Precursor Disorder-Mediated Crystallinity Regulation of Cu₂P₂O₇ for Optimized Cu⁺/Cu⁰ Interfaces toward Highly...

Electrochemical CO₂ reduction reaction (CO₂RR) to high-value C₂₊ products is pivotal for carbon neutrality, yet the rational design of Cu-based electrocatalysts with efficient C-C coupling and optimized Cu⁺/Cu⁰ active interfaces remains a formidable challenge. Herein, we propose a structural disorder engineering strategy to fabricate phosphorus-modified Cu-BTC-derived electrocatalysts with tailorable phase and crystallinity. By precisely regulating 2-hydroxyphosphonoacetic acid loading, disorder of precursors is tuned, inducing the evolution of calcined catalysts from CuO/amorphous species to monoclinic Cu₂P₂O₇ with gradient crystallinity. O-CuBTC-HPAA-3, featuring the lowest Cu₂P₂O₇ crystallinity, delivers superior CO₂RR performance, with a peak C₂₊ Faradaic efficiency of 79.2% at high current density, as well as good electrolysis stability. Comprehensive characterizations, in situ spectroscopy, and density functional theory (DFT) calculations confirm that the catalytic superiority of O-CuBTC-HPAA-3 is depending on dynamic reconstruction into an optimal Cu⁺/Cu⁰ ratio with abundant interfacial boundaries under CO₂RR conditions. Such structure accelerates the rate-determining *CO protonation to *CHO, stabilizes the key *COCHO intermediate, and enables low-energy-barrier asymmetric C-C coupling. DFT calculation further verifies that the 4Cu⁺/Cu⁰ model features an upshifted Cu d-band center, lowering the C₂₊ formation energy barrier and enhancing metal-intermediate interactions. This work establishes a new paradigm for advanced CO₂RR catalyst design via precursor engineering, reinforcing the fundamental understanding of structure-function relationships governing C₂₊ selectivity in CO₂RR.