Patent Publication Number: US-2022228277-A1

Title: Compact generator for generating sterilizing materials

Description:
BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     This invention relates to electrocatalytic generation of ozone (O 3 ), or electrocatalytic cogeneration of O 3  and hydrogen peroxide (H 2 O 2 ) for sanitation and disinfection. More specifically, the invention relates to compact generators for producing O 3  or O 3 /H 2 O 2  by directly electrolyzing tap water using DC 5 volt. The disinfectant-containing water can be applied to the desired surfaces for sterilization. 
     2. Description of the Prior Art 
     In the COVID 19 pandemic, sodium hypochlorite (NaClO), commonly known as bleach, and ethanol are called for sterilization against the virus. The said disinfectants have slow bactericidal activity, and they cost money to procure. Compared to NaClO and C 2 H 5 OH, O 3  and H 2 O 2  are benign, more potent, and quicker on killing microbes without residues. Most importantly, O 3  and H 2 O 2  can be freshly made at home and other places as needs occurred. This patent presents an affordable way to produce O 3 /H 2 O 2  using tap water at low power consumption and user friendly. As far as the application and safety of O 3 /H 2 O 2  on disinfection is concerned, there are tons of literature references available, which is accessible in many searching engines. Only a few selected examples are cited here. 
     O 3 -water has been investigated in a viral inactivation as seen in U.S. Patent Application No. U.S. 2005/0051497, coronavirus is included therein. An ozone hemofildiafiltration device is used for safe injection of O 3  into human body to kill cells of bacteria and virus in the blood as seen in US Patent Application No. U.S. 2003/0073945. Besides sterilization (U.S. Pat. Nos. 7,323,149 and 7,790,103), O 3  turns into O 2  at the end of its natural life in 20 to 30 minutes environment dependent. This feature grants O 3  a unique role in blood oxygen therapy by enhancing the blood oxygen level. Consequently, ozone is utilized in the cares of leukemia (U.S. Pat. No. 6,399,664), artificial lung (U.S. Pat. No. 7,498,275), acute ischemic brain stroke (US 2010/0318014), wounds (U.S. Pat. Nos. 8,597,689 and 9,687,503), and kidney disease (U.S. Pat. No. 10,335,538). The aforesaid uses of O 3  all require the disinfectant in tiny bubble forms. 
     Although the oxidation potential of H 2 O 2  (1.78V) is lower than that of O 3  (2.07V), meaning, O 3  is superior to H 2 O 2  on destructing microbes. However, H 2 O 2  contains more O 2  and H 2 O 2  works much longer than O 3 , which is shown by the fact that a sealed H 2 O 2 —H 2 O solution decays only 10% in a year. In reality, the history of applying H 2 O 2  to medication is much earlier and wider than O 3 . In 1920, H 2 O 2  was injected to treat patients during an epidemic of viral pneumonia. Many promoters of blood oxygen therapy endorsed the ideas of Otto Warburg, a German physiologist, medical doctor, and Nobel laureate of 1931. He claimed that cancer cells grow better under low blood oxygen levels, and cancer could be cured by raising the O 2  level. The key on utilizing H 2 O 2  for oxygenation mainly resides on the timely availability of fresh and pure H 2 O 2  at the right dosages. This patent presents a device that may meet the demands. 
     SUMMARY OF THE INVENTION 
     The present invention is to provide a compact generator for generating sterilizing materials. The compact generator includes an electrolysis module configured for electrolyzing water to generate at least one sterilizing material. The electrolysis module further includes an anode and a cathode. The anode is configured to generate oxygen (O 2 ) and ozone (O 3 ) during electrolyzing water. The cathode is configured on one side of the anode. The cathode is configured to produce hydrogen peroxide (H 2 O 2 ) by reducing O 2  generated from the anode during electrolyzing water. The material of the anode is Sb,Ni—SnO 2 /Ti. the material of the cathode is Co 3 O 4 -CNF/Ti, and the CNF is conductive carbon nanofilm. O 3  and H 2 O 2  are cogenerated to form the at least one sterilizing material, and the sterilizing material includes O 3 , peroxone (H 2 O 3 ), hydroxyl radical (.OH) and hydroperoxyl radical (HO 2 .). 
     Wherein, the precursor for the main body of anode catalysts, tin oxide (SnO 2 ), is tin oxalate (SnC 2 O 4 ). 
     Furthermore, the tin oxalate is formed by oxalic acid and Tin(II) salt. The Tin(II) salt may be selected from the group of Dibutyltin dichloride, Dibutyltin maleate, Tin(II) acetate, Tin(II) bromide, Tin(II) chloride, Tin(II) 2-hexylhexanoate, Tin(II) fluoride, Tin(II) fluoroborate, Tin(II) iodide, Tin(II) pyrophosphate, Tin(II) sulfate and Tin(II) sulfide. 
     Wherein, the compact generator includes at least one supercapacitor and a power source. The supercapacitor is coupled to the electrolysis module and the power source. The supercapacitor is configured to discharge and store power from the power source and provide power to the electrolysis module for electrolyzing water. 
     Wherein, the supercapacitor includes a plurality of bipolar electrodes, and the bipolar electrodes are stacked in series. 
     Furthermore, the end bipolar electrodes of the bipolar electrode stack are connected to a power source and to receive the polarity from the poles of the power source. 
     Wherein, the two end electrodes of the supercapacitor may perform direct current (DC) or alternating current (AC) property via polarity reversal modulated by a controller. 
     Wherein, at least two identical supercapacitors can form a power module linked to a rechargeable battery for continuous delivery of power. The supercapacitors include a first supercapacitor and a second supercapacitor. The first supercapacitor and second supercapacitor perform reciprocal charging and discharging swing to meet all power demands with high efficiency of energy utilization. 
     Wherein, the supercapacitor can harvest power, using reverse charging, of return current from loads to the negative poles of power source through the reverse sides of electrodes of the supercapacitor. 
     In one embodiment, the compact generator includes a standard universal serial bus (USB) connector connected to the supercapacitor and the power source. The supercapacitor storing power through the standard USB connector. 
     In one embodiment, the supercapacitor may store power by wireless charging as well. 
     For facile production of O 3 , as well as for making H 2 O 2  simultaneously, the present invention provides a compact generator comprised of 4 subsystems for the said goals. The 4 subsystems include: (1 an anode to form O 2  and O 3  from water electrolysis, (2) 2 kinds of cathode to support the operation of anode by forming H 2 , or by reducing O 2  from anode to H 2 O 2 , (3) a built-in energy storing arrays that can be charged with easy access everywhere, and (4) a smart IC circuitry that controls charging-discharging swing, for constant delivery of power at the desired level and a high efficiency of energy utilization. 
     Following are the four subsystems: 
     (1) Electrocatalytic Generation of O 2  and O 3    
     The two electrodes for electrolyzing water to generate O 2 —O 3  mixture employ antimony, nickel-doped tin oxide deposited on titanium metal (Sb,Ni—SnO 2 /Ti) as anode, which is coupled with H 2  evolution by a food-grade AISI (American Iron and Steel Institute) 304 or SS304 as cathode. There is no membrane or separator disposed between anode and cathode, wherein the electrodes are merely fixed at a selected gap. Tap water or other clean water serves as the electrolysis medium without the use of additives. This means that water is the source of ozone. Gaseous products on both of anode and cathode are first formed in sub-micron sizes, then, most of the gases will grow into bigger sizes that escape to the nearby open spaces. Only a small amount of the gases produced, about 0.3% or less of the total gas weight, can dissolve in water. Nevertheless, the concentration of gases in water may be increased by cumulation, pressurization or cooling. 
     (2) Electrocatalytic Co-Generation of O 3  and H 2 O 2    
     Same anode and electrode configuration as (1), but the cathode is replaced by a carbon nanofilm doped with cobalt oxide, which is thermally grown on titanium metal (Co 3 O 4 -CNT/Ti). The said cathode produces no H 2 , but it yields H 2 O 2  by reducing the products of anode, that is, O 2  and proton (H + ). The said products quickly diffuse to the cathode, thereon O 2  and H +  are reduced to H 2 O 2  by cobalt oxide catalyst via a 2-electron mechanism. Some O 3  may mix with H 2 O 2  to form peroxone (H 2 O 3 ), hydroxy radical (.OH) and hydroperoxyl radical (HO 2 .). The radicals are more potent than either O 3  or H 2 O 2 . Thus, the efficacy of sterilization is prolonged and the odor of O 3  is avoided. 
     (3) Built-In Energy Storing Arrays 
     Supercapacitor alone, or an integration of the capacitor with a secondary battery can constitute an on-board energy storing arrays for the compact generators. In the integration, the supercapacitor serves as an energy buffer for the battery, wherein charging and discharging will begin with the capacitor. In the charging mode, the charged energy is first stored in the supercapacitor due to the quick charging rates and the large acceptance of charging currents of the capacitor. Once the energy stored in the capacitor is full, it will be transferred to the battery for long-term storage and lower energy loss based on the current leakage of battery is lower. Thereby, the supercapacitor utilizes the battery as energy backup for meeting all power demands. 
     Under the management of a smart circuitry to be described below, battery can always charge the capacitor only by low charging rates. When the disinfection devices require power, all needs will be provided by the supercapacitor using the advantages of quick discharging rates and high power-density of the capacitor. Regardless of the power level of demands, the supercapacitor can always respond in high rates and in real-time speeds, which cause no hurt to the capacitor. Should the battery be used as demanding as the capacitor, the lifetime of battery will be seriously compromised. As an energy buffer, the supercapacitor is performing “load leveling” for the battery by preventing it from delivering large powers. Hence, the battery can always discharge at very low rates so that its energy is preserved and lifetime is prolonged. 
     (4) Smart Control Circuitry 
     Power is the driving force for the compact generators of this invention to produce the disinfectants of reactive oxygen species (ROS), namely, O 3 , H 2 O 2 , H 2 O 3 , .OH and HO 2 .. The energy refill and energy utilization of supercapacitor and the secondary battery are managed in the highest possible efficiency via the following innovative ways: 
     a. The energy-storage arrays are charged through a standard USB (Universal Serial Bus) Type A charger, which is widely utilized in cellular, laptops, desktop, tablets and other 3C merchandises. 
     b. Charging-Discharging Swing platform—Using 2 or more identical groups of supercapacitors in conjunction with 2° batteries for power provision, the energy content in each group of capacitors is controlled to release only their effective energy, which is the energy under the first ⅓ portion of the rated voltages. When the 1st group has discharged as scheduled, it will go into the charging mode, and the 2nd group immediately assumes the role of discharging. In the next cycle, the same sequence of reciprocal charging and discharging is repeated. The two groups of supercapacitors using the energy replenished by batteries to constantly deliver the required power in full until the demand is fulfilled. In the CD swing, the supercapacitors of this patent can incessantly provide power, which does not occur in the prevailing supercapacitors. An ASIC controller can direct the operation of CD Swing, wherein the level of output power can be decided by adjusting the switching frequency. 
     c. Reverse charging platform—The supercapacitors of this patent application are made of bipolar electrodes stacked juxtaposedly. Both sides of a bipolar electrode are coated with the same electrically active materials. While one side of the bipolar electrode is discharging, the reverse side is charged concurrently. It is the returning current, which returns from a load to the negative pole of a power source, provides the energy for harvest. On its way back, the return current charges the reverse side of a bipolar electrode. Hence, as one side of a bipolar electrode is discharging, the reverse side is being charged simultaneously at the same rate. Eventually, the reverse side of a bipolar electrode will develop a higher voltage but in negative polarity (−V) than the discharging side that is losing its positive voltage. In order to utilize the energy newly attained on the reverse side, the polarity of supercapacitor&#39;s leads must be reversed. By polarity reversal, energy can come from the side with a higher level of voltage. Reverse charging belongs to one kind of energy harvest, which imparts the energy utilization of supercapacitor high efficiency. 
    
    
     
       BRIEF DESCRIPTION OF THE APPENDED DRAWINGS 
       The present invention is best understood by reference to the embodiments described in the subsequent sections accompanied with the following drawings. 
         FIG. 1  is a schematic diagram of a pocket-size ozone pen, which is portable and battery driven. 
         FIG. 2A  to  FIG. 2D  are schematic diagrams of 4 kinds of compact portable devices for generating disinfectants. 
         FIG. 3  is a schematic diagram of an embodiment of a compact generator according to the present invention. 
         FIG. 4  is an exploded-view drawing of the compact generator in  FIG. 3 . 
         FIG. 5  is a logistic function blocks for providing a constant current for producing O 3  and H 2 O 2 . 
     
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     A detailed description of the hereinafter described embodiments of the disclosed apparatus and method are presented herein by way of exemplification with reference to the Figures. Although certain embodiments are shown and described in detail, it should be understood that various changes and modifications may be made without departing from the scope of the appended claims. The scope of the present invention will in no way be limited to the number of constituting components, the materials thereof, the shapes thereof, the relative arrangement thereof, etc., and are disclosed simply as an example of embodiments of the present invention. 
     Human beings are living in an environment filled with bacteria, pathogens, and viruses. We need a handy and effective means for guarding ourselves against the harmful and invisible microbes. Ozone (O 3 ) and hydrogen peroxide (H 2 O 2 ) are two well-known and powerful disinfectants for killing the invisible disease-inducers without byproducts produced. Most importantly, the two disinfectants can be generated under control and at a low cost whenever and wherever they are needed. 
     Please refer to  FIG. 1 .  FIG. 1  is a schematic diagram of a pocket-size ozone pen  1 , which is portable and battery driven. One of the inventors of the current patent application has proposed an ozone pen prototype more than a decade ago, which is described in US 2008/0181832. The original design of the O 3  pen is shown in  FIG. 1 , wherein the pen body has a lid  110 , which covers contents including a battery compartment  120 , rechargeable batteries  130 , IC board  140 , supercapacitor  150 , as well as a pair of electrodes  160 . At the time of filing, platinum plated on titanium (Pt/Ti) was used as anode, and SS304 served as cathode for the pen. In the afterwards development, a better anode material has been identified and implemented in this patent. Table 1 lists a group of the mostly tested anodic materials for making O 3  from water, with a material that can yield the O 3  gas from air is also included for comparison. 
     
       
         
           
               
             
               
                 TABLE 1 
               
             
            
               
                   
               
               
                 Comparison of Methods for Artificial Generation of Ozone Sources 
               
            
           
           
               
               
               
               
               
            
               
                   
                 Anodic 
                   
                 Power 
                   
               
               
                   
                 Materials/Gaseous 
                 Operation 
                 Consumed 
               
            
           
           
               
               
               
               
               
               
               
            
               
                 # 
                 By 
                 Method 
                 Volt (V) 
                 T (° C.) 
                 (kWh/kg O 3 ) 
                 Efficiency (%) 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 1 
                 H 2 O 
                 Pt 
                 5 
                 20-25 
                 20-40 
                 4 
               
               
                 2 
                   
                 Sb,Ni—SnO 2   
                 5-24 
                 20-25 
                 18-30 
                 24-54 
               
               
                 3 
                   
                 β-PbO 2   
                 3-5  
                  5-20 
                 65-54 
                 13-50 
               
               
                 4 
                   
                 Boron-doped 
                 30 
                 5 
                 130 
                 10  
               
               
                   
                   
                 diamond (BDD) 
               
               
                 5 
                 Air or O 2   
                 Dielectrics 
                 3,000 
                 20-25 
                 20-30 
                 4 
               
               
                   
                   
                 (Corona Discharge) 
               
               
                   
               
            
           
         
       
     
     In Table 1, the first four kinds of catalyst are employed in a technique named as electrocatalytic ozone (EO 3 ), wherein water is electrolyzed. Item #5 employs air or pure oxygen as the source of O 3 . Catalyst is the heart of EO 3  from the perspectives of performance and lifetime. Among the EO 3  anodes, Sb and Ni doped tin oxide (Sb,Ni—SnO 2 ) is the best choice of catalyst due to its low cost, high performance, high CP value, easy implementation and long service life. Nevertheless, it is not an easy job to realize the good merits of (Sb,Ni—SnO 2 ) for commercial uses viably. In the metal contents of the said catalyst, Sn is the majority at over 94% by weight, or over 96% by mole ratio, whereas Sb is secondly abundant at 3-5%, and Ni is in a “tiny” amount (0.2. atomic % to Sn). Though at almost trace level, the catalyst will produce no O 3  without Ni. Not only the presence of Ni is a pivotal role, the distribution of Ni on the surface of catalyst also determines the service life of anode for the O 3  generator. 
     By using SnO 2  lattice as a platform, Sb and Ni present themselves in Sb 2 O 5  and Ni 2 O 3 , respectively, in the adjacent vacancies of SnO 2  lattice. While Sb is doped to impart SnO 2  conductivity as in antimony-doped tin oxide (ATO), Ni drives the oxygen evolution potential of SnO 2  to a level where O 3  will be also formed. Together, Sb 5   +  and Ni 3   +  serve as an active site for the generation of O 3 . Since SnO 2  lattice is the foundation for the Sb 5   + —Ni 3   +  active sites of O 3  generation, the said lattice must be built in the right order and clean structure. It is the precursor of SnO 2  that principally determines the quality of Sb,Ni—SnO 2  catalyst. When the SnO 2  lattice is compromised by contaminants, the Sb 5   +—Ni   3   +  active sites would have no chance to build up adequately. In our long terms (decade-long) efforts of development towards EO 3  commercialization, we have verified that stannous oxalate or Ti(II) oxalate, SnC 2 O 4 , is the most suitable precursor for SnO 2  towards O 3  generation. Compared to the mostly chosen precursor of SnO 2  in the literatures, namely SnCl 4 , SnC 2 O 4  has the advantages of higher melting point (MP), 280° C. vs. 56° C., and free of chloride. Low MP causes tremendous loss of Sn at the drying stage of the coating solution if SnCl 4  is used. Also, chloride ion (Cl − ) of SnCl 4  will form HCl during the fabrication of catalyst, which is hazardous to operators and equipment. 
     SnC 2 O 4  can be facilely synthesized via metathesis reaction between a Sn(II) salt and oxalic acid (H 2 C 2 O 4 ) as described in equation (1) 
       SnX 2  (or SnY)+H 2 C 2 O 4 →SnC 2 O 4 ↓+2HX (or H 2 Y)   (1)
 
     In Equation (1), X is a singly charged anion (X −1 ) and Y has a charge count of 2 (Y −2 ). As soon as the two reactants are mixed, SnC 2 O 4  will spontaneously and quickly form as a white precipitate. Then, the precipitate is filtered, rinsed to eliminate the acid contaminant, HX or H 2 Y, finally the wet particles are dried before use. Table 2 lists a group of Sn(II) salts that may be employed as the precursor of SnC 2 O 4 . 
     
       
         
           
               
             
               
                 TABLE 2 
               
             
            
               
                   
               
               
                 Tin(II) Salts for Synthesizing SnC 2 O 4   
               
            
           
           
               
               
               
               
            
               
                   
                   
                   
                 CAS 
               
               
                 # 
                 Ti (II) Salts 
                 Formulas 
                 Number 
               
               
                   
               
            
           
           
               
               
               
               
            
               
                 1 
                 Dibutyltin 
                 (CH 3 C 3 H 6 ) 2 SnCl 2   
                 683-18-1 
               
               
                   
                 dichloride 
               
               
                 2 
                 Dibutyltin maleate 
                 (CH 3 C 3 H 6 ) 2 Sn[C 2 H 2 (COO) 2 ] 
                 78-04-6 
               
               
                 3 
                 Tin(II) acetate 
                 Sn(CH 3 COO) 2   
                 638-39-1 
               
               
                 4 
                 Tin(II) bromide 
                 SnBr 2   
                 10031-24-0 
               
               
                 5 
                 Tin(II) chloride 
                 SnCl 2   
                 7772-99-8 
               
               
                 6 
                 Tin(II) 
                 Sn[CH 3 (CH 2 ) 3 CH(C 2 H 5 )CO 2 ] 2   
                 301-10-0 
               
               
                   
                 2-ethylhexanoate 
               
               
                 7 
                 Tin(II) fluoride 
                 SnF 2   
                 7783-47-3 
               
               
                 8 
                 Tin(II) fluoroborate 
                 Sn(BF 4 ) 2   
                 13814-97-6 
               
               
                 9 
                 Tin(II) iodide 
                 SnI 2   
                 10294-70-9 
               
               
                 10 
                 Tin(II) 
                 Sn 2 P 2 O 7   
                 15578-26-4 
               
               
                   
                 pyrophosphate 
               
               
                 11 
                 Tin(II) sulfate 
                 SnSO 4   
                 7488-55-3 
               
               
                 12 
                 Tin(II) sulfide 
                 SnS 
                 1314-95-0 
               
               
                   
               
            
           
         
       
     
     So long as the two reactants of Equation (1) can be purified successfully, a high-quality SnC 2 O 4  may be prepared. The reactants may be an industrial grade, which will produce a significant advantage in cost. For example, pound for pound, oxalic acid of the reagent grade is at least 28 times higher than that of an industrial grade. 
     Please refer to  FIG. 1  and  FIG. 2  to  FIG. 2D .  FIG. 2A  to  FIG. 2D  are schematic diagrams of 4 kinds of compact portable devices 2,2′,2″,2′″ for generating disinfectants. Besides the quality upgrade of materials for the fabrication of EO 3  anode, we also digitize, miniaturize and functionalize the new products of disinfectant generator, which includes a replacement for O 3  pen of  FIG. 1 . In  FIG. 2 , four compact and portable disinfectant generators are fabricated for sanitary applications. They are: (A) submissible-in-water generator of ozonated water or peroxone water in  FIG. 2A , (B) hand-held sprayer for applying disinfectant on surfaces or objects to be sanitized in  FIG. 2B , (C) automatic sprayer of disinfectant mist for humidification and sanitation in  FIG. 2C , and (D) 3-in-one generator for sanitation-sweeping-mopping  FIG. 2D . Only the device in  FIG. 2A  is operated in a container of static water, or under running water to generate infectants, which include O 3  or O 3  mixed with H 2 O 2 , depending on the cathode material employed. Device in  FIG. 2A  is also an advancing version of ozone pen, and the new device can yield disinfectants more than O 3 . Devices in  FIG. 2B ,  FIG. 2C  and  FIG. 2D  are all equipped with a water compartment for electrodes to be plugged in the water to generate O 3  or O 3 —H 2 O 2 , continuously or batchwise until the refilling of water. There are more ways of designing various generators to meet various needs. 
     No matter how the disinfectant generators are varied, the heart of the devices is always the anode and cathode. While the anode is Ni,Sb—SnO 2 /Ti, the cathode can be AISI 304 or Co 3 O 4 -CNF/Ti. The next key component is the power source to drive the operation of electrodes. An advanced compact O 3  generator or O 3 —H 2 O 2  co-generator is configured in a form of 60 mm diameter disk. Through a standard USB (Universal Serial Bus) Type A Charging Cable, energy from a power source is charged the on-line storage to drive the devices to produce O 3 , or O 3  mixed with H 2 O 2 , which depends on the cathode material employed therein. The disk devices can be submerged in a container of water to generate O 3  water or peroxone (H 2 O 3 ) water for sanitation and disinfection at home or on the road. 
     Please refer to  FIG. 3  and  FIG. 4 .  FIG. 3  is a schematic diagram of an embodiment of a compact generator  3  according to the present invention.  FIG. 4  is an exploded-view drawing of the compact generator  3  in  FIG. 3 . In this embodiment, as shown in  FIG. 3  and  FIG. 4 , the compact generator  3  includes a case body  30  and an electrolysis module  31 . The case body  30  includes a top cover  301 , a peripheral frame  303 , a first separating spacer  304 , a second separating spacer  306 , and a bottom cover  308 . The peripheral frame  303  defines a containing space of the compact generator  3  under the top cover  301  and the bottom cover  308 . The electrolysis module  31  includes a first EO 3  cathode  312 , an EO 3  anode  315  and a second EO 3  cathode  317 . Furthermore. the compact generator  3  includes a power plug  32  with the charging cable. The power plug  32  includes a connector housing  329  with conducting cable, an anode conducting cable  320 , a cathode conduction cable  321 , a cathode connector  322  configured for linking the anode conducting cable  320  with two EO 3  cathodes  312 , 317 , an anode connector  323  configured for linking the cathode conduction cable  321  with EO 3  anode  315 , a LED indication light  324 , a control circuit board  325 , and a male connector  326  configured for plugging into a power source with USB plug socket. Moreover, the compact generator also can includes a hermetic seal between the top cover  301  and the bottom cover  308 , so that the compact generator  3  become water proof. 
     There are 3 electrodes to form a basic unit of electrode set for O 3  generator, or (O 3 +H 2 O 2 ) generator, as shown in  FIG. 3  and  FIG. 4 . The electrode set contains an anode sandwiched by two cathodes, wherein a ring spacer is placed between each of anode-cathode pair to define the electrode gap, as well as to prevent electrical short. While the anode is Sb,Ni—SnO 2 /Ti, the cathode can be either 304 stainless steel or cobalt oxide plated on carbon nanofilm that is grown on Ti substrate (Co 3 O 4 -CNF/Ti). The latter cathode is composed of a thin layer of conductive carbon nanofilm (CNF) directly grown via 700-800° C. on Ti plate substrate for accepting cobalt (ii, iii) oxide [Co 3 O 4 ] thereon. The said cobalt oxide is a catalyst that can catalyze the 2-electron reduction of O 2  into H 2 O 2 . 
     In one embodiment, the material of the first EO 3  cathode is SS304 and the material of the second EO 3  cathode is Co 3 O 4 -CNF/Ti in the compact generator  3 . In another one embodiment, the materials of the first EO 3  cathode and the second EO 3  cathode are Co 3 O 4 -CNF/Ti. 
     By using Sb,Ni—SnO 2 /Ti anode in conjunction with a SS304 cathode, the electrolysis of water will yield O 2 /O 3  on anode and H 2  on cathode, respectively, at then individual potential as specified in Equation (2) and (3): 
       Anode reaction: 5H 2 O→O 2 ↑+O 3 ↑+10H + +10e −  E°=1.60V   (2)
 
       Cathode reaction: 2H 2 O+2e − →H 2 ↑+OH −  E°=0.0 V   (3)
 
     where E° is the gas evolution potential at standard state (0° C., 1 atm). 
     On the other hand, water electrolysis by coupling the same anode with Co 3 O 4 -CNF/Ti cathode will give a different cathode reaction as shown in Equation (4): 
       Cathode reaction: O 2 +2H + +2e − →H 2 O 2  E°=0.67V   (4)
 
     Furthermore, in the presence of O 3 , H 2 O 2  evolved will react with O 3  from anode as described in Equation (5): 
       2H 2 O 2 +2O 3 →.OH+HO 2 .+3O 2 +H 2 O   (5)
 
     In reaction (4), O 2  and H +  produced on anode will automatically diffuse to Co 3 O 4  catalyst on cathode for reduction. Thus, O 2  evolution reaction (OER) on Sb,Ni—SnO 2 /Ti anode and O 2  reduction reaction (ORR) on Co 3 O 4 -CNF/Ti cathode constitute a self-sustained system for the cogeneration of O 3  and H 2 O 2  from a simple water electrolysis. Similar cogeneration of O 3  and H 2 O 2  can also be seen in the report, by K Ishiwata et al. of Abstract #2655, in the 214th ECS meeting in year 2008 February. In their setup, the anode is β-PbO 2 , and cathode is Ag marbles (Ag film deposited on Cu balls). The said anode and cathode electrodes are separated by an ion exchange membrane. Instead of using symmetrical electrodes as  FIG. 3  and  FIG. 4 , Ishiwata&#39;s report employed anode and cathode in incompatible shape and dimensions. Furthermore, O 2  is supplied by flowing air into the cathodic compartment rather than on-line generation. 
     Two powerful disinfectants are formed in Equation (5). They are hydorxy radical (.OH) and hydroperoxyl or perhydroxyl radical (HO 2 .), and they belong to reactive oxygen species (ROS) group. Using an unpaired electron, the said radicals can quickly extract one electron from bacteria, viruses and organic materials in water resulting in oxidation reaction of species being attacked, which will lead to the decomposition of the subjects. Ikai et al., in Antimicrobial Agents &amp; Chemotherapy, p. 5086-5091, December (2010), presented a study of oral disinfection by photolysis of H 2 O 2  by laser irradiation to form .OH for killing 4 species of pathogenic oral bacteria. In the presence of as low as 200-300 μM, or 3.4-5.1 ppm of .OH, a reduction of &gt;99.999% of viable bacteria counts is attained within 3 minutes of treatment. Compared with other .OH generation systems, including, Fenton reaction, Haber-Weiss reaction, sonolysis of H 2 O and photolysis of H 2 O 2 , the approach of this patent has the advantages of low-cost, convenience and environment friendly. 
     Online and in-situ production of a controllable dosages of O 3  and H 2 O 2  is very beneficial to the applications of sanitation, disinfection, personal hygiene and wastewater treatment. Two novel materials are involved in the cogeneration of O 3 —H 2 O 2 , one of them is Sb,Ni—SnO2/Ti anode that can consistently produce a constant source of pure O 2 /O 3  at 2:1 yield ratio from water electrolysis at low power consumption. The other is Co 3 O 4 -CNF/Ti cathode containing nano carbon and Co(ii,iii) oxide that provide a synergistic catalysis on reducing O 2  to H 2 O 2  through a 2-electron mechanism (Equation 4). On integrating Sb,Ni—SnO 2 /Ti anode with Co 3 O 4 -CNF/Ti cathode for water electrolysis, O 3  and H 2 O 2  can be quickly and simultaneously generated. But, the OER (oxygen evolution reaction) on anode and ORR (oxygen reduction reaction) on cathode are not equally made, they compete each other. Kinetically, O 2  evolution is faster than O 2  reduction or H 2 O 2  formation. In order to enhance the throughput of H 2 O 2 , Co 3 O 4 -CNF can be directly grown on metal balls. Then, many Co 3 O 4 -CNF coated marbles can fill a conductive metal mesh bucket to form a packed cathode. Each ball in the bucket is a particle cathode that can concurrently reduce whatever quantity of O 2  gas provided by multiple anodes to H 2 O 2 . Consequently, the throughput of H 2 O 2  can be scaled up for practical applications. 
     Please refer to  FIG. 5 .  FIG. 5  is a logistic function blocks for providing a constant current for producing O 3  and H 2 O 2 . Apparently, water electrolysis requires power, and power consumption should be compensated by the values of materials produced. If the pay back is far less than the cost, then, the technology is meaningless. Based on the efficient anode and cathode, namely, Sb,Ni—SnO 2 /Ti and Co 3 O 4 -CNF/Ti an efficient device that can conservatively provide power to the said electrodes to yield O 3 —H 2 O 2 —H 2 O 3  and their derives including .OH and HO 2 . (Equation 5), is needed. This patent application chooses supercapacitor as the desired power device. For a high efficiency of energy utilization via supercapacitor, this patent also applies the following 2 platforms for operating the supercapacitor: 
     1) Charge-discharge Swing (CD Swing) 
     2) Reverse Charging 
     All three said items, the capacitor and 2 platforms, have been elaborated in one of LRS&#39; prior applications, US2008/0181832. Only, a brief summary is provided for the 3 items in the current application. 
     Supercapacitors 
     Same as battery, the supercapacitor is also an energy-storing device. Both energy devices are built based on 2 electrodes, that is, an anode and a cathode. Also, a gel polymer electrolyte (GPE) can be disposed between the electrodes of the two devices. However, the capacitor can be configured in a very different way from battery, which makes the former unique. 
     In supercapacitor, the GPE can impart 3 functions to the capacitor: as (a) separator, (b) conductor and (c) adhesive. This patent intends to use the GPE to bind many pieces of electrodes into a stack, which is called element of the capacitor. Multiple electrodes may be stacked vertically, or juxtaposedly, into a desirable height of element. Only the end electrodes of the stack, that is, top and bottom, is one side coated with an electrically active material, whereas the middle electrodes are all 2-side coated. Moreover, the middle electrodes are bipolar, which means two sides of an electrode can carry different polarities. The polarity of electrodes is determined by the connection of end electrodes. In other words, only the end electrodes are equipped with connectors for linking to an outer power source for charging. Once a stacked supercapacitor is charged, the end electrode that is hooked to the positive pole of the source will become anode, and the other end electrode is cathode. Through the effect of induction, the middle electrodes, or bipolar electrodes, will be polarized to + or − accordingly. In the next charging, the polarity of all electrodes can be reversed simultaneously through an electronically control. Electronically, the polarity of supercapacitor&#39;s electrodes can be reversed at any frequency at real-time as needed, which can be done by reversing the polarity of end electrodes via a controller at the desired frequency. The controller may be a central processing unit (CPU), micro processing unit (MPU), micro control unit (MCU). Frequency-guide Polarity Reversal (FPR) permits the bipolar-based supercapacitors to perform in direct current (DC) or alternating current (AC) mode. Moreover, the stacking of electrodes is an in-housing serial link (ISL) of multiple unit cells of supercapacitor. Each unit cell will add a cellular voltage to the total working voltage of module stacked. Hence, the higher the stack, the greater the working voltage of the module will be. Not only storing energy, the bipolar electrodes also work as serial linkage connectors. This feature permits the supercapacitor to be made into modules of high-voltage with high energy density, and high power density as well. However, the devices will have small dimensions and a low consumption of construction materials. It is an ultimate goal for this patent that the supercapacitor will be employed in all electrolytic generation of O 3  alone, or O 3  and H 2 O 2  together. 
     Charging-Discharging Swing (CD Swing) Platform 
     It is well known that the charging-discharging speed of all kind of capacitors are very fast. This is due to the capacitors employ only the surface of their electrodes for storing energy, thus, the charging of a shallow room can be completed in a very short time. Like proverbial saying “easy come easy go”, the low content of energy in the capacitors can be discharged quickly to an empty state. Only after recharging to its full energy state, the capacitors can perform again. Thus, the power provision of capacitors is intermittent, which is unacceptable to loads consuming large power constantly such as electric vehicles. This is the major hurdle for the developers of supercapacitor to overcome. How to make a non-stop supercapacitor that can perform as lithium battery on delivering 200-400 miles of range per charge? The answer contains many aspects of endeavors. This patent has presented the approach of effective enlargement of voltage by ISL (in-housing serial link) of bipolar electrodes. Since the energy and power of supercapacitor is proportional to the square of voltage. When the voltage is doubled, both the energy density and the power density of supercapacitor will be up quadrupled. Moreover, the bipolar electrodes also impart a dual, DC and AC, property to the bipolar-based supercapacitors via FPR (frequency-guide polarity reversal). It means that the FPR technique grants the supercapacitors to perform as either DC or AC devices. The said added-feature allows the supercapacitors to be charged wirelessly or remotely. Although supercapacitor can manage many types of energy use, it also requires operating platforms for upgrading its utilization efficiency of energy. Charging-discharging swing and reverse charging are designed as the platforms to meet the goal. 
     Under uncontrolled conditions, discharging may quickly drain the voltage of supercapacitors to a level below the driving voltage of loads, which nullifies the devices. For a high efficiency of energy utilization, supercapacitor should be operated by the effective energy only. Roughly, the energy under the first ⅓ portion of the rated voltage is regarded effective. In order to discharge and replenish just the effective energy, at least two groups of supercapacitor are needed in an operation of continuous provision of power. As the 1st group of supercapacitors has clone its set discharging, it will go into charging mode, and the 2nd group will immediately assume the discharging role. In the next cycle, the charging and discharging reciprocal sequence is repeated. The two capacitors continuously perform the reciprocal charging and discharging until the demand is fulfilled. Since the effective energy is only ⅓ portion of the total energy content of capacitors, so the discharging and recharging can be executed swiftly. The power delivery is not only consistent, but also the power level can be decided by adjusting the swing frequency, which can be executed easily using an IC controller. 
     Reverse Charging Platform 
     During the discharging of supercapacitor modules made by ISL, it is observed that as the voltage of discharging side is fading, concurrently, the reverse side shows a building-up voltage in opposite polarity. The reverse charging is due to an energy harvesting on the return current from load via the supercapacitor back to the negative pole of the power source. Eventually, the “one side up and down the other” effect will impart the reverse side a higher value of volt in negative polarity than the number volt of the discharging side. On reversing the polarity of supercapacitor&#39;s leads by an IC controller, the exhausted super-capacitor can continuously discharge using the newly harvested energy. Thus, reverse charging may save energy from turning into heat, and it makes the supercapacitors based on bipolar electrodes unique and useful in many power applications. 
     Human beings live in a world filled with invisible microbes including viruses, pathogens and benign or infectious bacteria. They reside on the surface of fruits, vegetables, as well as seemingly fresh food and clean utensils. The microbial communities are ubiquitous, they are even identified to exist on human bodies. It is important to have an effective and affordable protecting means to stay healthy in our daily lives. The in-time provision of disinfectants, such as, the generators in this patent, will do the job. 
     EXAMPLE 
     Ozone molecule (O 3 ) can only dissolve in water at 29.9 μg per 1 ml of water, 29.9 μg/ml or 29.9 ppm, at 20° C. water. If water temperature is lower, more O 3  can dissolve in water. When waterborne O 3  is above 1 ppm, it can liberate O 3  into air more than the safety levels (OSHA workplace maximum=0.1 ppm). The O 3  level produced by the generators of this patent can reach and beyond 1 ppm. However, the throughput of O 3  and the application of O 3  are adjustable and concealed. In the cogeneration type of generators, O 3  and H 2 O 2  will form hydroxy radical (.OH) and hydroperoxyl radical (HO2.). The radicals not only are much more potent than O 3  on disinfection, also they inhibit O 3  leak from going above the allowed limit. 
       Straphylococcus aureus  (SA) is one kind of gem that about 1 in 3 people may carry in their noses and skin. Most of the time, SA does not cause any harm. Similarly,  Escherichia coli  ( E. coli ) is another gem that lives in human body, that is, in the intestines. Most types of  E.coli  are harmless. Nevertheless, serious infection by SA or  E. coli  can be deadly. SA and  E. coli  are just two of the 12 most common pathogenic bacteria. For evaluating the disinfectants produced by the devices of this patent, we have outsourced the validation to a reputable biology lab using our disinfectants on eliminating the cultured  E. coli  and SA separately. The said bacterial were cultured on blood agar plates under 37° C. for 18 hours to the concentration levels of 5×10 7 -5×10 8  CFU/ml. Then, the diluted bacteria solution was mixed with the O 3  water produced by the generator, at 100 μl bacteria liquid to 0.92 ml O 3 —H 2 O. In 10-minute reaction time, all tests showed that over 99.99%  E.coli  and SA were abated. 
     With the examples and explanations mentioned above, the features and spirits of the invention are hereinbefore well described. More importantly, the present invention is not limited to the embodiment described herein. Those skilled in the art will readily observe that numerous modifications and alterations of the device may be made while retaining the teachings of the invention. Accordingly, the above disclosure should be construed as limited only by the metes and bounds of the appended claims.