Chemistry on the electrodes: post-functionalization and stability enhancement of anchored dyes on mesoporous metal oxide photoelectrochemical cells with copper-free Huisgen cycloaddition reaction,Journal of Materials Chemistry A

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Chemistry on the electrodes: post-functionalization and stability enhancement of anchored dyes on mesoporous metal oxide photoelectrochemical cells with copper-free Huisgen cycloaddition reaction
Journal of Materials Chemistry A ( IF 10.7 ) Pub Date : 2020-06-09 , DOI: 10.1039/d0ta04982d
Yousra Bentounsi _{1,

2,

3,

4,

5} , Konstantinos Seintis _{6,

7,

8,

9} , Dorine Ameline _{1,

2,

3,

4,

5} , Stéphane Diring _{1,

2,

3,

4,

5} , David Provost _{1,

2,

3,

4,

5} , Errol Blart _{1,

2,

3,

4,

5} , Yann Pellegrin _{1,

2,

3,

4,

5} , Damien Cossement _{10,

11,

12} , Eric Vauthey _{6,

7,

8,

9} , Fabrice Odobel _{1,

2,

3,

4,

5}

Affiliation

Hybrid materials consisting of nanocrystalline metal oxide films coated with molecules have considerable implications for the development of optoelectronic devices. We report on a straightforward and versatile procedure to engineer stable layers made of molecules chemisorbed on the surface of mesoporous inorganic metal oxides. The procedure is based on a thermal copper-free Huisgen reaction, which is directly conducted on TiO₂ or NiO nanocrystalline films, between already bound diketopyrrolopyrrole sensitizers substituted by two azido groups and a crosslinking agent consisting of a tetrapropiolate ester. The procedure is mild and simple and does not require a catalyst, since quantitative conversion is obtained by a simple heating of the photoelectrode into a solution of the crosslinking agent. The photoelectrodes were characterized by ToF-SIMS, femtosecond transient absorption spectroscopy, electrochemistry and were finally used to fabricate dye-sensitized solar cells with iodide/triiodide and cobalt trisbipyridine complexes as redox mediators. Important increased stability of the crosslinked films was demonstrated by desorption and cyclic voltammetry experiments. Transient absorption spectroscopy and photovoltaic measurements showed that the dyes keep their initial photoelectrochemical properties upon crosslinking. This bottom-up approach is certainly broadly applicable and opens the possibility to make “chemistry on the electrode” to functionalize and crosslink dyes with any component.

中文翻译：

电极上的化学：无铜Huisgen环加成反应在中孔金属氧化物光电化学电池上固定染料的后功能化和稳定性增强

由涂有分子的纳米晶体金属氧化物膜组成的混合材料对光电器件的开发具有重要意义。我们报告了一种简单而通用的程序来设计由化学吸附在介孔无机金属氧化物表面上的分子制成的稳定层。该程序基于无热铜的惠斯根反应，该反应直接在TiO _2上进行在由两个叠氮基取代的已结合二酮吡咯并吡咯敏化剂与由四丙酸酯组成的交联剂之间形成一层或一层NiO纳米晶膜。该过程是温和且简单的，并且不需要催化剂，因为通过简单地将光电极加热到交联剂的溶液中即可实现定量转化。通过ToF-SIMS，飞秒瞬态吸收光谱，电化学对光电极进行了表征，最后将其用于制备染料敏化的太阳能电池，其中碘化物/三碘化物和钴三双吡啶复合物作为氧化还原介体。通过解吸和循环伏安法实验证明了交联膜的重要的增加的稳定性。瞬态吸收光谱法和光伏测量结果表明，染料在交联后仍保持其初始的光电化学性质。这种自下而上的方法无疑是广泛适用的，并开辟了使“电极上的化学物质”功能化并使染料与任何组分交联的可能性。

更新日期：2020-06-30

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