Molecular Electrochemical Catalysis of CO-to-Formaldehyde Conversion with a Cobalt Complex.

Formox, a highly energy-intensive process, currently serves as the primary source of formaldehyde (HCHO), for which there is a crucial and steadily growing chemical demand. The alternative electrochemical production of HCHO from C1 carbon sources such as CO2 and CO is still in its early stages, with even the few identified cases lacking mechanistic rationalization. In this study, we demonstrate that cobalt phthalocyanine (CoPc) immobilized on multiwalled carbon nanotubes (MW-CNTs) constitutes an excellent electrocatalytic system for producing HCHO with productivity through the direct reduction of CO, the two-electron reduction product of CO2. By carefully adjusting both the pH and the applied potential, we identified conditions that enable the production of HCHO with a partial current density of 0.64 mA cm-2 (17.5% Faradaic efficiency, FE) and a total FE of 61.2% for the liquid products (formaldehyde and methanol). A reduction mechanism is proposed.

Operando Spectroelectrochemistry Unravels the Mechanism of CO2 Electrocatalytic Reduction by an Fe Porphyrin.

Iron porphyrins are molecular catalysts recognized for their ability to electrochemically and photochemically reduce carbon dioxide (CO2). The main reduction product is carbon monoxide (CO). CO holds significant industrial importance as it serves as a precursor for various valuable chemical products containing either a single carbon atom (C1), like methanol or methane, or multiple carbon atoms (Cn), such as ethanol or ethylene. Despite the long-established efficiency of these catalysts, optimizing their catalytic activity and stability and comprehending the intricate reaction mechanisms remain a significant challenge. This article presents a comprehensive investigation of the mechanistic aspects of the selective electroreduction of CO2 to CO using an iron porphyrin substituted with four trimethylammonium groups in the para position [(pTMA)FeIII-Cl]4+. By employing infrared and UV-Visible spectroelectrochemistry, changes in the electronic structure and coordination environment of the iron center can be observed in real-time as the electrochemical potential is adjusted, offering new insights into the reaction mechanisms. Catalytic species were identified, and evidence of a secondary reaction pathway was uncovered, potentially prompting a re-evaluation of the nature of the catalytically active species.

Antenna Effect in Noble Metal-Free Dye-Sensitized Photocatalytic Systems Enhances CO2 -to-CO Conversion.

Dye-sensitized photocatalytic systems (DSPs) have been extensively investigated for solar-driven hydrogen (H2 ) evolution. However, their application in carbon dioxide (CO2 ) reduction remains limited. Furthermore, current solar-driven CO2 -to-CO DSPs typically employ rhenium complexes as catalysts. In this study, we have developed DSPs that incorporate noble metal-free components, specifically a zinc-porphyrin as photosensitizer (PS) and a cobalt-quaterpyridine as catalyst (CAT). Taking a significant stride forward, we have achieved an antenna effect for the first time in CO2 -to-CO DSPs by introducing a Bodipy as an additional chromophore to enhance light harvesting efficiency. The energy transfer from Bodipy to zinc porphyrin resulted in remarkable stability (turn over number (TON)=759 vs. CAT), and high CO evolution activity (42 mmol g-1 h-1 vs. CAT).

Backbone Engineering of Polymeric Catalysts for High-Performance CO2 Reduction in Bipolar Membrane Zero-Gap Electrolyzer.

Bipolar membranes (BPMs) have emerged as a promising solution for mitigating CO2 losses, salt precipitation and high maintenance costs associated with the commonly used anion-exchange membrane electrode assembly for CO2 reduction reaction (CO2RR). However, the industrial implementation of BPM-based zero-gap electrolyzer is hampered by the poor CO2RR performance, largely attributed to the local acidic environment. Here, we report a backbone engineering strategy to improve the CO2RR performance of molecular catalysts in BPM-based zero-gap electrolyzers by covalently grafting cobalt tetraaminophthalocyanine onto a positively charged polyfluorene backbone (PF-CoTAPc). PF-CoTAPc shows a high acid tolerance in BPM electrode assembly (BPMEA), achieving a high FE of 82.6 % for CO at 100 mA/cm2 and a high CO2 utilization efficiency of 87.8 %. Notably, the CO2RR selectivity, carbon utilization efficiency and long-term stability of PF-CoTAPc in BPMEA outperform reported BPM systems. We attribute the enhancement to the stable cationic shield in the double layer and suppression of proton migration, ultimately inhibiting the undesired hydrogen evolution and improving the CO2RR selectivity. Techno-economic analysis shows the least energy consumption (957 kJ/mol) for the PF-CoTAPc catalyst in BPMEA. Our findings provide a viable strategy for designing efficient CO2RR catalysts in acidic environments.

Visible-Light-Driven CO2 Reduction with Homobimetallic Complexes. Cooperativity between Metals and Activation of Different Pathways.

Visible-light-driven reduction of CO2 to both CO and formate (HCOO-) was achieved in acetonitrile solutions using a homobimetallic Cu bisquaterpyridine complex. In the presence of a weak acid (water) as coreactant, the reaction rate was enhanced, and a total of ca. 766 TON (turnover number) was reached for the CO2 reduction, with 60% selectivity for formate and 28% selectivity for CO, using Ru(phen)32+ as a sensitizer and amines as sacrificial electron donors. Mechanistic studies revealed that with the help of cooperativity between two Cu centers, a bridging hydride is generated in the presence of a proton source (water) and further reacts with CO2 to give HCOO-. A second product, CO, was also produced in a parallel competitive pathway upon direct coordination of CO2 to the reduced complex. Mechanistic studies further allowed comparison of the observed reactivity to the monometallic Cu quaterpyridine complex, which only produced CO, and to the related homobimetallic Co bisquaterpyridine complex, that has been previously shown to generate formate following a mechanism not involving the formation of an intermediate hydride species.

Electrocatalytic CO2 Reduction with a Binuclear Bis-Terpyridine Pyrazole-Bridged Cobalt Complex.

A pyrazole-based ligand substituted with terpyridine groups at the 3 and 5 positions has been synthesized to form the dinuclear cobalt complex 1, that electrocatalytically reduces carbon dioxide (CO2 ) to carbon monoxide (CO) in the presence of Brønsted acids in DMF. Chemical, electrochemical and UV-vis spectro-electrochemical studies under inert atmosphere indicate pairwise reduction processes of complex 1. Infrared spectro-electrochemical studies under CO2 and CO atmosphere are consistent with a reduced CO-containing dicobalt complex which results from the electroreduction of CO2 . In the presence of trifluoroethanol (TFE), electrocatalytic studies revealed single-site mechanism with up to 94 % selectivity towards CO formation when 1.47 M TFE were present, at -1.35 V vs. Saturated Calomel Electrode in DMF (0.39 V overpotential). The low faradaic efficiencies obtained (<50 %) are attributed to the generation of CO-containing species formed during the electrocatalytic process, which inhibit the reduction of CO2 .

Visible-light-driven methane formation from CO2 with a molecular iron catalyst.

Converting CO2 into fuel or chemical feedstock compounds could in principle reduce fossil fuel consumption and climate-changing CO2 emissions. One strategy aims for electrochemical conversions powered by electricity from renewable sources, but photochemical approaches driven by sunlight are also conceivable. A considerable challenge in both approaches is the development of efficient and selective catalysts, ideally based on cheap and Earth-abundant elements rather than expensive precious metals. Of the molecular photo- and electrocatalysts reported, only a few catalysts are stable and selective for CO2 reduction; moreover, these catalysts produce primarily CO or HCOOH, and catalysts capable of generating even low to moderate yields of highly reduced hydrocarbons remain rare. Here we show that an iron tetraphenylporphyrin complex functionalized with trimethylammonio groups, which is the most efficient and selective molecular electro- catalyst for converting CO2 to CO known, can also catalyse the eight-electron reduction of CO2 to methane upon visible light irradiation at ambient temperature and pressure. We find that the catalytic system, operated in an acetonitrile solution containing a photosensitizer and sacrificial electron donor, operates stably over several days. CO is the main product of the direct CO2 photoreduction reaction, but a two-pot procedure that first reduces CO2 and then reduces CO generates methane with a selectivity of up to 82 per cent and a quantum yield (light-to-product efficiency) of 0.18 per cent. However, we anticipate that the operating principles of our system may aid the development of other molecular catalysts for the production of solar fuels from CO2 under mild conditions.

Controlling the Hydrophilicity of the Electrochemical Interface to Modulate the Oxygen-Atom Transfer in Electrocatalytic Epoxidation Reactions.

The electrocatalytic epoxidation of alkenes at heterogeneous catalysts using water as the sole oxygen source is a promising safe route toward the sustainable synthesis of epoxides, which are essential building blocks in organic chemistry. However, the physicochemical parameters governing the oxygen-atom transfer to the alkene and the impact of the electrolyte structure on the epoxidation reaction are yet to be understood. Here, we study the electrocatalytic epoxidation of cyclooctene at the surface of gold in hybrid organic/aqueous mixtures using acetonitrile (ACN) solvent. Gold was selected, as in ACN/water electrolytes gold oxide is formed by reactivity with water at potentials less anodic than the oxygen evolution reaction (OER). This unique property allows us to demonstrate that a sacrificial mechanism is responsible for cyclooctene epoxidation at metallic gold surfaces, proceeding through cyclooctene activation, while epoxidation at gold oxide shares similar reaction intermediates with the OER and proceeds via the activation of water. More importantly, we show that the hydrophilicity of the electrode/electrolyte interface can be tuned by changing the nature of the supporting salt cation, hence affecting the reaction selectivity. At low overpotential, hydrophilic interfaces formed using strong Lewis acid cations are found to favor gold passivation. Instead, hydrophobic interfaces created by the use of large organic cations favor the oxidation of cyclooctene and the formation of epoxide. Our study directly demonstrates how tuning the hydrophilicity of electrochemical interfaces can improve both the yield and selectivity of anodic reactions at the surface of heterogeneous catalysts.

On the Existence and Role of Formaldehyde During Aqueous Electrochemical Reduction of Carbon Monoxide to Methanol by Cobalt Phthalocyanine.

A long-time challenge in aqueous CO2 electrochemical reduction is to catalyze the formation of products beyond carbon monoxide with selectivity. Formaldehyde is the simplest of these products and one of the most relevant due to its broad use in the industry. Paradoxically it is one of the less reported product. Such scarcity may be in part explained by difficult identification and quantification using conventional chromatography or proton nuclear magnetic resonance techniques. Likewise, indirect detection methods are usually not compatible with labelled studies for asserting product origin. Recently, the possible production of formaldehyde during electrochemical reduction of carbon monoxide to methanol at cobalt phthalocyanine molecular catalyst in basic media has been the object of contradictory reports. By applying an analytical procedure based on proton NMR along with labelled studies, we provide definitive evidence for HCHO formation. We have further identified the possible scenarios for methanol formation through formaldehyde and revealed that the formation of the intermediate and its subsequent reduction are taking place at the same single active site. These studies open a new perspective to improve selectivity toward formaldehyde formation and to develop a subsequent chemistry based on reacting it with nucleophiles.

Molecular Electrochemical Reductive Splitting of Dinitrogen with a Molybdenum Complex.

Nitrogen reduction under mild conditions (room T and atmospheric P), using a non-fossil source of hydrogen remains a challenge. Molecular metal complexes, notably Mo based, have recently been shown to be active for such nitrogen fixation. We report electrochemical N2 splitting with a MoIII triphosphino complex [(PPP)MoI3 ], at room temperature and a moderately negative potential. A MoIV nitride species was generated, which is confirmed by electrochemistry and NMR studies. The reaction goes through two successive one electron reductions of the starting Mo species, coordination of a N2 molecule, and further splitting to a MoIV nitride complex. Preliminary DFT studies support the formation of a bridging MoI N2 MoI dinitrogen dimer evolving to the Mo nitride via a low energy transition state. This example joins a short list of molecular complexes for N2 electrochemical reductive cleavage. It opens a door to electrochemical proton-coupled electron transfer (PCET) conversion studies of N2 to NH3 .

Highly Efficient Photocatalytic Reduction of CO2 to CO by In Situ Formation of a Hybrid Catalytic System Based on Molecular Iron Quaterpyridine Covalently Linked to Carbon Nitride.

Efficient and selective photocatalytic CO2 reduction was obtained within a hybrid system that is formed in situ via a Schiff base condensation between a molecular iron quaterpyridine complex bearing an aldehyde function and carbon nitride. Irradiation (blue LED) of an CH3 CN solution containing 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole (BIH), triethylamine (TEA), Feqpy-BA (qpy-BA=4-([2,2':6',2'':6'',2'''-quaterpyridin]-4-yl)benzaldehyde) and C3 N4 resulted in CO evolution with a turnover number of 2554 and 95 % selectivity. This hybrid catalytic system unlocks covalent linkage of molecular catalysts with semiconductor photosensitizers via Schiff base reaction for high-efficiency photocatalytic reduction of CO2 , opening a pathway for diverse photocatalysis.

Hybridization of Molecular and Graphene Materials for CO2 Photocatalytic Reduction with Selectivity Control.

In the quest for designing efficient and stable photocatalytic materials for CO2 reduction, hybridizing a selective noble-metal-free molecular catalyst and carbon-based light-absorbing materials has recently emerged as a fruitful approach. In this work, we report about Co quaterpyridine complexes covalently linked to graphene surfaces functionalized by carboxylic acid groups. The nanostructured materials were characterized by X-ray photoemission spectroscopy, X-ray absorption spectroscopy, IR and Raman spectroscopies, high-resolution transmission electron microscopy and proved to be highly active in the visible-light-driven CO2 catalytic conversion in acetonitrile solutions. Exceptional stabilities (over 200 h of irradiation) were obtained without compromising the selective conversion of CO2 to products (>97%). Most importantly, complete selectivity control could be obtained upon adjusting the experimental conditions: production of CO as the only product was achieved when using a weak acid (phenol or trifluoroethanol) as a co-substrate, while formate was exclusively obtained in solutions of mixed acetonitrile and triethanolamine.

Electrocatalytic and Photocatalytic Reduction of Carbon Dioxide by Earth-Abundant Bimetallic Molecular Catalysts.

Converting CO2 into useful resources by electrocatalysis and photocatalysis is a promising strategy for recycling of the gas and electrification of industries. Numerous studies have shown that multinuclear metal catalysts have higher selectivity and catalytic activity than monometallic catalysts due to the synergistic effects between the metal sites. In this review, we summarize some of the recent progress on the electrocatalytic and photocatalytic reduction of CO2 by earth-abundant bimetallic molecular catalysts.

Taming Electron Transfers: From Breaking Bonds to Creating Molecules.

The electron is the ultimate redox reagent to build and reshape molecular structures. Understanding and controlling the parameters underlying dissociative electron transfer (DET) reactivity and its coupling with proton transfer is crucial for combining selectivity, kinetics and energy efficiency in molecular chemistry. Reactivity understanding and mechanistic elements in DET processes are traced back and key examples of current research efforts are presented, demonstrating a large variety of applications. The involvement of DET pathways indeed encompasses a broad range of processes such as photoredox catalysis, CO2 reduction and alcohol oxidation. Interplay between these experimental examples and fundamental mechanistic study provides a powerful path to the understanding of driving force-rate relationships, which is crucial for the development of future generations of energy efficient catalytic schemes in redox organic chemistry.

Molecular quaterpyridine-based metal complexes for small molecule activation: water splitting and CO2 reduction.

Artificial photosynthesis is considered as one of the most promising strategies for solar-to-fuel conversion through sunlight-driven water splitting and CO2 reduction. This tutorial describes recent developments in the use of metal quaterpyridine complexes as electrocatalyts and photocatalysts for artificial photosynthesis.

Efficient Visible-Light-Driven CO2 Reduction by a Cobalt Molecular Catalyst Covalently Linked to Mesoporous Carbon Nitride.

Achieving visible-light-driven carbon dioxide reduction with high selectivity control and durability while using only earth abundant elements requires new strategies. Hybrid catalytic material was prepared upon covalent grafting a Co-quaterpyridine molecular complex to semiconductive mesoporous graphitic carbon nitride (mpg-C3N4) through an amide linkage. The molecular material was characterized by various spectroscopic techniques, including XPS, IR, and impedance spectroscopy. It proved to be a selective catalyst for CO production in acetonitrile using a solar simulator with a high 98% selectivity, while being remarkably robust since no degradation was observed after 4 days of irradiation (ca. 500 catalytic cycles). This unique combination of a selective molecular catalyst with a simple and robust semiconductive material opens new pathways for CO2 catalytic light-driven reduction.

The epiGenomic Efficient Correlator (epiGeEC) tool allows fast comparison of user datasets with thousands of public epigenomic datasets.

SUMMARY: In recent years, major initiatives such as the International Human Epigenome Consortium have generated thousands of high-quality genome-wide datasets for a large variety of assays and cell types. This data can be used as a reference to assess whether the signal from a user-provided dataset corresponds to its expected experiment, as well as to help reveal unexpected biological associations. We have developed the epiGenomic Efficient Correlator (epiGeEC) tool to enable genome-wide comparisons of very large numbers of datasets. A public Galaxy implementation of epiGeEC allows comparison of user datasets with thousands of public datasets in a few minutes. AVAILABILITY AND IMPLEMENTATION: The source code is available at https://bitbucket.org/labjacquespe/epigeec and the Galaxy implementation at http://epigeec.genap.ca. SUPPLEMENTARY INFORMATION: Supplementary data are available at Bioinformatics online.

Iron Porphyrin Allows Fast and Selective Electrocatalytic Conversion of CO2 to CO in a Flow Cell.

Molecular catalysts have been shown to have high selectivity for CO2 electrochemical reduction to CO, but with current densities significantly below those obtained with solid-state materials. By depositing a simple Fe porphyrin mixed with carbon black onto a carbon paper support, it was possible to obtain a catalytic material that could be used in a flow cell for fast and selective conversion of CO2 to CO. At neutral pH (7.3) a current density as high as 83.7 mA cm-2 was obtained with a CO selectivity close to 98 %. In basic solution (pH 14), a current density of 27 mA cm-2 was maintained for 24 h with 99.7 % selectivity for CO at only 50 mV overpotential, leading to a record energy efficiency of 71 %. In addition, a current density for CO production as high as 152 mA cm-2 (>98 % selectivity) was obtained at a low overpotential of 470 mV, outperforming state-of-the-art noble metal based catalysts.

Electrocatalytic O2 Activation by Fe Tetrakis(pentafluorophenyl)porphyrin in Acidic Organic Media. Evidence of High-Valent Fe Oxo Species.

O2 activation under mild conditions remains a weighty challenge for chemists. Herein we report a study of electrochemical O2 reductive activation catalyzed by FeIII(F20TPP)Cl, by means of cyclic voltammetry and UV-vis spectroelectrochemistry in acidic solutions of N,N-dimethylformamide. Two parallel catalytic pathways have been evidenced occurring at different overpotentials. At high overpotential a classical electron-proton (EPT) pathway where protonation of Fe peroxo ultimately leads to the formation of high-valent Fe oxo species dominates. At low overpotential a proton-electron (PET) pathway involving a hydrosuperoxo species has been identified.