Spin Manipulation in a Metal-Organic Layer through Mechanical Exfoliation for Highly Selective CO2 Photoreduction
Spin Manipulation in a Metal-Organic Layer through Mechanical Exfoliation for Highly Selective CO2 Photoreduction
复制标题
通过机械剥离在金属有机层中进行自旋操作以实现高选择性二氧化碳光还原
DOI：
10.1002/anie.202301925
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发表时间：
2023
期刊：
影响因子：
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通讯作者：
Zhang Zhi‐Ming
中科院分区：
文献类型：
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作者：
Wu Dayu;Yin Hua‐Qing;Wang Zeshi;Zhou Mingren;Yu Chengfeng;Wu Jing;Miao Huixian;Yamamoto Takashi;Zhaxi Wenjiang;Huang Zetao;Liu Luying;Huang Wei;Zhong Wenhui;Einaga Yasuaki;Jiang Jun;Zhang Zhi‐Ming
自旋操纵过渡金属催化剂在模拟酶的电子结构以提高活性和/或选择性方面具有很大的潜力。然而，如何控制催化中心的室温自旋状态仍然是一个巨大的挑战。在此，我们报告了一种机械剥离策略，以原位诱导铁中心从高自旋（s=5/2）到低自旋（s=1/2）的部分自旋交叉。由于催化中心的自旋转变，混合自旋催化剂的CO产率高达19.7 mmol g−1，选择性为91.6%，远优于高自旋体催化剂（选择性为50%）。密度泛函理论计算表明，低自旋3d轨道电子构型在促进co2吸附和降低激活势垒方面起着关键作用。因此，自旋操纵为优化自旋态设计高效仿生催化剂提供了新的思路。
Spin manipulation of transition‐metal catalysts has great potential in mimicking enzyme electronic structures to improve activity and/or selectivity. However, it remains a great challenge to manipulate room‐temperature spin state of catalytic centers. Herein, we report a mechanical exfoliation strategy to in situ induce partial spin crossover from high‐spin (s=5/2) to low‐spin (s=1/2) of the ferric center. Due to spin transition of catalytic center, mixed‐spin catalyst exhibits a high CO yield of 19.7 mmol g−1with selectivity of 91.6 %, much superior to that of high‐spin bulk counterpart (50 % selectivity). Density functional theory calculations reveal that low‐spin 3d‐orbital electronic configuration performs a key function in promoting CO2adsorption and reducing activation barrier. Hence, the spin manipulation highlights a new insight into designing highly efficient biomimetic catalysts via optimizing spin state.