in the figures are consistent with the theoretical rationale as discussed in the previous paragraph, supporting our hypothesis: the HER under densely buffered conditions is predominantly determined by the electrolyte nature, it is worth emphasizing thai, under buffered-neutral conditions, more acidic pH does not give higher HER performances.

Additionally, ail the typical electrolyte solutions (KH ₂ P0 ₄ , K ₂ HP0 ₄ , K ₃ P0 ₄ , LiH ₂ P0 ₄ , NaH ₂ P0 , NaHC0 ₃ , HCI0 and KOH) were examined for the HER as shown in Fig, 7. In the figure, potentials reaching -10 mA cm ^""2 are plotted as a function of the solute concentration, in ail the neutral-buffered electrolyte solutions (KH ₂ P0 ₄ , K ₂ HP0 ₄ , LiH ₂ P0 ₄ , NaH ₂ P0 ₄ and NaHC0 ₃ ), the overpotential was volcano-shaped with the solute concentration, giving its highest at around 1 .5 - 2.0 moi L ^"1 . This potential-concentration relationship is most likely ascribabie to the weak acid mass-transport, as previously demonstrated. ³⁵ When the solute concentration is as small as < 0.1 moi L ^"1 , observed overpotentials for the HER were quite huge: as high as 330 mV for 0.01 moi L ^"1 NaHC0 ₃ , which is much larger than the typical alkaline conditions (87.8 ± 0.9 mV in 0.1 moi L ^"1 KOH). interestingly, above that threshold concentration higher HER performances were observed under the buffered-neutral conditions than those in KOH or K ₃ P0 (alkaline) solutions. This is likely resulting from the difference in the reactant: the proton or weak acid is the reactant under buffered-neutral conditions, ^35"39 whereas the water is reduced at alkaline pH. ^30"32 At the all concentration regime, the HER was found to be the most facile under acidic conditions (HCIG ).

Notably, the solute concentration change in HCI0 ₄ electrolyte solution did not alter any apparent HER performances, consistent with the literature. ³⁰ One may wonder that denser HCI0 ₄ is more viscous which is expected to lower the diffusion coefficient. As described below in the section on the ORR, the HCI0 ₄ viscosity is little altered by its concentration. As a concluding remark in this section, indeed the hydrogen production can be tuned by the choice of electrolytes at neutral pH. The highest performance for the HER was found in 1 .5 moi L ^~ NaH ₂ P0 ₄ (37.8 ± 1 .0 mV), K-phosphate (1 .8 moi L ^~ K ⁺ & 1 .5 moi L ^"1 phosphate), which is predictable from the electrolyte properties of effective ion sizes, solution viscosity, and mean activity coefficient. Since the HER performance was predominantly determined by the identity and molarity of ion in the buffered near-neutral conditions as demonstrated, the same observation is expected in the HER using different electrodes. Indeed, the same electrolyte dependence was observed for Ni disk and Ni o electrode as shown in Figs. 8A-8B and 9A- 9B. The observation indicates the significance of electrolyte engineering.

Oxygen mass-transport: The ORR was also investigated for the evaluation of oxygen mass-transportation. According to the literature, ⁶² the following Levich equation has been well established describing the mass-transportation limited current (limiting diffusion current):

_A = o.62^ ^<5C Equation (12)

where j _L is the Levich current density; n defines the number of involved electron; F is the Faraday's constant; ω defines the disk rotation speed (3600 rpm ~ 377 rad s ^"1 ); v is the solution kinematic viscosity and <5C represents the difference in the reactant concentrations between the surface and bulk. Typically, when the equation is applied to the ORR and HOR, the properties of water is used to describe the limiting diffusion current. When denser solutions are utilized, however, the altered properties (kinematic viscosity, diffusion coefficient and reactant concentration) have to be taken into consideration. As previously reported,' ¹³ under buffered-neutral conditions, the solution viscosity increases, diffusion coefficient decreases and gas solubility decreases with increasing the solute concentration. The observed limiting diffusion current for the ORR is found to be well described by these altered properties. ⁴³ The finding here can apply to the ail the gas conversion reaction: by tuning of viscosity, diffusion coefficient and gas solubility, the mass-transportation can be well controlled.

To prove this concept, various electrolyte solutions were used for our ORR study, e.g., KH ₂ P0 ₄ , K2HPO4, K3PO4, LiH ₂ P0 _4l NaH ₂ P0 _4l NaHC0 ₃ , HCIO4 and KOH. The kinematic viscosity can be found in the literatu e, ⁵ ' ⁵⁶⁶ and the gas solubility is calculated with the Sechenov equation: ⁶ ' iog ∑(h, +h _G )c,

v Equation (13)

where c _G,0 and c _G represents the gas solubility in pure water and electrolyte solution, respectively; h, and h _G are constants depending on the ion and gas, respectively, and c, is the moiar salt concentration. The obtained oxygen solubility and kinematic viscosity for some solutions are compiled in Figs. 1 GA-1 QD. The oxygen solubility in all the buffered solution decreased with the solute concentration, and the kinematic viscosity was found to increase in denser solutions. Using the Stokes- Einstein equation, diffusion coefficients in such electrolytes were calculated. With ail the obtained valued of kinematic viscosity, diffusion coefficient and gas solubility, limiting diffusion currents were calculated and summarized in Fig. 10D. In ail the cases, smaller limiting diffusion currents were obtained with increasing the solute concentration, showing the following order in different electrolyte solutions at a given solute concentration:

NaHCOs = KH ₂ P0 ₄ > NaH ₂ P0 ₄ > K ₂ HPO. Equation (14)

This order most probably reflects the oxygen mass-transport flux.

The prediction was experimentally examined as shown in Figs. 11A-11 B. In Fig. 11 A, all ORR limiting diffusion currents got decreased with the solute concentration, except for HCI0 ₄ , and the following order of limiting diffusion currents was obtained in the neutral- buffered solutions:

NaHC0 ₃ > KH ₂ P0 ₄ > NaH ₂ PG ₄ > K ₂ HP0 ₄ Equation (15)

which totally agrees with the afore-described expectation of (14). Therefore, it can be concluded that each electrolyte exhibits its properties, which solely determines the gas mass-transportation. Notably, the kinds of gases merely change its solubility and effective size, so that the same argument is applicable to different gas conversion reactions, such as hydrogen oxidation reaction (HOR). As can be seen in the Fig. 11 B, where the observed limiting diffusion currents for the HOR are plotted against the solute concentration, the same order as (14) was obtained. These results reveal the universality of our concept: in various electrolyte solutions and for different kinds of gases, the mass-transportation can be well described by kinematic viscosity, diffusion coefficient and reactant concentration.

Hydrogen production in the presence of oxygen: Both the HER ad ORR under densely-buffered conditions have been shown to be majorly governed by the electrolyte properties, i.e., effective sizes of ions, (kinematic) viscosity of the solution, mean activity coefficient and gas solubility. Tuning the electrolyte property can lead to improved hydrogen production and lowered oxygen mass-transportation. Based on the experimental obsea'ation, in this section the separately measured HER and ORR are compared, and also the HER in the presence of oxygen is discussed.

in the previous sections, current densities were addressed:

(HER) at -50 mV vs. RHE with H ₂ bubbling

(ORR) at 400 mV vs. RHE with 0 ₂ bubbling

Also, it was experimentally examined the H ₂ production with Q ₂ bubbling. Fig. 12 compiles the measured current densities at -50 mV vs. RHE (HER in the presence of oxygen) against the sum of measured HER and ORR. A clearly linear relationship was observed, implying that the HER and ORR most likely do not interfere each other.

This finding allowed for quantification of the HER selectivity in the presence of oxygen (faradaic efficiency to the HER) based on the separately measured HER and ORR.

Selectivity to the HER =

HER + ORR Equation (16)

In Fig. 13, the calculated selectivity to the HER is summarized for ail the electrolyte solutions investigated (KH ₂ P0 ₄ , K ₂ HP0 ₄ , K ₃ P0 ₄ , LiH ₂ P0 ₄ , NaH ₂ PG ₄ , NaHC<¾, HCI0 ₄ , KOH, K-phosphate and Na-phosphate), Under neutral-buffered conditions, increasing the solute concentration led to the raised HER selectivity, it is consistent with the improving HER and lowered ORR as described in the previous sections. Notably, at alkaline pH (KOH and K ₃ P0 ₄ ), both the apparent HER activity and ORR limiting diffusion currents decreased with the solute concentration, which gives different selectivity dependence on the solute concentration from those at neutral. The highest selectivity was found as 89 % (2.1 mol L K-phosphate). The larger ones than 80 % were observed in denser solutions: >2.0 mol L ^"1 LiH ₂ P0 ₄ , >1 .5 mol L ^"1 NaH ₂ P0 ₄ , >1 .5 mol L ^~1 KH ₂ P0 ₄ , K-phosphate and Na-phosphate.

Finally, in Figs, 14A-14D typical linear-sweep voltammograms (LSVs) with various gases bubbling in the selected electrolyte solutions are shown: (highest HER selectivity) 2.1 mol L ^~1 K-phosphate, (lowest ORR) 3.0 mol L ^"1 K ₂ HP0 , (typical acidic solution) 1 .0 mol L ^~1 HCI0 ₄ and (typical alkaline solution) 1 .0 mol L ^""1 KOH. Substantial differences between LSVs in 0 ₂ and H ₂ were found in acidic and alkaline solutions. Under densely-buffered conditions, however, cathodic polarization curves in various gases below 0 V vs. RHE were too close to differentiate from each other. Especially, when the solution is significantly dense, e.g., in 3.0 mol L ^" K ₂ HP0 ₄ , the polarization curves overlap showing negligibly small gas mass- transportation, it should be emphasized thai, although the RDE configuration was applied to the study, the finding is applicable to the other cases. The RDE gives a defined diffusion layer thickness, ⁴³ which is smaller than not stirred and poorly stirred systems. In the system where the RDE is not used, the mass-transport is thus anticipated to be much slower, where much higher HER selectivity can be found.

Although this study describes a very fundamental aspect of H ₂ /0 ₂ aqueous electrochemistry, the resultant observation is quite promising. Notably, when the potential applied onto reduction catalyst during water splitting (tentatively considered as -50 mV vs. RHE in this study) is more negative, the selectivity to the HER can be much higher. A careful choice of electrolyte solutions can lead to drastically improved cell efficiency for electrochemical, photoelectrochemical and photocatalytic water splitting. The new insight provided herein can be used to advance and improve the existing water splitting devices.

Solution resistance: One of the parameters at the steady state operation of water electrolysis is the voltage loss originating from the solution resistance. The voltage loss can be calculated from the solution resistance R _so . multiplied by the operating current / (£ _i0 ss = iR), and therefore the operation at high current density leads to larger voltage loss. Densely buffered condition has additional benefits over the minimized solution resistance. Fig, 15 shows the solution resistance as a function of solute concentration. The higher the solute concentration is, the lower the solution resistance becomes. As discussed previously, this positive effect of minimized solution resistance is compensated with the detrimental effect of lowered diffusion coefficient of the ions. This consideration has been discussed at standard temperature, and thus high temperature will benefit both diffusion properties and resistivity, although heat supply may have to be additionally taken into account.

Conclusions: Toward oxygen tolerant hydrogen production, hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) were investigated in detail under neutral pH conditions. The controlled experiment revealed that both HER and ORR performances were quite predictable universally in various kinds of electrolyte. The factors governing HER are diffusion coefficient of buffered-species and mean activity coefficient, tuning of v/hich gave expected apparent HER performances. Benchmarking study in various electrolyte revealed optimal conditions for the HER at neutral pH, where -10 mA cm ^"2 (=10 % solar to hydrogen efficiency) was achievable with an overpotential less than 40 mV. Also, the present investigation showed predictable gases mass-transport flux governed by gas solubility, the kinematic viscosity and the diffusion coefficient. Combining the knowledge obtained in the HER and ORR study allows quantification of the hydrogen production in the presence of oxygen. At -50 mV vs. RHE, as high as 90 % of selectivity to the HER was observed in KH ₂ PO, _r K ₂ HP0 ₄ mixture (ratio of 4/8 at 1 .5 mo! L ^~ ) where -10 mA cm ^~2 for the HER was achieved over a conventional Pt catalyst. This shows the significance of electrolyte choice, which has been overlooked in many cases. It also highlights a capacity of electrolysis at neutral pH, where lower C0 ₂ solubility and more material choice are provided. This shows wider application of electrolysis for solar fuel production. References for Example 1

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Example 2

16A-16C show photographs of one embodiment of a rail reactor as described herein. Fig, 17 is a graph demonstrating hydrogen and oxygen evolution from the embodiment of the rail reactor shown in Figs, 16A-16C.