摘要：电催化乙炔还原(EAR)为实现乙炔(C2H2)半加氢生产乙烯(C2H4)提供了一条有前途的途径。然而，使电催化剂同时满足包括C2H2富集、活化、电子转移和活性位点在内的关键因素对于有效的EAR仍然是一个巨大的挑战。共价有机框架(COFs)由于具有引入功能基团和
本文要点：
电催化乙炔还原(EAR)为实现乙炔(C2H2)半加氢生产乙烯(C2H4)提供了一条有前途的途径。然而，使电催化剂同时满足包括C2H2富集、活化、电子转移和活性位点在内的关键因素对于有效的EAR仍然是一个巨大的挑战。共价有机框架(COFs)由于具有引入功能基团和通过共价键有效转移电子的优点而备受关注，是一种很有前途的电催化剂，但目前还没有利用COFs实现电致发光的研究。在本工作中，作者合理设计了一系列包含上述功能的多功能COF电催化剂，并通过调节活性中心的类型实现了高效电化学反应。其中，EA-16FCuPc COF在纯C2H2流中表现出C2H2到C2H4的100%法拉第效率。重要的是，对于含有1×104 ppm C2H2的工业粗C2H4流，EA-16FCuPc COF可以产生仅含有2.1 ppm C2H2杂质的聚合物级C2H4，并在大空速下连续产生纯C2H4流(C2H2 这项工作探索了COFs的设计，以将多种功能集成到一个催化剂上并实现高效的电化学反应，展示了多功能COFs在电催化领域的巨大潜力。Scheme 1. Background and Proposal
Figure 1. Schematic representation of metal phthalocyanine COFs by dioxin-linked linkage. (a) Schematic of the synthesis and structure of EA-16FMPc COF through the condensation of 16FMPc and EA. (b) Top view and side view for EA-16FMPc COF crystal structure. (c–e) Experimental and simulated PXRD patterns of EA-16FCuPc COF, EA-16FCoPc COF, and EA-16FNiPc COF.
Figure 2. Characterization and morphology of the EA-16FMPc COF. (a) FT-IR of EA-16FMPc COF. (b) C2H2 adsorption isotherms on EA-16FCuPc COF and 16FCuPc at 298 K. (c) TEM image of the EA-16FCuPc COF. (d) Mapping of EA-16FCuPc COF.
Figure 3. EAR performance of COFs in the pure C2H2 stream conditions. (a) LSV curves for the EA-16FMPc COF and carbon paper. (b) C2H4 Faraday efficiency of the potential range from −0.3 to −1.0 V. (c) Tafel plots. (d) Partial C2H4 current density of the EA-16FMPc COF and the TOF (h–1) of the EA-16FCuPc COF. (e) Stability of EA-16FCuPc COF at −0.8 V.
Figure 4. EAR performance of EA-16FCuPc COF in the crude C2H4 stream with a low concentration of C2H2. (a) Concentration of residual C2H2 at different voltages at a flow rate of 5 sccm for EA-16FCuPc COF. (b) Concentration of residual C2H2 under different flow rates of crude C2H4 at −0.8 V for EA-16FCuPc COF. (c) Long-term operation of EA-16FCuPc COF for crude C2H4 purification at −0.8 V.
Figure 5. Mechanism of the EAR. (a) Free energy diagram of C2H2 hydrogenation on the EA 16FMPc COF. (b) Free energy diagram of the hydrogenolysis reaction on EA-16FMPc COF. (c) Largest Gibbs energy difference of C2H2 hydrogenation and the adsorption energy of H.
来源：华算科技
