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

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.