设计 3d–2p–4f 梯度轨道耦合以增强电催化氧还原,Advanced Materials

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设计 3d–2p–4f 梯度轨道耦合以增强电催化氧还原
Advanced Materials ( IF 27.4 ) Pub Date : 2022-09-09 , DOI: 10.1002/adma.202206540
Xuan Wang ₁ , Jingwen Wang ₁ , Pu Wang ₁ , Liangcheng Li ₁ , Xinyue Zhang ₁ , Dongmei Sun ₁ , Yafei Li ₁ , Yawen Tang ₁ , Yu Wang ₁ , Gengtao Fu ₁

Affiliation

开发用于氧还原反应（ORR）的高效经济材料在实际的能量转换技术中起着关键作用。然而，内在的比例关系对实现高活性 ORR 电催化剂具有热力学抑制作用。_{在此，提出了一种新颖可行的梯度轨道耦合策略，通过在 Eu 2} O ₃ -Co 模型上构建 Co 3d-O 2p-Eu 4f 单元位点来调整 ORR 性能。通过梯度轨道耦合，Eu 和 O 原子之间的原始离子特性被赋予增加的共价性，从而优化了 e _g占据 Co 位点，并削弱 OO 键，从而最终打破 Co-O-Eu 单元位点 *OOH 和 *OH 之间的比例关系。与可逆氢电极相比，优化后的模型催化剂的起始电位和半波电位分别为 1.007 和 0.887 V，高于商业 Pt/C 和大多数 Co 基催化剂的值。此外，发现该催化剂具有优异的选择性和耐久性。在高功率/能量密度和长循环寿命方面，它还显示出比锌空气电池中的商用贵金属催化剂更好的电池性能。本研究通过构建梯度 3d-2p-4f 轨道耦合为电子调制策略提供了新的视角。

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Engineering 3d–2p–4f Gradient Orbital Coupling to Enhance Electrocatalytic Oxygen Reduction

The development of highly efficient and economical materials for the oxygen reduction reaction (ORR) plays a key role in practical energy conversion technologies. However, the intrinsic scaling relations exert thermodynamic inhibition on realizing highly active ORR electrocatalysts. Herein, a novel and feasible gradient orbital coupling strategy for tuning the ORR performance through the construction of Co 3d-O 2p-Eu 4f unit sites on the Eu₂O₃–Co model is proposed. Through the gradient orbital coupling, the pristine ionic property between Eu and O atoms is assigned with increased covalency, which optimizes the e_g occupancy of Co sites, and weakens the OO bond, thus ultimately breaking the scaling relation between *OOH and *OH at Co–O–Eu unit sites. The optimized model catalyst displays onset and half-wave potential of 1.007 and 0.887 V versus reversible hydrogen electrode, respectively, which are higher than those of commercial Pt/C and most Co-based catalysts ever reported. In addition, the catalyst is found to possess superior selectivity and durability. It also reveals better cell performance than commercial noble-metal catalysts in Zn–air batteries in terms of high power/energy densities and long cycle life. This study provides a new perspective for electronic modulation strategy by the construction of gradient 3d–2p–4f orbital coupling.

更新日期：2022-09-09

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