Name: preparation of polyoxometalate-based photo-responsive membranes for the photo-activation of manganese oxide catalysts
Uploaded: 2018-08-07T14:30:00
Description: Watch this Scientific Journal Video about Preparation of Polyoxometalate-based Photo-responsive Membranes for the Photo-activation of Manganese Oxide Catalysts at JoVE.com

A. Y. received financial support from the Global Center of Excellence for Mechanical Systems Innovation program of the University of Tokyo and from the University Tokyo Grant for Ph.D. Research. This work is partly supported by JSPS KAKENHI Grant-in-Aid for Young Scientists (B) (17K17718).

It is advisable to refer to all relevant material safety data sheets (MSDS) prior to using chemicals, as some used in these syntheses are highly acidic and corrosive. In addition, one polymer used in this work (polyacrylamide) may contain the carcinogenic monomer, acrylamide. The use of personal protective equipment (safety glasses, gloves, lab coat, full-length pants, closed-toe shoes) is required to prevent injuries from chemicals or heat. After conducting the cross-linking process, membrane samples should be stored in...

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It is critical to apply the cross-linking method introduced by Helen et al.14 to develop a self-standing membrane. When polyvinyl acetate was applied as the base polymer in this study, aggregation of H3PW12O40 occurred, which prevented formation of the self-standing membrane. However, when fabrication of the membrane was attempted utilizing Nafion as the base polymer, there was no progression of the reaction with Ce3+ and Co2+, althou...

The development of solar energy conversion systems using artificial photosynthesis or solar cells is necessary to enable the provision of alternative energy sources that can ameliorate global climate and energy issues1,2,3,4. Photo-functional materials can be broadly categorized into two groups, semiconductor-based systems and organic molecule-based systems. Although many different system types have been developed, improvements still need to be made because semiconductor systems suffer from a lack of precise charge transfer control, and organic molecule systems are not adequately durable with respect to photo-irradiation. However, the use of inorganic molecules as charge transfer unit components can improve these respective issues. For example, Frei et al. developed oxo-bridged metal systems grafted on the surface of mesoporous silica which can induce the metal-to-metal charge transfer (MMCT) by photo-irradiation and trigger photochemical redox reactions5,6,7,8,9.
Our group extended the single atomic system to a polynuclear system utilizing polyoxometalate (POM) as the electron acceptor10,11,12, with the expectation that use of the polynuclear system would be advantageous in the induction and control of the multi-electron transfer reaction, which is an important concept in energy conversion. In the protocol described here, we present the detailed method used to prepare the POM-based MMCT system, which works in a polymer matrix as we recently reported13. The membrane-type configuration is favorable for product separation between anodic and cathodic reaction products. The cross-linking method was applied, which enabled formation of a self-standing membrane, even with high POM contents. Photoelectrochemical measurements proved that appropriate selection of the donor metal is key to triggering the target. The POM/donor metal system works as a photo-sensitizer to activate multi-electron transfer catalysts under visible light irradiation. Although this work utilizes MnOx as a multi-electron transfer catalyst for the water oxidation reaction, this photo-functional system is also applicable for use with other types of reactions by utilizing various POMs, donor metals, and catalysts.

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			<td height="42" style="height:42px;width:287px;">Poly(vinyl Alcohol) 1000, Completely Hydrolyzed</td>
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			<td style="width:119px;">162-16325</td>
			<td style="width:295px;"></td>
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			<td height="42" style="height:42px;width:287px;">Polyacrylamide, Mv 6,000,000</td>
			<td style="width:119px;">Polyaciences, Inc.</td>
			<td style="width:119px;">2806</td>
			<td>May contain carcinogenic monomer, acrylamide.</td>
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			<td height="21" style="height:21px;width:287px;">12 Tungsto(VI)phosphoric Acid n-Hydrate</td>
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			<td>Highly acidic</td>
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			<td height="21" style="height:21px;width:287px;">Acetone 99.5 + %(GC)</td>
			<td style="width:119px;">Wako</td>
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			<td height="21" style="height:21px;width:287px;">Cobalt(II) Chloride Hexahydrate 99 + %(Ti)</td>
			<td style="width:119px;">Wako</td>
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			<td height="21" style="height:21px;width:287px;">Pottasium Permanganate 99.3 + %(Ti)</td>
			<td style="width:119px;">Wako</td>
			<td style="width:119px;">167-04182</td>
			<td>Highly oxydative</td>
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			<td height="42" style="height:42px;width:287px;">Sodium Thiosulfate Pentahydrate 99 + %(Ti)</td>
			<td style="width:119px;">Wako</td>
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			<td height="21" style="height:21px;width:287px;">Automatic spray gun</td>
			<td style="width:119px;">Lumina</td>
			<td style="width:119px;">ST-6</td>
			<td></td>
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preparation of polyoxometalate-based photo-responsive membranes for the photo-activation of manganese oxide catalysts

This paper presents a method to prepare charge-transfer chromophores using polyoxotungstate (PW12O403-), transition metal ions (Ce3+ or Co2+), and organic polymers, with the aim of photo-activating oxygen-evolving manganese oxide catalysts, which are important components in artificial photosynthesis. The cross-linking technique was applied to obtain a self-standing membrane with a high PW12O403- content. Incorporation and structure retention of PW12O403- within the polymer matrix were confirmed by FT-IR and micro-Raman spectroscopy, and optical characteristics were investigated by UV-Vis spectroscopy, which revealed successful construction of the metal-to-metal charge transfer (MMCT) unit. After deposition of MnOx oxygen evolving catalysts, photocurrent measurements under visible light irradiation verified the sequential charge transfer, Mn &#8594; MMCT unit &#8594; electrode, and&#160;the photocurrent intensity was consistent with the redox potential of the donor metal (Ce or Co). This method provides a new strategy for preparing integrated systems involving catalysts and photon-absorption parts for use with photo-functional materials.

Retention of the POM structure in the polymer matrix was confirmed by FT-IR and micro-Raman spectroscopy (Figure 1); vibration peaks corresponding to the Keggin structure of POM were observed, and peaks of the polymers were found to be shifted due to hydrogen bonding with POM. Spectroscopic analysis was very useful for determining successful construction of the charge transfer unit, and this was also confirmed by the apparent color change of the samples (<str...

Watch this Scientific Journal Video about Preparation of Polyoxometalate-based Photo-responsive Membranes for the Photo-activation of Manganese Oxide Catalysts at JoVE.com

Preparation of Polyoxometalate-based Photo-responsive Membranes for the Photo-activation of Manganese Oxide Catalysts

Here, we present a protocol to prepare charge transfer chromophores based on a polyoxometalate/polymer composite membrane.

This paper presents a method to prepare charge-transfer chromophores using polyoxotungstate (PW12O403-), transition metal ions (Ce3+ or Co2+), and organic ...

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