Efficient Acidic CO2 Electrolysis with Suppressed Crossover in a Separator-Based Membrane Electrode Assembly

Research output: Contribution to journalResearch articleContributedpeer-review

Contributors

  • Min Liu - , University of Toronto (Author)
  • Yuke Li - , University of Toronto (Author)
  • Jianan Erick Huang - , University of Toronto (Author)
  • Xingyuan Chu - , Center for Advancing Electronics Dresden (cfaed), Chair of Molecular Functional Materials (gB MPI-MSP) (Author)
  • Qian Sun - , University of Toronto (Author)
  • Feng Li - , University of Toronto (Author)
  • Yurou Celine Xiao - , University of Toronto (Author)
  • Mengyang Fan - , University of Toronto (Author)
  • Chengqian Wu - , University of Toronto (Author)
  • Zhizheng Wu - , University of Toronto (Author)
  • Qiyou Wang - , University of Toronto (Author)
  • Jiexin Zhu - , University of Toronto (Author)
  • Zunmin Guo - , University of Toronto (Author)
  • Xiaodong Li - , University of Toronto (Author)
  • Sekar Wibawa - , University of Toronto (Author)
  • Panagiotis Papangelakis - , University of Toronto (Author)
  • Loann Bonnenfant - , University of Toronto (Author)
  • Hyun Sik Moon - , University of Toronto (Author)
  • Cao Thang Dinh - , Queen's University Kingston (Author)
  • Rui Kai Miao - , University of Toronto (Author)
  • Edward H. Sargent - , University of Toronto, Northwestern University (Author)
  • David Sinton - , University of Toronto (Author)

Abstract

Performing acidic electrochemical CO2 reduction (CO2R) in flow cells suppresses CO2 crossover but requires thick catholyte layers that impose large ohmic losses. Removing the catholyte, however, shifts selectivity toward H2 due to excessive proton (H+) transport through cation exchange membranes (CEM). Here, we present a zero-gap membrane electrode assembly (MEA) incorporating an ∼100 μm electrolyte-filled hydrophilic porous separator. The separator uniquely enables zero-gap operation by regulating coupled H+ and K+ transport; however, at high potassium ion (K+) concentrations, stronger ion pairing between K+ and (bi)carbonates suppresses their protonation at the cathode, thereby increasing CO2 crossover. In contrast, a higher H+ to K+ ratio (2.4 M/0.2 M) establishes an H+-enriched yet K+-stabilized interface that promotes C2+ production while suppressing crossover. Controlling electrolyte permeance (∼1.5–3 mL h–1 cm–2) further limits (bi)carbonate electromigration. Using this approach, we reduce CO2 crossover to 0.19 sccm A–1 (∼5% of the CO2 converted to products), while achieving 75% multicarbon (C2+) Faradaic efficiency and 24% energy efficiency at 3.5 V (300 mA cm–2) using a 7,7,8,8-tetracyanoquinodimethane-modified copper oxide catalyst. This work demonstrates efficient acidic CO2 electrolysis with suppressed crossover using a separator-based MEA with copper catalysts.

Details

Original languageEnglish
Pages (from-to)15930-15938
Number of pages9
JournalJournal of the American Chemical Society
Volume148
Issue number15
Publication statusPublished - 22 Apr 2026
Peer-reviewedYes

External IDs

PubMed 41946582