近日，暨南大学范晓芸团队实现了压电增强载流子转移在高共轭镍(II)-乙酰基醚框架光催化CO₂还原。该项研究成果发表在2025年7月30日出版的《美国化学会志》上。

二维（2D）压电光催化剂中的压电场为提高载流子动力学将二氧化碳转化为有价值的化学物质提供了一种有前途的策略。然而，可用的二维压电光催化剂的多样性仍然有限。

研究组提出了一个高度共轭的NiII-乙酰基框架（HETP-Ni-GY），其特征是三角形的原子孔以六边形对称排列，通过NiII-二（乙酰基）键将NiII-配合物结合到石墨炔（GDY）框架中（- C≡C - Ni(PEt₃) ₂-C≡C -）。三角形的拓扑结构形成了密集而有序的π结构，有利于电子的高效转移。在HETP-Ni-GY/三乙乙醇胺（TEOA）催化体系中，光场和压电场的协同作用使得CO （129.80 μmol g^-1 h^-1）和CH₄（10.08 μmol g^-1 h^-1）的合成效率达到了78.44%。

实验和理论研究表明，由于结构畸变和非中心对称性增加，框架内的NiII-(PEt₃)₂单元显著增强了压电极化（e₁₁ = 2.46 × 10^-10 C m^-2, d₃₃ = 4.91 pm V^-1），促进了CO₂的转化。三苯基π-柱作为电子储层，而NiII-bis（乙酰基）嵌段通过π-d-π相互作用作为CO₂捕获和活化中心。这项研究为低成本金属-乙酰基醚框架的功能提供了基本的见解，并为高效的二维压电催化剂的合理设计提供了指导。

附：英文原文

Title: Piezoelectrically Enhanced Charge Carriers Transfer in a Highly Conjugated Nickel(II)-Acetylide Framework for Photocatalytic CO2 Reduction

Author: Mude Zhu, Hua Su, Fangzhou Yang, Yingying Qin, Fuku Chung-Hei Hui, Runzhe Zhang, Jianxin Geng, Kai Wang, Xiaoyun Fan, Wai-Yeung Wong, Linli Xu

Issue&Volume: July 30, 2025

Abstract: The piezoelectric field within two-dimensional (2D) piezo-photocatalysts offers a promising strategy for enhancing charge carrier kinetics to convert CO2 into valuable chemicals. However, the diversity of available 2D piezo-photocatalysts remains limited. Here, we present a highly conjugated NiII-acetylide framework (HETP-Ni-GY) featuring triangular atomic pores arranged in a hexagonal symmetry, constructed by incorporating NiII-complex into the graphdiyne (GDY) framework via NiII-bis(acetylide) linkages (–C≡C–Ni(PEt3)2–C≡C–). The triangular topology induces a densely packed yet ordered π-structure that facilitates efficient electron transfer. The synergistic interplay of light and piezoelectric field in the HETP-Ni-GY/triethanolamine (TEOA) catalytic system enables the efficient production of CO (129.80 μmol g–1 h–1) and CH4 (10.08 μmol g–1 h–1), with a total selectivity of 78.44%. Experimental and theoretical studies reveal that the NiII-(PEt3)2 units within the framework significantly enhance piezoelectric polarization (e11 = 2.46 × 10–10 C m–2, d33 = 4.91 pm V–1) due to increased structural distortion and noncentrosymmetry, facilitating the conversion of CO2. The triphenylene π-columns function as electron reservoirs, while NiII-bis(acetylide) blocks serve as CO2 capture and activation centers through π-d-π interactions. This study provides fundamental insights into the functionality of low-cost metal-acetylide frameworks and offers guidance for the rational design of efficient 2D piezocatalysts.

DOI: 10.1021/jacs.5c08037

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.5c08037