インターフェイス・プロトン・カップリング・電子移転のドナー依存運動
Megan N Jackson1, Yogesh Surendranath1
1Department of Chemistry, Massachusetts Institute of Technology , Cambridge, Massachusetts 02139, United States.
Journal of the American Chemical Society
|February 11, 2016
まとめ
陽子ドナー構造は,電解性水素の進化に大きく影響する. ステリカルに阻害されたドナーは,金面での協調型陽子電子伝送 (CPET) を遅らせ,エネルギー変換効率に影響を与える.
科学分野:
- 電気化学
- 表面科学
- カタリシス
背景:
- インターフェイス協調型陽子電子伝送 (CPET) は,電気触媒のエネルギー変換に不可欠です.
- CPETの運動に影響を与える要因を理解することは,効率的な触媒の設計に不可欠です.
研究 の 目的:
- インターフェイスのCPET運動に対する陽子ドナー構造の効果を調査する.
- ポリクリスタリンゴールドのCPET率の代理として水素進化反応 (HER) を使用する.
主な方法:
- ステリックプロファイルが異なるがpKaが同一のトライアルキラムニウムドナーを用いて水素進化率を研究した.
- アセトニトリルと水性電解質で運動研究を行った.
- 変換係数とH/Dの運動同位体効果を分析した.
主要な成果:
- トライエチルアモニウム (TEAH+) はアセトニトリル中のジソプロピレチルアモニウム (DIPEAH+) よりも20倍速いCPET運動を示した.
- ステリック効果は水性電解質では減少し,水の媒介的な役割を示している.
- TEAH+は,DIPEAH+ (β=0. 4) に比べて,より高い転移係数 (β=0. 7) と,潜在に依存する運動同位体効果を示した.
結論:
- 陽子ドナー構造は,固体表面でのCPETの自由エネルギー環境に大きな影響を及ぼします.
- 陽子ドナーは,電気触媒エネルギー変換の運動学において重要な役割を果たします.
- 溶媒の作用,特に水は,インターフェイスCPETにおけるステリック制約を軽減することができます.
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