(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 ...

We describe the selective formation of heterobimetallic complexes, exploiting the coordination trends of the developed bis-terpyridyl trans-1,2-cyclohexadiamine platform (L). Following a stepwise addition, we first reacted ligand L toward tetrakisacetonitrile transition metal precursors, [M(MeCN)4][BF4]2 (where M = Fe or Ni), to generate the monometallic complexes 1 ([FeL][BF4]2) and 2 ([NiL][BF4]2). These species were later combined with the tetrakisacetonitrile precursor [Cu(MeCN)4][BF4], generating the corresponding heterobimetallic complexes 3 ([FeCuL(MeCN)2][BF4]3) and 4 ([NiCuL(MeCN)2][BF4]3). The four species obtained, in high yields, have been structurally characterized. Their cyclic voltammetry analysis revealed the impact of the CuI-atom presence on the heterobimetallic complexes under argon and carbon dioxide (CO2) atmospheres. Controlled potential electrolysis studies revealed the instability of complexes 1–4 toward CO2RR, generating the heterogeneous material in solution and on the electrode surface. In contrast, CO2 photoreduction studies revealed higher stability and photocatalytic activity for the FeII-based complexes (1 and 3), generating CO with 88% selectivity.

While much of the current research in electrochemical CO2 reduction reaction (CO2RR) identified the CO2 single-pass conversion efficiency (SPCE) as a key performance metric for the technology practica...

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....

(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 ...

Manganese bipyridine tricarbonyl complexes show high efficiency and selectivity in electrochemical CO2 reduction (e-CO2RR) to CO. Efforts to shift selectivity toward HCOOH have been made by introducin...

The electrochemical CO2 reduction reaction (CO2RR) in a membrane electrode assembly (MEA) efficiently turns CO2 into a feedstock. However, unfavorable steady-state concentrations of ions in the catho...

The key role of morphological defects (e.g., irregular steps and dislocations) on the selectivity of model Cu catalysts for the electrocatalytic reduction of CO2 (CO2RR) is illustrated here. Cu(111) single-crystal surfaces prepared under ultrahigh vacuum (UHV) conditions and presenting similar chemical and local microscopic surface features were found to display different product selectivity during the CO2RR. In particular, changes in selectivity from hydrogen-dominant to hydrocarbon-dominant product distributions were observed based on the number of CO2RR electrolysis pretreatment cycles performed prior to a subsequent UHV surface regeneration treatment, which lead to surfaces with seemingly identical chemical composition and local crystallographic structure. However, significant mesostructural changes were observed through a micron-scale microscopic analysis, including a higher density of irregular steps on the samples producing hydrocarbons. Thus, our findings highlight that step edges are key for C–C coupling in the CO2RR and that not only atomistic but also mesoscale characterization of electrocatalytic materials is needed in order to comprehend complex selectivity trends.

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...

Electrochemical CO2 reduction (CO2RR) offers a promising strategy to recycle carbon by converting CO2 into valuable fuels and chemicals. So far, Cu-based catalysts remain the most effective for produc...

The electrification of chemical processes using renewable feedstocks and energy sources represents a key strategy toward a sustainable chemical industry. Coupling CO2 electroreduction (CO2RR) with ano...

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...

Direct electrochemical CO2 reduction (ECR) into carbon-based fuels and chemicals is a promising way to upgrade waste CO2 with renewable energy, contributing to closing carbon cycles and mitigating cli...

Copper is a highly promising catalyst for the electrochemical CO2 reduction reaction (CO2RR) since it is the only pure metal that can form highly added-value products such as ethylene and ethanol. Since the CO2RR takes place in aqueous solution, the detailed atomic structure of the water–copper interface is essential for unraveling the key reaction mechanisms. In this study, we investigate copper–water interfaces exhibiting nanometer-scale roughnesses. We introduce two molecular dynamics protocols to create rough copper surfaces, which are subsequently brought into contact with water. From these interfaces, we sample additional training configurations from machine-learning-interatomic-potential-driven molecular dynamics simulations containing hundreds of thousands of atoms. An active learning workflow is developed to identify regions with high spatially resolved uncertainty and convert them into DFT-feasible cells through a modified amorphous matrix embedding approach. Finally, we analyze the local environments at the interface using unsupervised machine-learning techniques. Unique environments emerge on the rough copper surfaces absent from model systems, including stacking-fault-induced configurations and undercoordinated corner atoms. Notably, corner atoms consistently feature chemisorbed water molecules in our simulations, indicating their potential importance in catalytic processes.

Developed a method to find the promising conditions for achieving the desired CO2RR product (high FECO and ξ) assisted by machine learning (ML). The predictive model was trained using multiple experi...

The electrochemical reduction of CO2 to CO using renewable electricity offers a compelling pathway for greenhouse gas recycling. The two-electron, two-proton process is particularly attractive due to its operational simplicity and scalability, with copper- and silver-based nanomaterials being the most widely studied catalysts as the field approaches industrial maturity. However, achieving the necessary efficiency and stability for practical applications remains a significant challenge. Recently, molecular catalysts immobilized on conductive surfaces with carbon-based inks have emerged as highly tunable hybrid systems capable of remarkable selectivity. In this work, we report that a straightforward cobalt phthalocyanine complex, simply modified with a single trimethylammonium group, delivers outstanding CO2-to-CO conversion rates and selectivity, reaching a Faradaic efficiency of 93% at a total current density of 700 mA/cm2 (jCO = 650 mA/cm2) at neutral pH. Notably, CO selectivity above 90% was sustained for over 42 h at 150 mA/cm2, illustrating the potential of simply designed molecular catalysts for large-scale applications.