Practical Method for Production of Water Fuel with Piezoelectric

[Nrgaway]

Mechanism for Direct-Water-Splitting Via Piezoelectrochemical Effect Papers
Inventors:     Xu; Huifang; (Madison, WI) ; Hong; Kuang-Sheng; (Madison, WI) ; Li; Xiaochun; (Madison, WI)
http://www.rexresearch.com/xu/xu.htm

I have provided a link (http://www.rexresearch.com/xu/xu.htm) to several articles written about and by Huifang Xu.  There is also the paper submitted to 'The Journal of Physical Chemistry Letters' (http://pubs.acs.org/doi/full/10.1021/jz100027t and patent application within the link.  There is a ton of valuable information in here that should help us.  In particular I will include a few excerpts.

[0127] 3. ZnO Fibers

[0128] A hydrothermal method was used to synthesize ZnO fibers (FIGS. 27-29). Hexamethylenetetramine (C.sub.6H.sub.12N.sub.4) and zinc nitrate hexahydrate (Zn(NO.sub.3).sub.2.6H.sub.2O) precursor solutions were mixed together (1:1 molar ratio) in Teflon cup with 60% capacity followed by magnetically stirring in 15 min. The mixture was then sealed tightly in a stainless steel autoclave. The closed bomb was heated at 95.degree. C. for 48 hr. After that the bomb was cooled naturally to room temperature. The final products were washed with DI water and dried at room temperature.

[0129] Hydrogen Production from Water Using Ultrasonic Vibrations and Fibers of Piezoelectric Material

[0130] In support of the above theory, testing was done utilizing zinc oxide (ZnO) micro-fibers synthesized using the bottom-up method (i.e. hydrothermal synthesis method). Nano-fibers of quartz and other materials can be fabricated using photolithography, dry-cutting and other methods, some of which were discussed previously.

[0131] The micro-fibers were positioned in a pure water aqueous environment to which a suitable ultrasonic vibration generator was connected in order to direct ultrasonic vibrations at the fibers within the aqueous environment. An identical trial utilizing a similar aqueous environment without any ZnO micro-fibers was also conducted to provide a control for the experiment. Initially, the aqueous environments were left alone in order to measure any hydrogen production from the aqueous environments. This was done for an initial forty (40) minute time period with a suitable hydrogen gas detection device such as described previously used to detect any hydrogen produced by the micro-fiber containing and control aqueous systems. After the initial time period, the ultrasonic vibration generator was activated to direct vibrations through the aqueous environment at the micro-fibers to deflect and "mechanically strain" the micro-fibers. The ultrasonic vibration generator was left active for a second forty (40) minute time period, and the hydrogen production from the system during this period was measured in the same manner as during the initial time period.

[0132] The results of this experiment are shown in FIG. 23, in which the evolution of H.sub.2 from pure water under an application of ultrasonic waves. As seen in the graph, during the initial forty (40) minute period where the ultrasonic vibration generator inactive, no hydrogen was produced in either the micro-fiber containing or control aqueous environments. Regarding the control system, no hydrogen production was detected during the second time period as well. However, when the ultrasonic generator was activated during the second time period in the system including the ZnO micro-fibers, rapid hydrogen production was obtained at an initial rate of 12.9 ppmh.sup.-1. This hydrogen gas production upon mechanical vibration of the ZnO micro-fibers in the aqueous environment agrees with the previous experiments, in which the strained ZnO powders were also active to split water into hydrogen and oxygen.

[0133] This is because, in a mechanism similar to that caused by the deformation of the structure of ZnO grains by ball milling, with regard to micro- and nano-scale fibers, ZnO fibers will build up electric potentials on the surface through deformation caused as a result in an aqueous environment, the mechanical or strain induced electric potential caused by the vibrations is transformed on the fibers into the chemical energy that is utilized to split water into hydrogen and oxygen gas.

[0134] The performance of direct water-splitting was further investigated showing the capabilities of ZnO fibers and BaTiO.sub.3 dendrites for scavenging vibrational waste energies from urban environments to generate hydrogen and oxygen gases from pure water. In order to first measure hydrogen gas production, ultrasonic wave vibrations at a frequency of 40 kHz using a Branson 5510-MT Ultrasonic Cleaner were applied to 5.0 mL of DI water in a Pyrex glass tube to determine the results of the piezoelectrochemical effect on as-synthesized ZnO fibers prepared on a Si (100) wafer of 1.times.1 cm.sup.2. The results for hydrogen gas production for the ZnO and the BaTiO.sub.3 are shown in FIGS. 30 and 32. A control experiment was also conducted with a cleaned Si wafer (1.times.1 cm.sup.2), without ZnO fibers in the system. In the first period when external vibration was used (0.about.40.sup.th minute), rapid hydrogen production was obtained at an initial rate of 3.4.times.10.sup.-3 ppm per second (ppm/s). The reaction cell was then evacuated at the 40.sup.th minute allowing a fresh run beginning at the 41.sup.st minute. Ultrasonic wave vibration was turned off at the beginning of the 41.sup.st minute, and the H.sub.2 production was measured again. It was found that hydrogen generation stopped when the ultrasonic wave vibration was turned off, leading to a negligible H.sub.2 production rate (<0.0001 ppm/s). This is similar to the control experiment (0.about.40.sup.th minute). A possible reason for the low gas concentration in the experiments without ultrasonic vibration or the control experiment could be due to contamination from air in the room.

[0135] The oxygen production performance of ZnO fibers via the piezoelectrochemical effect was also investigated. Oxygen concentration was measured in solution as a function of time as shown in FIG. 31. The response of the ZnO fibers to external vibrations was demonstrated by turning the ultrasonic wave in the system on and off. Consistent with the hydrogen production test, when ultrasonic waves were applied to ZnO fibers, oxygen concentration grew rapidly at an initial rate of 1.7.times.10.sup.-3 (ppm/s).Oxygen production stopped in the 41.sup.st to 80.sup.th minutes, corresponding to when the ultrasonic waves were turned off. ZnO fibers in DI water with applied ultrasonic vibrations evolved hydrogen and oxygen gases with a stoichiometric equivalent of H.sub.2O.sub.2=2:1. As with the previous experiments, no oxygen production was observed for the Si wafer control experiment.

[0136] Thus, based on the hydrogen and oxygen production tests utilizing the fibers of piezoelectric materials (e.g., ZnO, quartz, BaTiO.sub.3) in an aqueous environment, there is a direct conversion of mechanical energy (ultrasonic vibration) into the chemical energy (water splitting) as a result of the mechanical strain placed in the fibers. This is believed as a very important step forward to recycling the waste energy into alternative fuel in the future.

[0137] The micro- or nano-scale fibers of these materials create high levels of hydrogen production in the aqueous environment conditions as utilized in the above experiments, because the piezoelectric materials are more chemically stable, and able to generate greater electrical potential on the surface for further chemical reactions. In addition, quartz and certain other piezoelectric materials are much cheaper to obtain than other piezoelectric materials, further reducing the barriers to effective use of the piezoelectrochemical effect to generate useful energy from waste energy.

[0138] Similarly, when the external mechanical input is turned off, electrical charges will no longer accumulate on the fiber surface. Thus no sufficient potential can be used to reduce or oxidize the water molecules into hydrogen and oxygen, respectively. This is evidenced by the fact that we did not observe a rapid gas growth rate without vibration compared to the vibration mode. Our conclusions are that quartz, ZnO fibers and BaTiO.sub.3 dendrites show very good responses to the application of ultrasonic vibrations by generating H.sub.2 and O.sub.2 directly from water. Based on the gas production tests above, we have confirmed the piezoelectrochemical (PZEC) effect by using the quartz, ZnO and BaTiO.sub.3 fibers in wet conditions.

[Nrgaway]

Originally Power To Be wanted us to house the crystals in an envelope.  Later he said to just put them in the water.  I think he just wanted us to jump in there and see how effective the crystals were when used in the equation.  I think folks were taking to long to get their envelopes and get on with their experimentation and he was trying to get them to experiment quickly and see how impressive the addition of the crystals was.  He said later that we needed to decide how to adhere the crystals to a surface.  He said that there were many ways to do this and that we needed to find a suitable way to do that.  He later said that he attached his crystals to a rigid structure while some attached theirs to a flexible structure.  He never mentioned what structure he was referring to.  I jumped to a conclusion that maybe it was the inner surface of the bowl, but I have since changed my mind about that.  I think that the acoustical properties of the brass bowl would be adversely affected if the inner part was coated with the crystals.  I'm more inclined now to find some sort of envelope arrangement for my crystals and have it affixed to the side of the cell beneath the water.  I may affix my envelopes to the bottom of the cell around the transducers.  The brass acoustical horn will ring out and be deflected back into the water by the resonating brass bowl.  Therefore, the envelopes would house the crystals and keep them from going all over the place and possibly being lost and also perfectly position them where they will be a good target from waves being deflected back from the resonating brass bowls.

I've been doing a lot of thinking about this and don't know if I'm right or wrong, but it seems like a good idea.

For what it's worth, the link to the paper published in the post above contains very detailed procedures that can be used to replicate most parts of this experiment.  They used very simple devices for their chamber. (I do think this was only for the quartz part of the experiment, since paragraph 131 specifies that they used an aqueous environment for the ZnO portions.)

[0094] The experiments of water splitting to hydrogen and oxygen were carried out using sealed glass tube and samples in water under a standard condition. Glass tubes a half-inch diameter and one-foot in length were used for the experiment. The reaction cell (glass tube) was filled with nitrogen gas after adding samples of the piezoelectric material being tested. To monitor the hydrogen and oxygen concentration variation, the gas inside the cell was extracted by syringe and inject into the external hydrogen analyzer. Hydrogen and oxygen production kinetics were obtained by calculating the evolved hydrogen concentration as a function time.

[0131] The micro-fibers were positioned in a pure water aqueous environment to which a suitable ultrasonic vibration generator was connected in order to direct ultrasonic vibrations at the fibers within the aqueous environment. An identical trial utilizing a similar aqueous environment without any ZnO micro-fibers was also conducted to provide a control for the experiment. Initially, the aqueous environments were left alone in order to measure any hydrogen production from the aqueous environments. This was done for an initial forty (40) minute time period with a suitable hydrogen gas detection device such as described previously used to detect any hydrogen produced by the micro-fiber containing and control aqueous systems. After the initial time period, the ultrasonic vibration generator was activated to direct vibrations through the aqueous environment at the micro-fibers to deflect and "mechanically strain" the micro-fibers. The ultrasonic vibration generator was left active for a second forty (40) minute time period, and the hydrogen production from the system during this period was measured in the same manner as during the initial time period.

In the article written on http://www.greencarcongress.com/2010/03/pzec-20100316.html they also mention using barium titanate crystals as well.  It is also mentioned in the paper.

The researchers, led by UW-Madison geologist and crystal specialist Huifang Xu, grew nanocrystals of two common crystals, zinc oxide and barium titanate, and placed them in water. When pulsed with ultrasonic vibrations, the nanofibers flexed and catalyzed a chemical reaction to split the water molecules into hydrogen and oxygen.

Paragraph 134 specifies an additional test where they use a Branson 5510-MT Ultrasonic Cleaner @ 40 kHz where a crystal coated wafer was applied to 5 mL of distilled water in a Pyrex glass.

[0134] The performance of direct water-splitting was further investigated showing the capabilities of ZnO fibers and BaTiO.sub.3 dendrites for scavenging vibrational waste energies from urban environments to generate hydrogen and oxygen gases from pure water. In order to first measure hydrogen gas production, ultrasonic wave vibrations at a frequency of 40 kHz using a Branson 5510-MT Ultrasonic Cleaner were applied to 5.0 mL of DI water in a Pyrex glass tube to determine the results of the piezoelectrochemical effect on as-synthesized ZnO fibers prepared on a Si (100) wafer of 1.times.1 cm.sup.2. The results for hydrogen gas production for the ZnO and the BaTiO.sub.3 are shown in FIGS. 30 and 32. A control experiment was also conducted with a cleaned Si wafer (1.times.1 cm.sup.2), without ZnO fibers in the system. In the first period when external vibration was used (0.about.40.sup.th minute), rapid hydrogen production was obtained at an initial rate of 3.4.times.10.sup.-3 ppm per second (ppm/s). The reaction cell was then evacuated at the 40.sup.th minute allowing a fresh run beginning at the 41.sup.st minute. Ultrasonic wave vibration was turned off at the beginning of the 41.sup.st minute, and the H.sub.2 production was measured again. It was found that hydrogen generation stopped when the ultrasonic wave vibration was turned off, leading to a negligible H.sub.2 production rate (<0.0001 ppm/s). This is similar to the control experiment (0.about.40.sup.th minute). A possible reason for the low gas concentration in the experiments without ultrasonic vibration or the control experiment could be due to contamination from air in the room.

This is getting exciting!!!

[Slovenia]

I went back and studied what Power To Be shared about the crystals in all of his posts on Energetic as well as OU and it became clear to me that his recipe for us regarding the zinc crystals was strictly a home brew kind of thing that would work.  He admitted that there were very complicated processes used for making the crystals but he was trying to come up with a recipe for the guy who wanted to make them in his home.  He also said that for best results you should use the technique in the referenced pdf.

Anyway, Power To Be was trying to help us!! 

Thanks Power To Be!!!!

[Slovenia]

NEW Power To Be Archived Files Available

Well guys, I have a complete compilation of all of Power To Be's posts in one place now.  I have uploaded them to Scribd and you can download them at the following links:

Power To Be Complete Compilation of Posts to date:
http://www.scribd.com/doc/52177573/Compilation-of-Power1-Posts

Romo Complete Compilation of Posts with regard to Power To Be Project:
http://www.scribd.com/doc/52177635/Compilation-of-Romo-Posts

[Nrgaway]

I went back and studied what Power To Be shared about the crystals in all of his posts on Energetic as well as OU and it became clear to me that his recipe for us regarding the zinc crystals was strictly a home brew kind of thing that would work.  He admitted that there were very complicated processes used for making the crystals but he was trying to come up with a recipe for the guy who wanted to make them in his home.  He also said that for best results you should use the technique in the referenced pdf.

Anyway, Power To Be was trying to help us!! 

Thanks Power To Be!!!!

I am aware The Power To Be has provided a home based recipe.  This of course is awesome and allows us to run this experiment at home!

He also stated that some steps were purposely missing.  Thats why I posted the information above so we can try to figure out what was missing.  I think we have all the information we need now if the home grown crystals work. 

The whole process seems very simple and easy to understand.  I don't understand why you would need horns or bowls or even fancy ways to attach the crystals.  I think if the crystals are formed correctly you will get a reaction within 20 minutes that should be measurable. 

I am not saying you don't need the horns and bowls, I just say I don't understand why it would not work without them.  For that matter I figure the process should work (but maybe not as efficient) even if you are not tuned into the 'exact' / correct frequency based on my understanding of the piezoelectric effect..

When [the crystals are] pulsed with ultrasonic vibrations, the nanofibers flexed and catalyzed a chemical reaction to split the water molecules into hydrogen and oxygen.

When the fibers bend, asymmetries in their crystal structures generate positive and negative charges and create an electrical potential. This phenomenon, called the piezoelectric effect, has been well known in certain crystals for more than a century and is the driving force behind quartz clocks and other applications.

I applaud everyone's effort so far and am looking forward to a successful replication very soon. 
Thanks for listening.

Correction to post #411:
I mistakingly stated they used distilled water, I meant deionized water