Patent Description:
As an energy conversion technology utilizing the energy of sunlight, there is a need for practical application of hydrogen and oxygen production technology by means of water decomposition reaction using a photocatalyst. It is necessary to utilize visible light to achieve the practical efficiency of energy conversion, and development of visible light responding type photocatalysis is underway. As a complete water decomposition technology using visible light, a two-step excitation (Z-scheme) method that combines two types of optical semiconductors (hydrogen generation side and oxygen generation side) and a mediator (redox based) has been reported.

Regarding the redox of the Z-scheme type water decomposition by visible light, the following patent literature <NUM> to <NUM> is available.

Patent literature <NUM> has disclosed a technology for separately generating hydrogen and oxygen by giving and receiving electrons between a conductive wire and a redox pair in a two-chamber cell type hydrogen generating cell that is divided by a diaphragm.

Patent literature <NUM> relates to a Z-scheme type visible light active photocatalyst-based method using the Fe3+/Fe2+ redox, and describes that the difference in adsorption amount suppresses the reverse reaction and that it is effective under the pH2. <NUM> acidic condition.

Patent literature <NUM> describes the complete water decomposition that utilizes visible light usable under the alkaline condition using the iodine compound (IO3-/I-) redox.

Patent literature <NUM> discloses a method for producing hydrogen and oxygen, comprising the steps of: (i) oxidising a mediator at a working electrode to yield an oxidised mediator, and reducing protons at a counter electrode to yield hydrogen; and (ii) reducing an oxidised mediator at a working electrode to yield a mediator, and oxidising water at a counter electrode to yield oxygen, wherein the oxygen generation step is performed non-simultaneously to the hydrogen generation step, and the oxidised mediator of step (i) is used as the oxidised mediator of step (ii), or the mediator of step (ii) is used as the mediator of step (i), and the mediator has a reversible redox wave lying between the onset of the oxygen evolution reaction and the hydrogen evolution reaction.

Patent literature <NUM> relates to a photochemical reaction device which includes: a solar cell; an electrolytic tank having a first tank storing a first solution including an oxidant and/or reductant of a redox medium and a second tank storing a second solution including water and/or proton; a first electrode set in the first tank, connected to a positive electrode of the solar cell through a first switching element, and connected to a negative electrode of the solar cell through a second switching element; and a second electrode set in the second tank, connected to the positive electrode of the solar cell through a third switching element, and connected to the negative electrode of the solar cell through a fourth switching element.

In the technology for separately generating hydrogen and oxygen, disclosed in patent literature <NUM>, the hydrogen generating reaction depends on [Red]/[Ox] of the redox pair and the redox pair becomes disproportionate. This will easily cause reverse reaction, thereby inhibiting the efficient hydrogen generating reaction.

As mentioned above, in the Z-scheme type water decomposition by visible light using a redox compound, as the concentration polarization of the initially loaded redox pair increases, reverse reaction progresses, which may cause hydrogen and oxygen generating reaction to stop. However, this problem is not mentioned in both patent literature <NUM> and patent literature <NUM>.

To solve the above problems of the conventional technologies, the present invention provides a photochemical reaction system and method capable of recovering the efficiency of the hydrogen and oxygen generating reaction without loading additional redox compounds and replacing electrolytic solutions.

The aforementioned object is solved by the invention by a photochemical reaction device and a photochemical method as defined claims <NUM> and <NUM> respectively. Further preferred developments are described by the dependent claims.

In particular, it is provided a photochemical reaction system that includes a hydrogen generating cell containing a hydrogen generating type photocatalyst, an aqueous medium including a redox compound, an electrolytic solution, and a first electrode; an oxygen generating cell containing an oxygen generating type photocatalyst, an aqueous medium including a redox compound, an electrolytic solution, and a second electrode; and/or an ion-permeable ion-exchange membrane for separating the hydrogen generating cell and the oxygen generating cell, wherein the photochemical reaction system further includes a redox compound concentration polarization elimination part for eliminating the concentration polarization of the redox compound in the hydrogen generating cell generated as a result of generating hydrogen gas from the hydrogen generating cell by irradiating the hydrogen generating cell with light and the concentration polarization of the redox compound in the oxygen generating cell generated as a result of generating oxygen gas from the oxygen generating cell by irradiating the oxygen generating cell with light. The redox compound concentration polarization elimination part eliminates the above generated concentration polarization of the redox compound by performing temperature difference power generation between the hydrogen generating cell and the oxygen generating cell.

Moreover, it is provided a photochemical reaction method that generates hydrogen gas from a hydrogen generating cell containing a hydrogen generating type photocatalyst, an aqueous medium including a redox compound, and/or an electrolytic solution by irradiating the hydrogen generating cell with light, and generates oxygen gas from an oxygen generating cell containing an oxygen generating type photocatalyst, an aqueous medium including a redox compound, and an electrolytic solution by irradiating the oxygen generating cell with light. In this method, temperature difference is generated between a hydrogen generating cell side first electrode and an oxygen generating cell side second electrode to thereby cause temperature difference power generation to occur between the first electrode and the second electrode. By doing so, eliminating of the concentration polarization of the redox compound generated as a result of generating hydrogen gas from the hydrogen generating cell by irradiating the hydrogen generating cell with light and the concentration polarization of the redox compound generated as a result of generating oxygen gas from the oxygen generating cell by irradiating the oxygen generating cell with light is performed.

According to the present invention, the photochemical reaction system for generating hydrogen and oxygen by utilizing visible light is capable of eliminating the concentration polarization of the redox compound that causes reverse reaction, by means of the temperature difference. As a result, it is possible to recover the efficiency of hydrogen and oxygen generating reaction without loading additional redox compounds and replacing electrolytic solutions, thereby increasing the operation rate of the photochemical reaction system.

The present invention relates to a Z-scheme type artificial photosynthesis system and provides a hydrogen generating cell and a hydrogen generating cell control system capable of eliminating the concentration polarization of the redox compound that causes reverse reaction, by means of temperature difference in the hydrogen generating cell for generating hydrogen and oxygen utilizing visible light. As a result, it is possible to increase the efficiency of generating hydrogen and oxygen, thereby increasing the operation rate of the system.

That is, the present invention provides a hydrogen generating cell and a hydrogen generating cell control system that are characterized in that the hydrogen generating cell for generating hydrogen utilizing visible light includes a hydrogen generating type photoelectrode, an oxygen generating type photoelectrode, and an aqueous medium including a redox compound (mediator) that is a redox ion, and that a plurality of paired electrodes for applying temperature difference are disposed in the aqueous medium.

Also, the present invention relates to a photochemical reaction system and method for eliminating the concentration polarization by means of operation control to apply temperature difference during night-time with no sunlight irradiation. As a result, it is possible to recover the efficiency of hydrogen and oxygen generating reaction without loading additional redox compounds or replacing electrolytic solutions, thereby enabling long-term operation.

Furthermore, the present invention relates to a hydrogen generating cell and a hydrogen generating cell control system that are characterized in that a switch for turning ON/OFF the current in a plurality of electrodes and a switching part for switching the switch according to the presence/absence of incident visible light are provided.

Moreover, the present invention provides a method of producing hydrogen and oxygen using a Z-scheme type water decomposition system by visible light that includes a hydrogen generating type photoelectrode, an oxygen generating type photoelectrode, an aqueous medium, and a redox compound functioning as a mediator, wherein temperature difference is applied in a reactor.

The Z-scheme type water decomposition system by visible light has a structure that a pair of conductive electrodes connected by a conductive wire are disposed near the hydrogen generating type photoelectrode and near the oxygen generating type photoelectrode in the reactor so as to apply temperature difference between the paired electrodes in the reactor by applying high temperature to one electrode and low temperature to the other electrode.

Furthermore, the Z-scheme type water decomposition system by visible light is so designed that when the redox compound is an N-type (thermoelectromotive force α><NUM>), high temperature will be applied to the vicinity of the hydrogen generating type photoelectrode and low temperature will be applied to the vicinity of the oxygen generating type photoelectrode so as to apply temperature difference; consequently, the vicinity of the hydrogen generating electrode becomes [Ox]>[Red] and the oxygen generating electrode side becomes [Red]>[Ox], thereby inhibiting the reverse reaction in each photoelectrode.

Furthermore, the Z-scheme type water decomposition system by visible light is characterized in that when the redox compound is a P type (thermoelectromotive force α<<NUM>), in case that low temperature will be applied to the vicinity of the hydrogen generating type photoelectrode and high temperature will be applied to the vicinity of the oxygen generating type photoelectrode so as to apply temperature difference; consequently, the vicinity of the hydrogen generating electrode becomes [Ox]>[Red] and the oxygen generating electrode side becomes [Red]>[Ox], thereby inhibiting the reverse reaction in each photoelectrode.

Moreover, the Z-scheme type water decomposition system by visible light is characterized in that the reactor is provided with an ion-selective permeable diaphragm (positive-ion permeation membrane or negative-ion permeation membrane), which allows only ions with an opposite sign of the electrical charge of the redox pair to permeate.

The same sign is provided for the portion having the same function in the drawings used for describing the embodiments, and repetitive description will be omitted.

The present invention is not limited to the description of the embodiments provided below. Various modifications are possible without departing from the technical concept of the invention as is understood by those skilled in the art.

<FIG> shows the structure of a photochemical reaction system <NUM> as an example of the Z-scheme type water decomposition system by visible light according to this example.

The photochemical reaction system <NUM> according to this example includes a hydrogen and oxygen production part <NUM> for generating hydrogen and oxygen by photochemical reaction using water as raw material, a hydrogen production and efficiency recovery control system <NUM> for controlling the production of hydrogen and oxygen in the hydrogen and oxygen production part <NUM>, a temperature difference application mechanism part <NUM> for controlling the temperature of the hydrogen and oxygen production part <NUM> so as to eliminate the concentration difference of the redox compound, and a switch <NUM> for turning ON/OFF the electrical circuit of the hydrogen and oxygen production part <NUM>.

The hydrogen and oxygen production part <NUM> includes a photochemical reaction apparatus with a temperature difference application mechanism <NUM>, wherein water <NUM> introduced to the inside of the photochemical reaction apparatus with a temperature difference application mechanism <NUM> is irradiated with sunlight <NUM> to generate a photochemical reaction, thereby generating oxygen gas (O<NUM>) <NUM> and hydrogen gas (H<NUM>) <NUM>.

The hydrogen production and efficiency recovery control system <NUM> includes an illuminance and weather information acquisition part <NUM>, a hydrogen production volume and STH efficiency calculation part <NUM>, an oxygen production volume and STO efficiency calculation part <NUM>, a voltage and current measurement (monitor) part <NUM>, a temperature difference application part <NUM>, a liquid replacement instruction display part <NUM>, and a control part <NUM>.

The illuminance and weather information acquisition part <NUM> acquires information about the illuminance of sunlight <NUM> entering the photochemical reaction apparatus with a temperature difference application mechanism <NUM> and about the weather of the area where the photochemical reaction apparatus with a temperature difference application mechanism <NUM> is installed.

The hydrogen production volume and STH efficiency calculation part <NUM> acquires information about the volume of hydrogen gas <NUM> generated by the photochemical reaction apparatus with a temperature difference application mechanism <NUM>, and the oxygen production volume and STO efficiency calculation part <NUM> acquires information about the volume of oxygen gas <NUM> generated by the photochemical reaction apparatus with a temperature difference application mechanism <NUM>.

The voltage and current measurement (monitor) part <NUM> measures the current and voltage flowing between electrodes, described later, of the photochemical reaction apparatus with a temperature difference application mechanism <NUM>. The temperature difference application part <NUM> heats up or cools down the heat source mounted to the photochemical reaction apparatus with a temperature difference application mechanism <NUM>.

The liquid replacement instruction display part <NUM> indicates the time for replacing the redox compound supplied to the photochemical reaction apparatus with a temperature difference application mechanism <NUM>, and the control part <NUM> controls the entire photochemical reaction system <NUM> including the hydrogen production and efficiency recovery control system <NUM>.

The temperature difference application mechanism part <NUM> for controlling the temperature of the hydrogen and oxygen production part <NUM> to eliminate the concentration difference of the redox compound includes a temperature difference application apparatus <NUM> for applying temperature difference between an oxygen generating cell and a hydrogen generating cell, described later, of the photochemical reaction apparatus with a temperature difference application mechanism <NUM>, and a voltage measuring apparatus <NUM> for measuring the voltage between electrodes, described later, of the photochemical reaction apparatus with a temperature difference application mechanism <NUM>.

The detailed structure of the photochemical reaction apparatus with a temperature difference application mechanism <NUM> in the hydrogen and oxygen production part <NUM> according to this example will be described with reference to <FIG>.

<FIG> shows the state of the photochemical reaction apparatus with a temperature difference application mechanism <NUM> in the daytime, where incident sunlight decomposes water, thereby generating hydrogen and oxygen.

<FIG> shows the state of the photochemical reaction apparatus with a temperature difference application mechanism <NUM> in the night-time, where sunlight is not shining and the concentration polarization of the redox compound is being eliminated.

In the structure shown in <FIG>, <FIG> denotes an oxygen generating cell, <NUM> denotes a hydrogen generating cell, <NUM> denotes an electrode, <NUM> denotes an electrolytic solution supplied to the inside of the oxygen generating cell <NUM> and the hydrogen generating cell <NUM>, <NUM> denotes a redox compound supplied to the inside of the oxygen generating cell <NUM> and the hydrogen generating cell <NUM>, 7a denotes an ion-selective permeable diaphragm (ion-exchange membrane) formed by a positive-ion-exchange membrane or a negative-ion-exchange membrane, 8a denotes a visible-light responding oxygen generating photocatalyst, and 9a denotes a visible-light responding hydrogen generating photocatalyst.

The ion-selective permeable diaphragm 7a is an ion-exchange membrane that does not allow the redox compound <NUM> to permeate but allows the counterion to permeate. By using such an ion-selective permeable diaphragm 7a as a diaphragm between the oxygen generating cell <NUM> and the hydrogen generating cell <NUM>, it is possible to separately generate oxygen and hydrogen in the oxygen generating cell <NUM> and the hydrogen generating cell <NUM>.

As for the redox compound <NUM>, it is desirable that the redox level be between <NUM> and +<NUM>. 23V (vs NHE, pH=<NUM>). For example, it is possible to adopt an Fe3+/Fe2+ type redox or an IO3-/I- type redox.

Oxygen generated in the oxygen generating cell <NUM> and hydrogen generated in the hydrogen generating cell <NUM> are separately recovered by a recovery apparatus, not shown.

A low-temperature-side heat source <NUM> and a circulating water pipe <NUM> for circulating cooling water in the low-temperature-side heat source <NUM> are buried in the area outside the oxygen generating cell <NUM>. Also, a high-temperature-side heat source <NUM> and a circulating water pipe <NUM> for circulating hot water in the high-temperature-side heat source <NUM> are buried in the area outside the hydrogen generating cell <NUM>.

Furthermore, the oxygen generating cell <NUM> side electrode <NUM> and the hydrogen generating cell <NUM> side electrode <NUM> are connected by a conductive wire <NUM> connected to a switch <NUM>.

In the above structure, if sunlight <NUM>, denoted by hv, shines while the switch <NUM> is open as shown in <FIG>, reduction reaction by the redox compound <NUM> occurs near the surface of the visible-light responding oxygen generating photocatalyst 8a in the oxygen generating cell <NUM>, thereby generating oxygen O<NUM>. As the reduction reaction progresses, concentration of reductants increases in the oxygen generating cell <NUM>.

On the other hand, oxidation reaction by the redox compound <NUM> occurs near the surface of the visible-light responding hydrogen generating photocatalyst 9a in the hydrogen generating cell <NUM>, thereby generating hydrogen H<NUM>. As the oxidation reaction progresses, concentration of oxidants increases near the surface of the visible-light responding hydrogen generating photocatalyst 9a in the hydrogen generating cell <NUM>.

At this time, neither hot water nor cooling water circulates through the circulating water pipes <NUM> and <NUM>, and both the high-temperature-side heat source <NUM> and the low-temperature-side heat source <NUM> are at room temperature.

On the other hand, for example, in the night-time when sunlight <NUM> is not shining, the switch <NUM> is closed to electrically connect the oxygen generating cell <NUM> side electrode <NUM> and the hydrogen generating cell <NUM> side electrode <NUM> as shown in <FIG>. In this state, the hydrogen generating cell <NUM> side electrode <NUM> is heated by circulating hot water in the high-temperature-side heat source <NUM> through the circulating water pipe <NUM>, and the oxygen generating cell <NUM> side electrode <NUM> is cooled by circulating cooling water in the low-temperature-side heat source <NUM> through the circulating water pipe <NUM>,.

By doing so, temperature of the hydrogen generating cell <NUM> side electrode <NUM> increases. In this state, reduction reaction occurs in the hydrogen generating cell <NUM> and the oxidant is converted to the reductant. Accordingly, the redox ratio in the hydrogen generating cell <NUM> that has been reduced due to the irradiation of the sunlight <NUM> increases.

On the other hand, temperature of the oxygen generating cell <NUM> side electrode <NUM> drops. In this state, oxidation reaction occurs in the oxygen generating cell <NUM> and the percentage of reductants decreases and the percentage of oxidants increases.

In this state, based on the principle of thermochemical battery, redox pairs permeate the ion-selective permeable diaphragm 7a, causing the temperature difference between the oxygen generating cell <NUM> side electrode <NUM> and the hydrogen generating cell <NUM> side electrode <NUM>, and move around in the electrolytic solution <NUM> between those electrodes, thereby generating a thermoelectromotive force. Consequently, the switch <NUM> closes and electric power is continuously generated among the oxygen generating cell <NUM> and the hydrogen generating cell <NUM> via the oxygen generating cell <NUM> side electrode <NUM> and the hydrogen generating cell <NUM> side electrode <NUM> that are electrically connected.

With reference to <FIG>, an explanation will be given about the generation of oxygen and hydrogen by means of sunlight irradiation and the state of oxidation reaction and reduction reaction caused as a result of heating the hydrogen generating cell <NUM> side electrode <NUM> and cooling the oxygen generating cell <NUM> side electrode <NUM>, which are stated above. <FIG> correspond to the state shown in <FIG> and show the state with sunlight irradiation. <FIG> correspond to the state shown in <FIG> and show the state in which the high-temperature-side heat source <NUM> and the low-temperature-side heat source <NUM> are operating in the night-time with no sunlight irradiation.

<FIG> shows the state immediately after the start of sunlight irradiation in the daytime. In this state, the switch <NUM> is open (OFF). In both the oxygen generating cell <NUM> and the hydrogen generating cell <NUM>, the ratio of oxidants ([Ox]) <NUM> to reductants ([Red]) <NUM> (redox concentration ratio), expressed by [Ox]/[Red], is <NUM>.

<FIG> shows the state when many hours have passed after irradiation of sunlight started in the daytime. Reduction reaction progresses in the oxygen generating cell <NUM> to generate oxygen, and the percentage of reductants ([Red]) <NUM> increases and the percentage of oxidants ([Ox]) <NUM> decreases near the visible-light responding oxygen generating photocatalyst 8a. At this time, the ratio of oxidants ([Ox]) <NUM> to reductants ([Red]) <NUM>, expressed by [Ox]/[Red], is sufficiently smaller than <NUM>.

On the other hand, in <FIG>, oxidation reaction progresses in the hydrogen generating cell <NUM> thereby generating hydrogen, and the percentage of oxidants ([Ox]) <NUM> increases and the percentage of reductants ([Red]) <NUM> decreases near the visible-light responding hydrogen generating photocatalyst 9a. At this time, the ratio of oxidants ([Ox]) <NUM> to reductants ([Red]) <NUM>, expressed by [Ox]/[Red], is sufficiently larger than <NUM>, indicating the progress of polarization of redox concentration.

<FIG>shows the initial state in the night-time with no sunlight irradiation. In this state, by closing (turning ON) the switch <NUM>, the oxygen generating cell <NUM> side electrode <NUM> and the hydrogen generating cell <NUM> side electrode <NUM> are electrically connected by a conductive wire <NUM> as shown in <FIG>.

<FIG> shows the state shortly after the high-temperature-side heat source <NUM> and the low-temperature-side heat source <NUM> started operating. In this state and according to the present invention, based on the principle of thermochemical battery, redox pairs permeate the ion-selective permeable diaphragm 7a, causing the temperature difference between the oxygen generating cell <NUM> side electrode <NUM> and the hydrogen generating cell <NUM> side electrode <NUM>, and move around in the electrolytic solution <NUM> between those electrodes, thereby generating a thermoelectromotive force and continuously generating electric power.

Consequently, in the oxygen generating cell <NUM>, the percentage of oxidants ([Ox]) <NUM> increases and the percentage of reductants ([Red]) <NUM> decreases near the visible-light responding oxygen generating photocatalyst 8a due to the oxidation reaction when compared with the state shown in <FIG>. As a result, the ratio of oxidants ([Ox]) <NUM> to reductants ([Red]) <NUM>, expressed by [Ox]/[Red], is smaller than <NUM> but larger than the value shown in <FIG>.

Furthermore, in <FIG>, in the hydrogen generating cell <NUM>, the percentage of reductants ([Red]) <NUM> increases and the percentage of oxidants ([Ox]) <NUM> decreases near the visible-light responding hydrogen generating photocatalyst 9a due to the reduction reaction when compared with the state shown in <FIG>. At this time, the ratio of oxidants ([Ox]) <NUM> to reductants ([Red]) <NUM>, expressed by [Ox]/[Red], is larger than <NUM> but smaller than the value shown in <FIG>.

<FIG> shows the state some time after the state shown in <FIG> in the night-time. In this state, the oxidation reaction in the oxygen generating cell <NUM> and the reduction reaction in the hydrogen generating cell <NUM> have sufficiently progressed, causing the electromotive force to decrease, and the voltage between the oxygen generating cell <NUM> side electrode <NUM> and the hydrogen generating cell <NUM> side electrode <NUM> becomes almost zero. In this state, in both the oxygen generating cell <NUM> and the hydrogen generating cell <NUM>, the ratio of oxidants ([Ox]) <NUM> to reductants ([Red]) <NUM>, expressed by [Ox]/[Red], is <NUM>, which indicates that the polarization of redox concentration has been eliminated.

In this state, the process returns to the state shown in <FIG>, and then the sunlight is applied with the switch <NUM> open to generate hydrogen and oxygen.

As shown in <FIG>, for the redox concentration ratio, expressed by [Ox]/[Red], the reductant ([Red]) <NUM> becomes rich in the oxygen generating cell <NUM> and the oxidant ([Ox]) <NUM> becomes rich in the hydrogen generating cell <NUM> because of the daytime Z-scheme reaction, thereby generating the polarization of redox concentration.

Thus, if the reductant ([Red]) <NUM> increases in the oxygen generating cell <NUM> and if the oxidant ([Ox]) <NUM> increases in the hydrogen generating cell <NUM>, polarization of redox concentration progresses in each cell, causing a reverse reaction to occur. As a result, there is a possibility that the oxygen generation and the hydrogen generation will stop.

In contrast, as described in <FIG>, in the system according to this example, the heating and cooling means disposed outside the oxygen generating cell <NUM> and the hydrogen generating cell <NUM> apply temperature difference between the electrode installed in the oxygen generating cell <NUM> (visible-light responding oxygen generating photocatalyst 8a) and the electrode installed in the hydrogen generating cell <NUM> (visible-light responding hydrogen generating photocatalyst 9a) in the night-time when hydrogen gas is not generated due to the reduction of illuminance so that the polarization of redox concentration can be eliminated in each cell. With this, the efficiency of hydrogen generating reaction during the daytime is recovered, thereby enabling the system to be repetitively used.

Herein, when applying temperature difference between electrodes from outside the oxygen generating cell <NUM> and the hydrogen generating cell <NUM> so as to eliminate the polarization of redox concentration in each cell, by closing the switch <NUM> as shown in <FIG>, to electrically connect the oxygen generating cell <NUM> side electrode <NUM> and the hydrogen generating cell <NUM> side electrode <NUM>, thermoelectromotive force α is generated based on the principle of thermochemical battery. In this state, the voltage (equilibrium potential E) between the oxygen generating cell <NUM> side electrode <NUM> and the hydrogen generating cell <NUM> side electrode <NUM> is measured by the voltage measuring apparatus <NUM>.

From the Nernst equation, equilibrium potential E is expressed by the redox concentration ratio [Ox]/[Red].

[Equation <NUM>] <MAT>
[Equation <NUM>] <MAT>.

[Equation <NUM>] <MAT>
[Equation <NUM>] <MAT>
[Equation <NUM>] <MAT>
[Equation <NUM>] <MAT> where.

The above ΔE in (Equation <NUM>) and ΔE in (Equation <NUM>) are equations with the same meaning.

If the voltage measured by the voltage measuring apparatus <NUM> becomes a constant voltage according to either (Equation <NUM>) or (Equation <NUM>), it is indicated that the concentration difference has been eliminated.

Very little electric power generated by the temperature difference power generation can be used for charging storage battery so as to be used for the bias voltage assist and the power to auxiliary devices.

The sign of the thermoelectromotive force α that varies according to redox species will determine which cell to set at high temperature, the oxygen generating cell <NUM> or the hydrogen generating cell <NUM>. In the case of type N (α><NUM>), in order to inhibit the reverse reaction in the hydrogen generating cell <NUM> by converting excessive oxidants ([Ox]) <NUM> to reductants ([Red]) <NUM> to eliminate the concentration difference and make the concentration ratio close to <NUM>, the hydrogen generating cell <NUM> is set at a high temperature as described in <FIG>.

On the other hand, in the case of type P (α<<NUM>), in order to inhibit the reverse reaction in the oxygen generating cell <NUM> by converting excessive reductants ([Red]) <NUM> to oxidants ([Ox]) <NUM> to eliminate the concentration difference and make the concentration ratio close to <NUM>, the oxygen generating cell <NUM> is set at a high temperature as opposed to the description provided in <FIG>.

In (Equation <NUM>) or (Equation <NUM>), temperature difference ΔT between the oxygen generating cell <NUM> side electrode <NUM> and the hydrogen generating cell <NUM> side electrode <NUM> is set (input) and ΔE is measured (output). Since α is an eigenvalue determined by the redox species, αΔT of the right hand first term is determined by temperature difference ΔT. The concentration ratio defines the right hand second term. Whether the concentration ratio is large or small can be judged by whether or not the measured electromotive force ΔE is no longer different from αΔT. As the concentration ratio becomes large, ΔE becomes large, and as the concentration ratio becomes small, ΔE becomes small.

Herein, each time the redox concentration ratio of the high temperature pole and the low temperature pole changes by <NUM>, the value of electromotive force E changes by approximately <NUM> mV.

Next, with reference to the flow chart in <FIG>, description will be given about the procedures for operating the photochemical reaction system <NUM> provided with a photochemical reaction apparatus with a temperature difference application mechanism <NUM>, as shown in <FIG>.

First, the light entering the photochemical reaction apparatus with a temperature difference application mechanism <NUM> is measured by means of an illuminance meter, not shown. Then, the information about illuminance and weather that has been stored in the illuminance and weather information acquisition part <NUM> of the hydrogen production and efficiency recovery control system <NUM> is input to the control part <NUM> (S501).

Next, information about the volume of hydrogen produced in the hydrogen and oxygen production part <NUM> is input into the control part <NUM> (S502). The volume of hydrogen produced in the hydrogen and oxygen production part <NUM> was detected by a hydrogen detector, not shown, and has been stored in the hydrogen production volume and STH efficiency calculation part <NUM>.

Subsequently, based on the information about the volume of produced hydrogen input in S502, the control part <NUM> determines whether hydrogen is being generated from the hydrogen and oxygen production part <NUM> (S503).

When it is determined that hydrogen is generated from the hydrogen and oxygen production part <NUM> (Yes in S503), the volume of hydrogen to be generated in the hydrogen and oxygen production part <NUM> is estimated based on the illuminance information input in S501, and in comparison with the volume of hydrogen produced in the hydrogen and oxygen production part <NUM> input in S502, it is determined whether the volume of hydrogen estimated from the illuminance is being generated in the hydrogen and oxygen production part <NUM> (S504).

When it has been determined in S504 that the volume of hydrogen estimated from the illuminance is being generated in the hydrogen and oxygen production part <NUM> (Yes in S504), it is determined whether to maintain the photochemical reaction (S505). When maintaining the photochemical reaction is determined (Yes in S505), the process will return to S501 and the hydrogen generation process will continue.

On the other hand, when not maintaining the photochemical reaction is determined (No in S505), the process of producing hydrogen will be terminated.

Furthermore, when it is determined in S503 that hydrogen is not being generated in the hydrogen and oxygen production part <NUM> (No in S503), the control part <NUM> instructs the switch <NUM> to close, as described in <FIG>, to electrically connect the oxygen generating cell <NUM> side electrode <NUM> and the hydrogen generating cell <NUM> side electrode <NUM>. Furthermore, hot water is circulated through the circulating water pipe <NUM> in the high-temperature-side heat source <NUM> to heat up the hydrogen generating cell <NUM>, and cooling water is circulated through the circulating water pipe <NUM> in the low-temperature-side heat source <NUM> to cool down the oxygen generating cell <NUM>. By doing so, temperature of the hydrogen generating cell <NUM> side electrode <NUM> increases and temperature of the oxygen generating cell <NUM> side electrode <NUM> decreases.

Consequently, oxidants are converted to reductants by the reduction reaction in the hydrogen generating cell <NUM>, thereby increasing the redox ratio and eliminating the concentration difference between the oxidant and the reductant in the hydrogen generating cell <NUM>. On the other hand, the percentage of reductants decreases and the percentage of oxidants increases due to the oxidation reaction in the oxygen generating cell <NUM>, thereby eliminating the concentration difference between the oxidant and the reductant in the oxygen generating cell <NUM> (S506).

While hot water is circulated through the circulating water pipe <NUM> in the high-temperature-side heat source <NUM> to heat up the hydrogen generating cell <NUM> and cooling water is circulated through the circulating water pipe <NUM> in the low-temperature-side heat source <NUM> to cool down the oxygen generating cell <NUM>, temperature difference power generation is performed between the oxygen generating cell <NUM> and the hydrogen generating cell <NUM>, and potential difference (voltage) is generated between the oxygen generating cell <NUM> side electrode <NUM> and the hydrogen generating cell <NUM> side electrode <NUM>. Information about the potential difference, measured by the voltage measuring apparatus <NUM>, is stored in the voltage and current measurement (monitor) part <NUM>. ΔE obtained by the above (Equation <NUM>) through (Equation <NUM>) or (Equation <NUM>) corresponds to the potential difference stored in the voltage and current measurement (monitor) part <NUM>. The control part <NUM> determines whether the potential difference, expressed by ΔE, between the oxygen generating cell <NUM> side electrode <NUM> and the hydrogen generating cell <NUM> side electrode <NUM> has reached the predetermined value (S507).

When it has been determined that ΔE has reached the predetermined value (Yes in S507), the control part <NUM> instructs the switch <NUM> to open so as to electrically disconnect the oxygen generating cell <NUM> side electrode <NUM> and the hydrogen generating cell <NUM> side electrode <NUM>, and the process will return to S501.

On the other hand, when it has been determined that ΔE has not reached the predetermined value (No in S507), it is determined whether the predetermined time has passed after the process proceeded to S506 (S508). When it has been determined that the predetermined time has not passed yet (No in S508), steps S506 and S507 will continue.

On the other hand, when it has been determined that the predetermined time has passed (Yes in S508), the liquid replacement instruction display part <NUM> of the hydrogen production and efficiency recovery control system <NUM> prompts the replacement of the electrolytic solution <NUM> and the redox compound <NUM> contained in the oxygen generating cell <NUM> and the hydrogen generating cell <NUM>, and the procedures will be terminated.

Furthermore, when it has been determined in S504 that the volume of hydrogen estimated from the illuminance has not been generated in the hydrogen and oxygen production part <NUM> (No in S504), based on the information stored in the hydrogen production volume and STH efficiency calculation part <NUM> about the volume of hydrogen gas <NUM> produced in the photochemical reaction apparatus with a temperature difference application mechanism <NUM>, and the information stored in the oxygen production volume and STO efficiency calculation part <NUM> about the volume of oxygen gas <NUM> produced in the photochemical reaction apparatus with a temperature difference application mechanism <NUM>, it is determined whether the ratio of hydrogen gas <NUM> to oxygen gas <NUM>, produced in the photochemical reaction apparatus with a temperature difference application mechanism <NUM>, is <NUM>:<NUM>.

As a result, when it has been determined that the ratio of hydrogen gas <NUM> to oxygen gas <NUM> is <NUM>:<NUM> (Yes in S510), process will proceed to S505, and the photochemical reaction will continue.

On the other hand, when it has been determined that the ratio of hydrogen gas <NUM> to oxygen gas <NUM> is not <NUM>:<NUM> (No in S510), the process will proceed to S506 where concentration difference between the oxidant and the reductant in the oxygen generating cell <NUM> and the hydrogen generating cell <NUM> is eliminated by increasing the temperature of the hydrogen generating cell <NUM> side electrode <NUM> and decreasing the temperature of the oxygen generating cell <NUM> side electrode <NUM>. Subsequent procedures are the same as those previously explained, and therefore, description will be omitted.

Furthermore, <FIG> show the example of the structure using the visible-light responding oxygen generating photocatalyst 8a and the visible-light responding hydrogen generating photocatalyst 9a, each formed into a sheet. However, these photocatalysts may be substituted by the visible-light responding oxygen generating photocatalyst particles 8b and the visible-light responding hydrogen generating photocatalyst particles 9b that will be described later in example <NUM>.

Moreover, <FIG> show the example of the structure in which the oxygen generating cell <NUM> and the hydrogen generating cell <NUM> are separated only by the ion-selective permeable diaphragm 7a. However, the structure may be designed so that the oxygen generating cell <NUM> and the hydrogen generating cell <NUM> are separated by combining the ion-selective permeable diaphragm 7a and other material so as to reduce the area of the ion-selective permeable diaphragm 7a.

According to this example, the method of producing hydrogen and oxygen by means of water decomposition by sunlight includes means for eliminating the concentration polarization of the redox compound. This makes it possible to prevent the stagnation of water decomposition due to the disproportion of concentration of the redox compound near the electrodes as a result of continuing the water decomposition, thereby allowing the redox compound to be used continuously for comparatively long time without replacing it. Thus, hydrogen and oxygen can be produced repetitively every day by means of the sunlight water-splitting.

<FIG> show the structure where the oxygen generating cell <NUM> and the hydrogen generating cell <NUM> are separated by the ion-selective permeable diaphragm 7a. However, the oxygen generating cell <NUM> and the hydrogen generating cell <NUM> may be separated by a separation barrier using an insulator made of resin etc. without using the ion-selective permeable diaphragm 7a. In this case, instead of adopting the high-temperature-side heat source <NUM> and the low-temperature-side heat source <NUM>, it is possible to replace half of the liquid in the oxygen generating cell <NUM> and half of the liquid in the hydrogen generating cell <NUM> in which concentration polarization of the redox compound has progressed as a result of continuing water-splitting.

A second example of the present invention will be described with reference to <FIG>. The same number is provided for the same portion as was explained in example <NUM>, and description will be omitted.

The structure of the photochemical reaction apparatus with a temperature difference application mechanism <NUM>-<NUM>, shown in <FIG>, corresponds to the photochemical reaction apparatus with a temperature difference application mechanism <NUM>, described in example <NUM> with reference to <FIG>.

When compared with the structure of the photochemical reaction apparatus with a temperature difference application mechanism <NUM>, explained in example <NUM> with reference to <FIG>, the photochemical reaction apparatus with a temperature difference application mechanism <NUM>-<NUM>, shown in <FIG>, has a different structure where the ion-selective permeable diaphragm 7a is substituted by a divider 7b, the visible-light responding oxygen generating photocatalyst 8a is substituted by visible-light responding oxygen generating photocatalyst particles 8b, and the visible-light responding hydrogen generating photocatalyst 9a is substituted by visible-light responding hydrogen generating photocatalyst particles 9b.

However, as described in example <NUM>, the visible-light responding oxygen generating photocatalyst particles 8b may be substituted by the visible-light responding oxygen generating photocatalyst 8a formed into a sheet, as explained in example <NUM>, and the visible-light responding hydrogen generating photocatalyst particles 9b may also be substituted by the visible-light responding hydrogen generating photocatalyst 9a.

In example <NUM>, the oxygen generating cell <NUM> and the hydrogen generating cell <NUM> are completely separated by the ion-selective permeable diaphragm 7a, constituting two chambers. In contrast, in this example, the oxygen generating cell <NUM>-<NUM> and the hydrogen generating cell <NUM>-<NUM> are not completely separated, and these cells substantially constitute one chamber.

In this example, the oxygen generating cell <NUM>-<NUM> and the hydrogen generating cell <NUM>-<NUM> are separated by a divider 7b that is lower than the ion-selective permeable diaphragm 7a in example <NUM>. The divider 7b has the role of dividing the visible-light responding oxygen generating photocatalyst particles 8b in the oxygen generating cell <NUM>-<NUM> and the visible-light responding hydrogen generating photocatalyst particles 9b in the hydrogen generating cell <NUM>-<NUM> so that they do not mix.

Since the divider 7b is low, the upper part of the oxygen generating cell <NUM>-<NUM> and the upper part of the hydrogen generating cell <NUM>-<NUM> are not separated; therefore, an electrolytic solution <NUM> and a redox compound <NUM> contained in the oxygen generating cell <NUM>-<NUM> are mixed with an electrolytic solution <NUM> and a redox compound <NUM> contained in the hydrogen generating cell <NUM>-<NUM>.

In the state shown in <FIG>, oxygen gas generated in the oxygen generating cell <NUM>-<NUM> and hydrogen gas generated in the hydrogen generating cell <NUM>-<NUM> as a result of irradiation of sunlight <NUM> are extracted as a mixture. However, by separating the mixed gas by a gas separation means, not shown, for separating a hydrogen gas and an oxygen gas (for example, hydrogen separation membrane), it is possible to separately recover the oxygen gas and the hydrogen gas.

That is, even if the oxygen generating cell <NUM>-<NUM> and the hydrogen generating cell <NUM>-<NUM> are not completely separated and substantially constitute one chamber, as shown in this example, it is possible to generate an oxygen gas and a hydrogen gas and separately recover those gases.

In such a structure, as shown in <FIG>, according to the same method as explained in example <NUM> with reference to <FIG>, in the time zone (night-time) with no sunlight irradiation, temperature of the hydrogen generating cell <NUM>-<NUM> side electrode <NUM> is increased and temperature of the oxygen generating cell <NUM>-<NUM> side electrode <NUM> is decreased, thereby performing temperature difference power generation. By doing so, the hydrogen generating cell <NUM>-<NUM> generates the reduction reaction, converting the oxidant to the reductant, and thus the redox ratio in the hydrogen generating cell <NUM>-<NUM> that has been reduced due to the irradiation of sunlight <NUM> increases. Furthermore, the oxygen generating cell <NUM>-<NUM> generates the oxidation reaction, thereby decreasing the percentage of reductants and increasing the percentage of oxidants, and thus the percentage of oxidants in the oxygen generating cell <NUM>-<NUM> that has been reduced due to the irradiation of sunlight <NUM> increases.

Operation procedures in this example are the same as those explained in example <NUM> with reference to <FIG>, and therefore, description will be omitted.

In this example, in the same manner as example <NUM>, the method of producing hydrogen and oxygen by water decomposition by sunlight includes means for eliminating the concentration polarization of the redox compound, which makes it possible to prevent the stagnation of water decomposition due to the disproportion of concentration of the redox compound near the electrodes as a result of continuing the water decomposition, thereby allowing the redox compound to be used continuously for comparatively long time without replacing it. Thus, hydrogen and oxygen can be produced repetitively every day by means of the water decomposition by sunlight.

In the above example, description was given about the method of eliminating the concentration polarization of the redox compound by applying temperature difference between the oxygen generating cell <NUM>-<NUM> side electrode <NUM> and the hydrogen generating cell <NUM>-<NUM> side electrode <NUM> by using the high-temperature-side heat source <NUM> and the low-temperature-side heat source <NUM>. However, instead of using the high-temperature-side heat source <NUM> and the low-temperature-side heat source <NUM>, but by using a screw etc., it is possible to diffuse the liquid in the oxygen generating cell <NUM>-<NUM> and the liquid in the hydrogen generating cell <NUM>-<NUM> in which concentration polarization of the redox compound has progressed as a result of continuing water splitting.

A third example of the present invention will be described with reference to <FIG>.

The structure, shown in <FIG>, corresponds to the photochemical reaction apparatus with a temperature difference application mechanism <NUM>, explained in example <NUM> with reference to <FIG>. Differences from the structure shown example <NUM> are the arrangement of the visible-light responding oxygen generating photocatalyst and the visible-light responding hydrogen generating photocatalyst, and the incident direction of the sunlight entering the oxygen generating cell and the hydrogen generating cell. The electrolytic solution and the redox compound used are the same as those used in example <NUM>.

In the structure shown in <FIG>, <NUM> denotes an oxygen generating cell, <NUM> denotes a hydrogen generating cell, <NUM> denotes a separation barrier, <NUM> denotes an electrolytic solution supplied to the inside of the oxygen generating cell <NUM> and the hydrogen generating cell <NUM>, <NUM> denotes a redox compound supplied to the inside of the oxygen generating cell <NUM> and the hydrogen generating cell <NUM>, <NUM> denotes an ion-selective permeable diaphragm formed by a positive-ion-exchange membrane or a negative-ion-exchange membrane, <NUM> denotes a visible-light responding oxygen generating photocatalyst, and <NUM> denotes a visible-light responding hydrogen generating photocatalyst.

<NUM> denotes a high-temperature-side heat source in which a circulating water pipe (not shown) for circulating hot water is buried. <NUM> denotes a low-temperature-side heat source in which a circulating water pipe (not shown) for circulating cooling water is buried.

<NUM> denotes an oxygen generating cell side electrode made of transparent conductive material. <NUM> denotes a hydrogen generating cell side electrode made of transparent conductive material. <NUM> denotes a switch, and <NUM> denotes an electric wire that connects the oxygen generating cell side electrode <NUM> and the hydrogen generating cell side electrode <NUM> via the switch <NUM>.

The ion-selective permeable diaphragm <NUM> is an ion-exchange membrane which does not allow the redox compound <NUM> to permeate but allows the counterion to permeate.

Thus, by separating the oxygen generating cell <NUM> and the hydrogen generating cell <NUM> by means of the separation barrier <NUM> and the ion-selective permeable diaphragm <NUM>, in the same manner as example <NUM>, it is possible to separately generate oxygen gas and hydrogen gas in the oxygen generating cell <NUM> and the hydrogen generating cell <NUM>.

The oxygen gas generated in the oxygen generating cell <NUM> and the hydrogen gas generated in the hydrogen generating cell <NUM> are separately recovered by a recovery apparatus, not shown.

In such a structure, as shown in <FIG>, while the switch <NUM> is open, by irradiating the inside of the oxygen generating cell <NUM> through the transparent oxygen generating cell side electrode <NUM> from both sides with the sunlight <NUM>, denoted by hv, reduction reaction occurs due to the redox compound <NUM> near the surface of the visible-light responding oxygen generating photocatalyst <NUM> in the oxygen generating cell <NUM>, thereby generating oxygen O<NUM>. As the reduction reaction progresses, concentration of reductants in the oxygen generating cell <NUM> increases.

On the other hand, by irradiating the inside of hydrogen generating cell <NUM> through the transparent hydrogen generating cell side electrode <NUM> with the sunlight <NUM>, denoted by hv, oxidation reaction occurs due to the redox compound <NUM> near the surface of the visible-light responding hydrogen generating photocatalyst <NUM> in the hydrogen generating cell <NUM>, thereby generating hydrogen H<NUM>. As the oxidation reaction progresses, concentration of oxidants near the surface of the visible-light responding hydrogen generating photocatalyst <NUM> in the hydrogen generating cell <NUM> increases.

At this time, the high-temperature-side heat source <NUM> and the low-temperature-side heat source <NUM> are at room temperature.

On the other hand, for example, in the night-time etc. with no irradiation of the sunlight <NUM>, in the same manner as explained in example <NUM> with reference to <FIG>, the switch <NUM> is closed to electrically connect the oxygen generating cell side electrode <NUM> and the hydrogen generating cell side electrode <NUM>, and the hydrogen generating cell <NUM> is heated by circulating hot water in the high-temperature-side heat source <NUM>, and the oxygen generating cell <NUM> is cooled by circulating cooling water in the low-temperature-side heat source <NUM>.

As a result, temperature of the hydrogen generating cell side electrode <NUM> in the hydrogen generating cell <NUM> increases, and temperature of the oxygen generating cell side electrode <NUM> in the oxygen generating cell <NUM> decreases. In this state, reduction reaction occurs in the hydrogen generating cell <NUM>, converting the oxidant to the reductant. By doing so, the percentage of the redox compound in the hydrogen generating cell <NUM> that has been reduced as a result of the irradiation of the sunlight <NUM> increases. As a result, the oxidant and the reductant are present in almost equal proportion in the hydrogen generating cell <NUM>,.

On the other hand, oxidation reaction occurs in the oxygen generating cell <NUM>, the percentage of reductants decreases and the percentage of oxidants increases. Consequently, the percentage of the redox compound in the hydrogen generating cell <NUM> that has been reduced as a result of the irradiation of the sunlight <NUM> increases. As a result, the oxidant and the reductant are present in almost equal proportion in the hydrogen generating cell <NUM>.

In this example, in the same manner as example <NUM>, the method of producing hydrogen and oxygen by water decomposition by sunlight includes means for eliminating the concentration polarization of the redox compound, which makes it possible to prevent the stagnation of water-splitting due to the disproportion of concentration of the redox compound near the electrodes as a result of continuing the water decomposition, thereby allowing the redox compound to be used continuously for comparatively long time without replacing it. Thus, hydrogen and oxygen can be produced repetitively every day by means of the water decomposition by sunlight.

Claim 1:
A photochemical reaction system (<NUM>), comprising:
a hydrogen generating cell (<NUM>, <NUM>) containing a hydrogen generating type photocatalyst, an aqueous medium including a redox compound (<NUM>, <NUM>), and an electrolytic solution (<NUM>);
the photochemical reaction system being characterised by:
an oxygen generating cell (<NUM>, <NUM>) containing an oxygen generating type photocatalyst, an aqueous medium including a redox compound (<NUM>, <NUM>), and an electrolytic solution (<NUM>); wherein
said hydrogen generating cell (<NUM>, <NUM>) and said oxygen generating cell (<NUM>, <NUM>) are separated by an ion-exchange membrane (7a);
a first electrode (<NUM>) contained in said hydrogen generating cell (<NUM>, <NUM>);
a second electrode (<NUM>) contained in said oxygen generating cell (<NUM>, <NUM>);
a temperature difference application part (<NUM>) configured to generate a temperature difference between said hydrogen generating cell (<NUM>, <NUM>) and said oxygen generating cell (<NUM>, <NUM>)to cause the redox compound (<NUM>, <NUM>) permeating the ion-exchange membrane (7a) and moving around in the electrolytic solution (<NUM>) between the first electrode (<NUM>) and the second electrode (<NUM>) thereby generating a thermoelectromotive force and continuously generating electric power for eliminating the concentration polarization of said redox compound (<NUM>, <NUM>) generated as a result of generating a hydrogen gas (<NUM>) from said hydrogen generating cell (<NUM>, <NUM>) by irradiating said hydrogen generating cell (<NUM>, <NUM>) with light and the concentration polarization of said redox compound (<NUM>, <NUM>) generated as a result of generating an oxygen gas (<NUM>) from said oxygen generating cell (<NUM>, <NUM>) by irradiating said oxygen generating cell (<NUM>, <NUM>) with light.