【摘要】 采用不同芳香环数目的有机炔单体苯乙炔,2-乙炔基萘,9-乙炔基菲与铜试剂进行配位,制备了苯乙炔铜（PACU）2-乙炔基萘铜（NACU）和9-乙炔基菲铜（FACU）3种铜炔基光催化剂。对其结构、组成和性能进行了表征,并系统研究了其在光催化CO₂还原反应中的性能与机制。结果表明,随着单体共轭尺寸增大,Cu⁺价态与Cu—C≡配位结构保持不变,但空间位阻效应显著增强,导致分子堆积有序性和结晶性下降。光电性能测试显示,共轭扩展有利于促进电荷分离并降低激子结合能,从而提升光催化活性。其中,基于2-乙炔基萘的NACU催化剂表现出最优的CO₂还原性能,CO生成量达到35.27μmol/g,是同条件下PACU产率的2倍。研究说明在保持配位结构稳定的前提下,需合理调控共轭尺寸以平衡空间位阻与电荷传输性能,为理性设计高效炔铜光催化剂提供了重要依据。更多还原

【Abstract】 In this study,we synthesized three copper-alkynyl photocatalysts,phenylacetylene copper（PACU）,2-ethynylnaphthalene copper（NACU） and 9-ethynylphenanthrene copper（FACU）-by coordinating organic alkyne monomers with varying aromatic ring numbers,phenylacetylene,2-ethynylnaphthalene and 9-ethynylphenanthrene.The structures,compositions,and properties of these catalysts were thoroughly characterized,and their performance and mechanisms in photocatalytic CO₂ reduction reactions were systematically investigated.The results show that as the conjugation length of the monomer increases,the Cu valence state and the Cu—C≡ coordination structure remain unchanged.However,the steric hindrance effect is significantly enhanced,leading to a decrease in molecular packing order and crystallinity.Photoelectrochemical tests indicate that the extended conjugation improves charge separation and reduces exciton binding energy,thereby enhancing photocatalytic activity.Among the three catalysts,NACU,based on 2-ethynylnaphthalene,exhibited the best CO₂ reduction performance,with a CO generation rate of 35.27 μmol/g,which is twice that of PACU under identical conditions.This study demonstrates that,while maintaining a stable coordination structure,it is crucial to optimize the conjugation size to balance steric hindrance and charge transport,offering valuable insights for the rational design of efficient copper-alkynyl photocatalysts.更多还原