雑誌会((190904)の回答

Abstract

It is highly desirable to discover molecular catalysts with controlled selectivity for visible-light-driven CO2  reduction to fuels. In the design of catalysts employing earth-abundant metals, progress has been made for CO production, but formate generation has been observed more rarely. Here, we report a binuclear Co complex bearing a bi-quaterpyridine ligand that can selectively reduce CO2  to HCOO −  or CO under visible light irradiation. Selective formate production (maximum of 97%) was obtained with  a turnover number of up to 821 in basic acetonitrile solution. Conversely, in the presence of a weak acid, CO2  reduction affords CO with high selectivity (maximum of 99%) and a maximum turnover number of 829. The catalytic process is controlled by the two Co atoms acting synergistically, and the selectivity can be steered towards the desired product by simply changing the acid co-substrate.


質問１
yield求め方

yieldは珍しいのですがµmolでかかれていました。
錯体の濃度はentry1,2,3,6で50 µM、entry4が20 µM、entry5,7では20 µMとなっています。溶液は全部で2 mLなので、例えばentry1では錯体が0.1 µmol含まれていることになり、HCOO-が11 µmol生成しているのでTONは110となります。


質問2
電気化学的分光法のやり方・装置

今回用いられた上の測定はSpectro-electrochemistry  (SEC)と呼ばれる手法で、このケースは赤外領域に関して測定しています。ここで使用されている装置は
 The infrared SEC experiments were performed with a home-made cell (thickness of 0.3 mm), equipped with two KBr windows. The working electrode was a platinum grid, placed on the infrared beam. A Ag wire was used as pseudo-reference and a Pt grid as counterelectrode. Two spectra (one spectrum every 1 min, four scans) were registered at each potential step.
と書いてあったので筆者らのオリジナルのようです。
このような装置は難しいかもしれませんがUV-visの範囲であれば市販の電気化学セルを使えばできる気もします。
UV,IRの範囲で安定でない化合物の情報を得たい場合は電気化学的に酸化還元ができるこのような手法も検討してみると良いかもしれないです。