An Integrated Design with new Metal‐Functionalized Covalent Organic Frameworks for the Effective Electroreduction of CO₂

Abstract

One of the long-standing issues that prohibits large-scale CO reutilization is the low aqueous solubility of CO and the incurring inefficient mass transport of CO . Herein, we suggest a feasible way to promote the CO reutilization by integrating the storage and reduction, with a new covalent organic framework (COF) series constituted by cobalt-phthalocyanine and boronic acid linkers. We find that the porous structure of the cobalt COF is competitive in the CO storage and can sustain a high CO concentration around the reduction center, whereas the mass transport of CO as well as the efficiency of the CO reduction is significantly improved. The predicted cobalt COF exhibits an overpotential of 0.27 V and a CO production rate, which is 97.7 times higher than in aqueous solution, for the CO reduction. Our work provides a promising candidate for the CO reutilization, with valuable insights and an important prototype for future practical design.

Covalent Organic Frameworks for the Capture, Fixation, or Reduction of CO2

“…The advent of reticular chemistry has inspired computational chemists to simulate COFs for the hope of better optimizing CO 2 capture (Zeng et al, 2016). Chemists have been able to incorporate a litany of catalytic centers within COF materials that enable the conversion of CO 2 to cyclic carbonates (Roeser et al, 2012;Saptal et al, 2016;Xu et al, 2017;Yu et al, 2018;Zhi et al, 2018) and CO (Lin et al, 2015;Diercks et al, 2018a;Lin and Chen, 2018;Liu et al, 2018; Yang et al, 2018;Yao et al, 2018). Some of the most recently developed and advanced COFs for CO 2 adsorption are listed in Table 1.…”

“…More recent work on cobalt containg COFs for the production of CO consists of three new COFs, Co-Pc-PBBA, Co-PcbPBBA, and Co-Pc-tPBBA; analyzed by Yao et al (2018). In this computational work the cobalt atoms were held in the center of phthalocyanine linkers.…”

“…This computational observation dictates that the large-pored COFs would be more efficient at higher pressures. Yao et al (2018) selected Co-Pc-bPBBA for their computational study. The reduction pathway from CO 2 to CO and various other hydrocarbons as elucidated by Yao et al is depicted in Figure 18 with free energies of the reaction pathways are shown below in Table 2.…”

“…CO 2 adsorption into Co-Pc-bPBBA as modeled byYao et al (2018). Reprinted with permission copyright 2018 Wiley VCH.…”

“…The G of CO 2 to CO, methane and methanol at U = 0 V vs. the reversible hydrogen electrode (RHE) as determined byYao et al (2018).…”