The electrochemical CO2 reduction reaction (CO2RR) can convert CO2 into value-added chemicals, but its efficiency and selectivity are limited by the thermodynamic stability of CO2 and competing hydrogen evolution reaction (HER). hydrogen bonding offers a design strategy beyond direct metal-site modification by stabilizing CO2-derived intermediates and mediating proton transfer. In homogeneous catalysts, hydrogen bonding units in the molecular outer sphere stabilize metal-bound intermediates and guide protonation pathways. In heterogeneous systems, analogous functions are implemented at solid–liquid interfaces, where catalyst-surface modification alters the stability of surface-bound intermediates and regulates proton transport pathways. This review highlights hydrogen bonding as a shared design element that bridges molecular precision and interfacial regulation in CO2RR catalysis, identifying common design requirements for balancing intermediate stabilization, proton delivery, and HER suppression.

We proposed a self−redox strategy to synthesize highly dispersed Cu2O/CeO2 interfacial catalysts, for constructing non−covalent interactions between *CO and H2O. The resulted reaction microregion innovatively promoted the *CO attack on the α carbon of *C2 intermediates by participating the crucial protonation pathway, thereby overcoming the selectivity plateau in n-propanol electrosynthesis at high current densities. ABSTRACT Selective electroreduction of CO2 (CO2RR) to n-propanol represents a promising route for low-carbon chemical synthesis. However, achieving high selectivity at industrially relevant current densities remains challenging due to inefficient *CO utilization and strong competition from C2 products. Herein, we demonstrate that a Cu2O/CeO2 interfacial catalyst overcomes these limitations by constructing a *CO─H2O reaction microregion that facilitates selective C1─C2 coupling. Isotope-competitive in situ differential electrochemical mass spectrometry (DEMS) reveals that the CeO2-induced interfacial structure shifts protonation pathway of activated CO2 from adsorbed hydrogen to solvent hydrogen, thereby generating high local *CO flux. Under CO2RR conditions, the *CO─H2O reaction microregion arises from non−covalent interaction between high-density *CO and loosely H-bonded water molecules. Time-resolved pulsed spectroscopy and theoretical calculations confirmed that this microregion dynamically confines *CO and reduces their molecular orbital degeneracy, enhancing *CO availability for C─C coupling reaction. Site-specific kinetics isotope effect experiments further indicate the reaction microenvironment promotes *CO attack on the α carbon of *C2 intermediates, effectively steering reaction pathway toward n-propanol. As a result, the catalyst achieves n-propanol Faradaic efficiency (FE) of 26.1%. These findings underscore the significance of non-covalent interactions between intermediates and electrolyte in controlling proton-related surface reaction, offering opportunities for steering electrocatalytic pathways toward valuable products.

Electrochemical CO2 reduction reaction (CO2RR) offers a highly sustainable pathway for converting carbon emissions into valuable chemicals; however, d…

Source: https://doi.org/10.1021/jacs.6c13568 At a glance During electrochemical CO₂ reduction on TM–N₄ single-atom catalysts, CO yield often rises, reaches a plateau and then declines as the applie...

PBFA-QA, a poly(bisfluorene)-based anion exchange membrane containing alkyl chains, enables excellent performance and durability in zero-gap CO2RR cells. It achieves a CO partial current density of 331.7 mA cm−2, which is substantially higher than those of commercial PiperION and X37-50 RT anion exchange membranes. At 200 mA cm−2, a PBFA-QA-based cell operates stably for 200 h while maintaining an FECO above 92.3%, without cathode flooding or salt precipitation.

Chalcogenide-based thin-film solar cell optimized for rear illumination and used for CO2 reduction is presented. Central to this innovation is a thinner, Cu(In,Ga)S2 chalcopyrite absorber coated with...

Carbonate formation constitutes a major obstacle in the electrochemical CO2 reduction reaction (CO2RR), restricting the industrial implementation of this reaction. Even when adopting mild acidic elect...

Nano-ZnO is a potential catalyst material for carbon dioxide electrocatalytic reduction (CO2RR), but its effective Faraday efficiency (FE) is still below 90% and the current density is less than 300 m...

(Bi)carbonate salt formation has been widely recognized as a primary factor in poor operational stability of the electrochemical carbon dioxide reduction reaction (CO2RR). We demonstrate that flowing ...

(Bi)carbonate salt formation has been widely recognized as a primary factor in poor operational stability of the electrochemical carbon dioxide reduction reaction (CO2RR). We demonstrate that flowing ...

Understanding the transient physicochemical properties at the cathode/catholyte interface is a prerequisite to shedding light on the complex electrochemical CO2 reduction reaction (CO2RR) mechanism as...

Bismuth-based electrocatalysts are widely recognized for their high formate selectivity in the CO2 reduction reaction (CO2RR), primarily attributed to the exposure of the Bi (012) facet. We demonstrate that anisotropic alloying with yttrium stabilizes metallic Bi and shifts the active facets to Bi (00z). Bi90.4Y9.6 nanoparticles (NPs) with anisotropic lattice strain exhibit a Faradaic efficiency (FEformate) greater than 90% between −1.1 and −1.4 V vs reversible hydrogen electrode (RHE), attaining ∼95% at −1.3 V. Facet-specific structural and microscopic analyses show Y incorporation along the <00z> axis, which induces localized tensile and compressive strain, promoting the exposure of (003) facet, in contrast to (012) in the relatively strain-free Bi100 NPs. In situ Raman spectroscopy indicates the reversible formation of Bi2O2CO3 at low cathodic potentials and the dominance of metallic Bi at potentials coinciding with high FEformate. First-principles calculations reveal that strong Bi–Y d-p orbital hybridization and Bi site metallization generate electron-deficient Y-centers, promoting CO2 activation through O–Y interactions and selective stabilization of the adsorbed HCOO intermediate. These findings underscore the role of lattice strain engineering and electronic modulation in optimizing the CO2RR activity.

The reconstruction of Cu electrocatalysts during CO2 reduction is an impediment to the stability of this technology, yet a clear picture of the species involved in this process remains elusive. Here, ...

The development of effective catalysts for the CO2 reduction reaction (CO2RR) is essential for transforming atmospheric CO2 into valuable chemical scaffolds.. The development of appropriate CO2RR cata...