Enhancement of electrocatalytic oxygen evolution by chiral molecular functionalization of hybrid 2D electrodes.
Enhancement of electrocatalytic oxygen evolution by chiral molecular functionalization of hybrid 2D electrodes.
复制标题
DOI：
10.1038/s41467-022-31096-8
复制
发表时间：
2022-06-10
影响因子：
16.6
通讯作者：
中科院分区：
文献类型：
--
作者：
可持续的未来需要高效的能量转换和储存过程，其中电催化起着至关重要的作用。电催化剂的活性由反应中间体的结合能决定，而标度关系阻止催化体系超过其火山图极限的改进。为了克服这些限制，不完全由表面结合能决定的非常规方法可能是有帮助的。在这里，我们使用有机手性分子，即，杂螺烯，如噻二唑-[7]螺烯和双（噻二唑）-[8]螺烯，以促进析氧反应（OER）高达约。130%（在相对于RHE的1.65 V的电势下），在最先进的2D Ni基和NiFe基催化剂下，通过自旋极化机制。我们的研究结果表明，手性分子功能化能够提高催化剂的OER活性超过火山极限。通过手性分子功能化的混合2D电极的催化活性的优化的指导方针。虽然太阳能燃料催化需要仔细转移电子，但理解电子自旋如何促进反应性仍然存在挑战。在这里，作者采用手性稠合噻二唑-螺烯来控制析氧电催化剂中的自旋极化。
A sustainable future requires highly efficient energy conversion and storage processes, where electrocatalysis plays a crucial role. The activity of an electrocatalyst is governed by the binding energy towards the reaction intermediates, while the scaling relationships prevent the improvement of a catalytic system over its volcano-plot limits. To overcome these limitations, unconventional methods that are not fully determined by the surface binding energy can be helpful. Here, we use organic chiral molecules, i.e., hetero-helicenes such as thiadiazole-[7]helicene and bis(thiadiazole)-[8]helicene, to boost the oxygen evolution reaction (OER) by up to ca. 130 % (at the potential of 1.65 V vs. RHE) at state-of-the-art 2D Ni- and NiFe-based catalysts via a spin-polarization mechanism. Our results show that chiral molecule-functionalization is able to increase the OER activity of catalysts beyond the volcano limits. A guideline for optimizing the catalytic activity via chiral molecular functionalization of hybrid 2D electrodes is given. While solar-to-fuel catalysis requires the careful transfer of electrons, there are still challenges understanding how electron spin contributes to reactivity. Here, authors employ chiral fused thiadiazole-helicenes to control spin polarization in oxygen evolution electrocatalysts.
登录
查看更多内容
DOI：
10.1073/pnas.1821674116
发表时间：
2020-06-09
影响因子：
11.1
作者：
Eisenberg, Richard;Gray, Harry B.;Crabtree, George W.
通讯作者：
Crabtree, George W.
影响因子：
29.4
作者：
Chen, Riccardo Ruixi;Sun, Yuanmiao;Xu, Zhichuan J.
通讯作者：
Xu, Zhichuan J.
影响因子：
4.9
作者：
Fuhr, Javier D.;van der Meijden, Maarten W.;Lingenfelder, Magali
通讯作者：
Lingenfelder, Magali
影响因子：
5.7
作者：
Ghosh, Supriya;Mishra, Suryakant;Waldeck, David H.
通讯作者：
Waldeck, David H.
影响因子：
9.5
作者：
Dette, Christian;Hurst, Michael R.;Boettcher, Shannon W.
通讯作者：
Boettcher, Shannon W.