Photochemical Energy Storage and Electrochemically Triggered Energy Release in the Norbornadiene-Quadricyclane System: UV Photochemistry and IR Spectroelectrochemistry in a Combined Experiment

被引：66

作者：

Brummel, Olaf ^{[1
]}

Waidhas, Fabian ^{[1
]}

Bauer, Udo ^{[1
]}

Wu, Yanlin ^{[2
]}

Bochmann, Sebastian ^{[2
]}

Steinrueck, Hans-Peter ^{[1
]}

Papp, Christian ^{[1
]}

Bachmann, Julien ^{[2
]}

Libuda, Joerg ^{[1
]}

机构：

[1] Friedrich Alexander Univ Erlangen Nurnberg, Lehrstuhl Phys Chem 2, Egerlandstr 3, D-91058 Erlangen, Germany

[2] Friedrich Alexander Univ Erlangen Nurnberg, Lehrstuhl Anorgan & Allgemeine Chem, Egerlandstr 1, D-91058 Erlangen, Germany

来源：

JOURNAL OF PHYSICAL CHEMISTRY LETTERS | 2017年 / 8卷 / 13期

关键词：

PHOTOASSISTED VALENCE ISOMERIZATION; ELECTRODE-ELECTROLYTE INTERPHASE; STRAINED ORGANIC-MOLECULES; SOLAR THERMAL STORAGE; INFRARED-SPECTROSCOPY; METHANOL OXIDATION; PHOTOISOMERIZATION; CATALYSTS; PT(111); ELECTROCATALYSTS;

D O I：

10.1021/acs.jpclett.7b00995

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The two valence isomers norbornadiene (NBD) and quadricyclane (QC) enable solar energy storage in a single molecule system. We present a new photoelectrochemical infrared reflection absorption spectroscopy (PEC-IRRAS) experiment, which allows monitoring of the complete energy storage and release cycle by in situ vibrational spectroscopy. Both processes were investigated, the photochemical conversion from NBD to QC using the photosensitizer 4,4'-bis(dimethylamino)benzophenone (Michler's ketone, MK) and the electrochemically triggered cycloreversion from QC to NBD. Photochemical conversion was obtained with characteristic conversion times on the order of 500 ms. All experiments were performed under full potential control in a thin layer configuration with a Pt(111) working electrode. The vibrational spectra of NBD, QC, and MK were analyzed in the fingerprint region, permitting quantitative analysis of the spectroscopic data. We determined selectivities for both the photochemical conversion and the electrochemical cycloreversion and identified the critical steps that limit the reversibility of the storage cycle.

引用

页码：2819 / 2825

页数：7

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[1] Catalytically Triggered Energy Release from Strained Organic Molecules: The Surface Chemistry of Quadricyclane and Norbornadiene on Pt(111) [J].