先进能源材料化学教育部重点实验室（南开大学） Key Laboratory of Advanced Energy Materials Chemistry, Ministry of Education (Nankai University)

单晶、一维(1D)聚合物的合成非常重要，但也是一个巨大的挑战。在此，作者报道了通过动态共价化学在溶液中合成单晶1D梯形聚合物。三维电子衍射技术用于严格解析结晶聚合物的结构，揭示了每个聚合物链通过双共价桥连接，并且所有聚合物链通过π-π堆积和氢键相互作用以交错和交织的方式堆积，使得结晶聚合物在热和化学稳定性方面高度稳定。通过动态穿透实验验证，合成的单晶聚合物具有永久性微孔，能够有效去除C₂H₂/CO₂混合物中的CO₂，获得高纯度的C₂H₂。这项工作证明了在溶液中构建具有双共价桥的单晶1D多孔梯形聚合物用于有效分离C₂H₂/CO₂的第一个例子。

Scheme 1. Reported Examples of Synthesizing Single-Crystal 1D Covalent Polymers and Our Work

Scheme 2. (a) Synthetic Route of M-CHO and (b) Its Single-Crystal Structure: (I) Pd(PPh₃)₂Cl₂, CuI, Et₃N, THF, r.t., 24 h; (II) Pd(PPh₃)₄, K₂CO₃, THF, H₂O, 85 °C, 12 h; (III) Co₂ (CO)₈, 1,4-Dioxane, 115 °C, 24 h

Figure 1. Synthetic route of CLCP-1 and -2 and their structure diagram.

Figure 2. Characterization. (a) FT-IR spectra of CLCP-1. (b) 13C CP-MAS NMR spectra of CLCP-1. (c) PXRD patterns of CLCP-1. (d) SEM image of CLCP-1. (e) HR-TEM image of CLCP-1. (f) Partial enlarged view of (e).

Figure 3. (a) 2D projections of the reconstructed reciprocal lattice of CLCP-1 from 3D ED data. (b) Single chain of CLCP-1. (c) Adjacent chains of CLCP-1 on the ac plane. (d) Chain stacking of CLCP-1 on the ac plane and the interaction between chains. (e) Adjacent chains of CLCP-1 along the b axis and the interaction between chains.

Figure 4. (a) N2 adsorption (solid symbols) and desorption (open symbols) isotherms at 77 K of CLCP-1 and -2. (b) PXRD patterns of CLCP-1 after treatment under various harsh conditions.

Figure 5. (a) Single-component adsorption isotherms of C₂H₂ and CO₂ for CLCP-1 at 298 K. (b) Qst curves of C₂H₂ and CO₂ for CLCP-1 at 298 K. (c) Experimental breakthrough curves of C₂H₂/CO₂ mixtures (1/1, v/v) for CLCP-1 with a total inlet flow rate of 2.0 mL/min at 298 K. (d) Cyclic breakthrough curves of C₂H₂/CO₂ mixtures (1/1, v/v) for CLCP-1 at 298 K under 1 bar.

https://pubs.acs.org/doi/10.1021/jacs.3c10812#

来源：COF催化在线