Molecular Catalysts Research Articles

Potential Dependent Reorientation Controlling Activity of a Molecular Electrocatalyst.

The activity of molecular electrocatalysts depends on the interplay of electrolyte composition near the electrode surface, the composition and morphology of the electrode surface, and the electric field at the electrode-electrolyte interface. This interplay is challenging to study and often overlooked when assessing molecular catalyst activity. Here, we use surface specific vibrational sum frequency generation (VSFG) spectroscopy to study the solvent and potential dependent activation of Mo(bpy)(CO)4, a CO2 reduction catalyst, at a polycrystalline Au electrode. We find that the parent complex undergoes potential dependent reorientation at the electrode surface when a small amount of N-methyl-2-pyrrolidone (NMP) is present. This preactivates the complex, resulting in greater yields at less negative potentials, of the active electrocatalyst for CO2 reduction.

Key Experimental Considerations When Evaluating Functional Ionic Liquids for Combined Capture and Electrochemical Conversion of CO2.

Ionic liquids (ILs) are considered functional electrolytes for the electrocatalytic reduction of CO2 (ECO2R) due to their role in the double-layer structure formation and increased CO2 availability at the electrode surface, which reduces the voltage requirement. However, not all ILs are the same, considering the purity and degree of the functionality of the IL. Further, there are critical experimental factors that impact the evaluation of ILs for ECO2R including the reference electrode, working electrode construction, cosolvent selection, cell geometry, and whether the electrochemical cell is a single compartment or a divided cell. Here, we describe improved synthesis methods of imidazolium cyanopyrrolide IL for electrochemical studies in consideration of precursor composition and reaction time. We explored how IL with cosolvents (i.e. acetonitrile, dimethylformamide, dimethyl sulfoxide, propylene carbonate, and n-methyl-2-pyrrolidone) affects conductivity, CO2 mass transport, and ECO2R activation overpotential together with the effects of electrode materials (Sn, Ag, Au, and glassy carbon). Acetonitrile was found to be the best solvent for lowering the onset potential and increasing the catalytic current density for the production of CO owing to the enhanced ion mobility in combination with the silver electrode. Further, the ECO2R activity of molecular catalysts Ni(cyclam)Cl2 and iron tetraphenylsulfonato porphyrin (FeTPPS) on the carbon cloth electrode maintained high Faradaic efficiencies for CO in the presence of the IL. This study presents best practices for examining nontraditional multifunctional electrolytes amenable to integrated CO2 capture and conversion technologies for homogeneous and heterogeneous ECO2R.

Ultrafast Electron Transfer from CuInS2 Quantum Dots to a Molecular Catalyst for Hydrogen Production: Challenging Diffusion Limitations.

Systems integrating quantum dots with molecular catalysts are attracting ever more attention, primarily owing to their tunability and notable photocatalytic activity in the context of the hydrogen evolution reaction (HER) and CO2 reduction reaction (CO2RR). CuInS2 (CIS) quantum dots (QDs) are effective photoreductants, having relatively high-energy conduction bands, but their electronic structure and defect states often lead to poor performance, prompting many researchers to employ them with a core-shell structure. Molecular cobalt HER catalysts, on the other hand, often suffer from poor stability. Here, we have combined CIS QDs, surface-passivated with l-cysteine and iodide from a water-based synthesis, with two tetraazamacrocyclic cobalt complexes to realize systems which demonstrate high turnover numbers for the HER (up to >8000 per catalyst), using ascorbate as the sacrificial electron donor at pH = 4.5. Photoluminescence intensity and lifetime quenching data indicated a large degree of binding of the catalysts to the QDs, even with only ca. 1 μM each of QDs and catalysts, linked to an entirely static quenching mechanism. The data was fitted with a Poissonian distribution of catalyst molecules over the QDs, from which the concentration of QDs could be evaluated. No important difference in either quenching or photocatalysis was observed between catalysts with and without the carboxylate as a potential anchoring group. Femtosecond transient absorption spectroscopy confirmed ultrafast interfacial electron transfer from the QDs and the formation of the singly reduced catalyst (CoII state) for both complexes, with an average electron transfer rate constant of <kET> ≈ (10 ps)-1. These favorable results confirm that the core tetraazamacrocyclic cobalt complex is remarkably stable under photocatalytic conditions and that CIS QDs without inorganic shell structures for passivation can act as effective photosensitizers, while their smaller size makes them suitable for application in the sensitization of, inter alia, mesoporous electrodes.

Thermodynamic and Kinetic Activity Descriptors for the Catalytic Hydrogenation of Ketones.

Activity descriptors are a powerful tool for the design of catalysts that can efficiently utilize H2 with minimal energy losses. In this study, we develop the use of hydricity and H- self-exchange rates as thermodynamic and kinetic descriptors for the hydrogenation of ketones by molecular catalysts. Two complexes with known hydricity, HRh(dmpe)2 and HCo(dmpe)2, were investigated for the catalytic hydrogenation of ketones under mild conditions (1.5 atm and 25 °C). The rhodium catalyst proved to be an efficient catalyst for a wide range of ketones, whereas the cobalt catalyst could only hydrogenate electron-deficient ketones. Using a combination of experiment and electronic structure theory, thermodynamic hydricity values were established for 46 alkoxide/ketone pairs in both acetonitrile and tetrahydrofuran solvents. Through comparison of the hydricities of the catalysts and substrates, it was determined that catalysis was observed only for catalyst/ketone pairs with an exergonic H- transfer step. Mechanistic studies revealed that H- transfer was the rate-limiting step for catalysis, allowing for the experimental and computation construction of linear free-energy relationships (LFERs) for H- transfer. Further analysis revealed that the LFERs could be reproduced using Marcus theory, in which the H- self-exchange rates for the HRh/Rh+ and ketone/alkoxide pairs were used to predict the experimentally measured catalytic barriers within 2 kcal mol-1. These studies significantly expand the scope of catalytic reactions that can be analyzed with a thermodynamic hydricity descriptor and firmly establish Marcus theory as a valid approach to develop kinetic descriptors for designing catalysts for H- transfer reactions.

NMR Spectroscopic Signatures of Cationic Surface Sites from Supported Coinage Metals Interacting with N-Heterocyclic Carbenes.

N-heterocyclic carbenes (NHCs) have been extensively studied to modulate the reactivity of molecular catalysts, colloids, and their supported analogues, being isolated sites, clusters, or nanoparticles. While the interaction of NHCs on metal surfaces has been discussed in great detail, showing specific coordination chemistry depending on the type of NHC ligands, much less is known when the metal is dispersed on oxide supports, as in heterogeneous catalysts. Herein, we study the interaction of NHC ligands with Au surface sites dispersed on silica, a nonreducible oxide support. We identify the easy formation of bis-NHC ligated Au(I) surface sites parallel to what is found on metallic Au surfaces. These species display a specific 13C NMR spectroscopic signature that clearly distinguishes them from the mono-NHC Au(I) surface sites or supported imidazoliums. We find that bis-ligated surface species are not unique to supported Au(I) species and are found for the corresponding Ag(I) and Cu(I) species, as well as for the isolobal surface silanols. Furthermore, the interaction of NHC ligand with silica-supported Au nanoparticles also yields bis-NHC ligated Au(I) surface sites, indicating that metal atoms can also be easily extracted from nanoparticles, further illustrating the dynamics of these systems and the overall favorable formation of such bis-ligated species across a range of systems, besides what has been found on crystalline metal facets.

Large-Area Conductive MOF Ultrathin Film Controllably Integrating Dinuclear-Metal Sites and Photosensitizers to Boost Photocatalytic CO2 Reduction with H2O as an Electron Donor.

Owing to the electrical conductivity and periodic porosity, conductive metal-organic framework (cMOF) ultrathin films open new perspectives to photocatalysis. The space-selective assembly of catalytic sites and photosensitizers in/on cMOF is favorable for promoting the separation of photogenerated carriers and mass transfer. However, the controllable integration of functional units into the cMOF film is rarely reported. Herein, via the synergistic effect of steric hindrance and an electrostatic-driven strategy, the dinuclear-metal molecular catalysts (DMC) and perovskite (PVK) quantum dot photosensitizers were immobilized into channels and onto the surface of cMOF ultrathin films, respectively, affording [DMC@cMOF]-PVK film photocatalysts. In this unique heterostructure, cMOF not only facilitated the charge transfer from PVK to DMC but also guaranteed mass transfer. Using H2O as an electron donor, [DMC@cMOF]-PVK realized a 133.36 μmol·g-1·h-1 CO yield in photocatalytic CO2 reduction, much higher than PVK and DMC-PVK. Owing to the excellent light transmission of films, multilayers of [DMC@cMOF]-PVK were integrated to increase the CO yield per unit area, and the 10-layer device realized a 1115.92 μmol·m-2 CO yield in 4 h, which was 8-fold higher than that of powder counterpart. This work not only lightens the development of cMOF-based composite films but also paves a novel avenue for an ultrathin film photocatalyst.

Insights into the Interfacial Charge Transfer Dynamics in Semiconductor–Molecular Catalyst Assemblies for Photo–Induced CO2 Reduction

AbstractThis mini–review summarises examples of photo and photoelectrochemical CO2 reduction reactions (CO2RR) using semiconductor–molecular catalyst–based hybrid assemblies in which studies of charge transfer dynamics were also performed. In these catalysts, the grand challenges are controlling ultra–fast one–electron charge separation and simultaneously governing its impact on the efficiency and product selectivity in the multielectron and multi–proton–assisted CO2RR. In practice, several unwanted electron recombination processes occur in the femtosecond to millisecond timescale range impacting the overall catalysis efficiency. Titanium di‐oxide (TiO2) nanoparticle, mesoporous TiO2 film, copper indium sulphide (CuInS2) quantum dots were used as semiconductor materials, in turn rhenium (I) bipyridine, cobalt (II) terpyridine, cobaloxamine complex, and iron (III) porphyrins were investigated as molecular catalysts. The results of the charge transfer dynamic studies operating in such hybrid systems shed light on their charge accumulation processes, their rate constants for the intramolecular charge transfer processes and the decay lifetimes of the different excited state species that are produced. Moreover, a comprehensive understanding of the catalysts’ charge transfer dynamics is crucial to identifying detrimental charge recombination pathways. These undesired pathways can be used as rational basis for improving the design of future multi–redox–driven hybrid catalysts.

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.

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

AbstractBipolar 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.

Efficient Visible-Light-Driven Carbon Dioxide Reduction using a Bioinspired Nickel Molecular Catalyst.

Inspired by natural enzymes, this study presents a nickel-based molecular catalyst, [Ni‖(N2S2)]Cl2 (NiN2S2, N2S2=2,11-dithia[3,3](2,6)pyridinophane), for the photochemical catalytic reduction of CO2 under visible light. The catalyst was synthesized and characterized using various techniques, including liquid chromatography-high resolution mass spectrometry (LC-HRMS), UV-Visible spectroscopy, and X-ray crystallography. The crystallographic analysis revealed a slightly distorted octahedral coordination geometry with a mononuclear Ni2+ cation, two nitrogen atoms and two sulfur atoms. Photocatalytic CO2 reduction experiments were performed in homogeneous conditions using the catalyst in combination with [Ru(bpy)3]Cl2 (bpy=2,2'-bipyridine) as a photosensitizer and 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole (BIH) as a sacrificial electron donor. The catalyst achieved a high selectivity of 89 % towards CO and a remarkable turnover number (TON) of 7991 during 8 h of visible light irradiation under CO2 in the presence of phenol as a co-substrate. The turnover frequency (TOF) in the initial 6 h was 1079 h-1, with an apparent quantum yield (AQY) of 1.08 %. Controlled experiments confirmed the dependency on the catalyst, light, and sacrificial electron donor for the CO2 reduction process. These findings demonstrate this bioinspired nickel molecular catalyst could be effective for fast and efficient photochemical catalytic reduction of CO2 to CO.

Synthesis of Bifunctional Catalysts for the Cycloaddition of CO2 to Epoxides through an Epoxide‐Driven Strategy

AbstractThe design of molecular scaffolds bearing multiple functional groups for the activation and ring‐opening of epoxides is a crucial challenge for the synthesis of efficient homogeneous and heterogeneous catalysts that are used for the cycloaddition reaction of CO2 to epoxides. Traditional approaches to prepare such multifunctional catalysts often imply multistep synthetic procedures and expensive building blocks. In this work we show that bifunctional catalysts for the cycloaddition of CO2 to epoxides bearing a Lewis acid metal and a quaternary ammonium halide group can be prepared in just two steps starting from an opportunely designed epoxide precursor by using inexpensive substrates. Such a readily accessible catalyst was applied for the cycloaddition of CO2 to a series of epoxides under atmospheric conditions generally leading to quantitative substrate conversion and high carbonate selectivities. Importantly, we also show that the epoxide‐driven concept developed for the preparation of the molecular catalyst, could be applied to prepare recyclable heterogeneous systems for the target cycloaddition reaction.

Co(O)4(N)‐type single‐atom‐based catalysts and ligand‐driven modulation of electrocatalytic properties for reducing oxygen molecules

AbstractSingle‐atom‐based catalysts are intriguing electrocatalytic platforms that combine the advantages of molecular catalysts and conductive carbon‐based materials. In this work, hybrids (Co‐NrGO‐1 and Co‐NrGO‐2) were generated by wet‐reactions between organometallic complexes (Co(CH3COO)2 and Co[CH3(CH2)3CH(C2H5)COO]2, respectively) and N‐doped reduced graphene oxide at 25°C. Various characterizations revealed the formation of atomically dispersed Co(O)4(N) species in Co‐NrGO‐2. Density functional theory (DFT) calculations explained the effect of the aliphatic C7 group in Co2 on the formation processes. The Co‐NrGO‐2 hybrid showed excellent catalytic performance, such as onset (0.94 V) and half‐wave (0.83 V) potentials, for electrochemical oxygen reduction reaction (ORR). Co‐NrGO‐2 outperformed Co‐NrGO‐1, which was explained by more back donation to the antibonding orbitals of O2 from electron‐rich aliphatic groups. DFT calculations support this feature, with mechanistic investigations showing favored ORR reactions and facile breakage of double bonds in O2.

Antioxidant-driven activity and stability enhancement in multiphase bicarbonate hydrogenation catalysis with a Ru-PNP pincer complex

Herein, we present a practical strategy to enhance the performance of a multiphase system for bicarbonate hydrogenation based on a molecular Ru-PNP pincer catalyst. This study demonstrates that the use of organic antioxidants not only mitigates catalyst degradation but also significantly boosts its intrinsic activity. This enables efficient catalyst recycling at ultra-low concentrations. Systematic screening and optimization of a range of organic antioxidants has identified TDTBP (tris(2,4-di-tert-butylphenyl) phosphite) as being exceptionally efficient in stabilizing and enhancing the performance of the Ru-PNP catalyst. With the optimized system an unprecedented integral turnover frequency (TOF) of 115,000 h−1 and a total turnover number (TTON) of 9.43×106 across four recycling tests were demonstrated, conducted at a reaction temperature of 90 ºC and H2 pressure of 50 bar. These findings represent a substantial advancement in sustainable formate/formic acid production, offering a scalable and highly efficient method suitable for industrial-scale application.

Modulating the Electronic Structure of Cobalt in Molecular Catalysts via Coordination Environment Regulation for Highly Efficient Heterogeneous Nitrate Reduction

AbstractAmmonia (NH3) is pivotal in modern industry and represents a promising next‐generation carbon‐free energy carrier. Electrocatalytic nitrate reduction reaction (eNO3RR) presents viable solutions for NH3 production and removal of ambient nitrate pollutants. However, the development of eNO3RR is hindered by lacking the efficient electrocatalysts. To address this challenge, we synthesized a series of macrocyclic molecular catalysts for the heterogeneous eNO3RR. These materials possess different coordination environments around metal centers by surrounding subunits. Consequently, electronic structures of the active centers can be altered, enabling tunable activity towards eNO3RR. Our investigation reveals that metal center with an N2(pyrrole)‐N2(pyridine) configuration demonstrates superior activity over the others and achieves a high NH3 Faradaic efficiency (FE) of over 90 % within the tested range, where the highest FE of approximately 94 % is obtained. Furthermore, it achieves a production rate of 11.28 mg mgcat−1 h−1, and a turnover frequency of up to 3.28 s−1. Further tests disclose that these molecular catalysts with diverse coordination environments showed different magnetic moments. Theoretical calculation results indicate that variated coordination environments can result in a d‐band center variation which eventually affects rate‐determining step energy and calculated magnetic moments, thus establishing a correlation between electronic structure, experimental activity, and computational parameters.

Modulating the Electronic Structure of Cobalt in Molecular Catalysts via Coordination Environment Regulation for Highly Efficient Heterogeneous Nitrate Reduction.

Ammonia (NH3) is pivotal in modern industry and represents a promising next-generation carbon-free energy carrier. Electrocatalytic nitrate reduction reaction (eNO3RR) presents viable solutions for NH3 production and removal of ambient nitrate pollutants. However, the development of eNO3RR is hindered by lacking the efficient electrocatalysts. To address this challenge, we synthesized a series of macrocyclic molecular catalysts for the heterogeneous eNO3RR. These materials possess different coordination environments around metal centers by surrounding subunits. Consequently, electronic structures of the active centers can be altered, enabling tunable activity towards eNO3RR. Our investigation reveals that metal center with an N2(pyrrole)-N2(pyridine) configuration demonstrates superior activity over the others and achieves a high NH3 Faradaic efficiency (FE) of over 90 % within the tested range, where the highest FE of approximately 94 % is obtained. Furthermore, it achieves a production rate of 11.28 mg mgcat -1 h-1, and a turnover frequency of up to 3.28 s-1. Further tests disclose that these molecular catalysts with diverse coordination environments showed different magnetic moments. Theoretical calculation results indicate that variated coordination environments can result in a d-band center variation which eventually affects rate-determining step energy and calculated magnetic moments, thus establishing a correlation between electronic structure, experimental activity, and computational parameters.

Covalent Tethering of Cobalt Porphyrins on Phenolic Resins for Electrocatalytic Oxygen Reduction and Evolution Reactions.

Using functionalized supporting materials for the immobilization of molecular catalysts is an appealing strategy to improve the efficiency of molecular electrocatalysis. Herein, we report the covalent tethering of cobalt porphyrins on phenolic resins (PR) for improved electrocatalytic oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). A cobalt porphyrin bearing an alkyl bromide substituent was covalently tethered on phenolic resins, through the substitution reaction of alkyl bromides with phenolic hydroxyl groups, to afford molecule-engineered phenolic resins (Co-PR). The resulted Co-PR was efficient for electrocatalytic ORR and OER by displaying an ORR half-wave potential of E1/2=0.78 V versus RHE and an OER overpotential of 420 mV to get 10 mA/cm2 current density. We propose that the many residual phenolic hydroxyl groups on PR will surround the tethered Co porphyrin and play critical roles in facilitating proton and electron transfers. Importantly, Co-PR outperformed unmodified PR and PR loaded with Co porphyrins through simple physical adsorption (termed Co@PR). The zinc-air battery assembled using Co-PR displayed a performance comparable to that using Pt/C+Ir/C. This work is significant to present phenolic resins as a functionalized material to support molecular electrocatalysts and demonstrate the strategy to improve molecular electrocatalysis with the use of phenolic resin residues.

Enhancing CO catalytic oxidation performance over Cu-doping manganese oxide octahedral molecular sieves catalyst

The CO oxidation catalytic activity of catalysts is strongly influenced by the oxygen vacancy defects (OVDs) concentration and the valence state of active metal. Herein, a defect engineering approach was implemented to enhance the oxygen vacancy defects and to modify the valence of metal ions in manganese oxide octahedral molecular sieves (OMS-2) by the introduction of copper (Cu). The characterization and theoretical calculation results reveal that the incorporation of Cu2+ ion into the OMS-2 structure led to a rise in specific surface area and pore volume, weakening of Mn-O bonds, higher proportion of the low-coordinated oxygen species adsorbed in oxygen vacancies (Oads) and an increase in the average oxidation state of manganese. These structural modifications were discovered to considerably reduce the apparent activation energy (Ea), thus ultimately significantly enhancing the CO oxidation activity (T99 at 148 ℃at GHSV = 13,200 h−1) than the original OMS-2 (T99 = 215 ℃ at GHSV = 13,200 h−1). Furthermore, In-situ diffuse reflectance infrared Fourier transform (DRIFT) and In-situ near-ambient pressure X-ray photoelectron spectroscopy (in situ NAP-XPS) results indicate that the bimetallic synergy enhanced by doping strategy accelerates the conversion of oxygen to chemisorbed oxygen species and the reaction rate of CO oxidation through Mn3++Cu2+↔Mn4++Cu+ redox cycle. The findings of this study offer novel perspectives on the design of catalysts with exceptional performance in CO oxidation.

One-Step Electrochemical Ethylene-to-Ethylene Glycol Conversion over a Multitasking Molecular Catalyst.

Ethylene glycol is an essential commodity chemical with high demand, which is conventionally produced via thermocatalytic oxidation of ethylene with huge fossil fuel consumption and CO2 emission. The one-step electrochemical approach offers a sustainable route but suffers from reliance on noble metal catalysts, low activity, and mediocre selectivity. Herein, we report a one-step electrochemical oxidation of ethylene to ethylene glycol over an earth-abundant metal-based molecular catalyst, a cobalt phthalocyanine supported on a carbon nanotube (CoPc/CNT). The catalyst delivers ethylene glycol with 100% selectivity and 1.78 min-1 turnover frequency at room temperature and ambient pressure, more competitive than those obtained over palladium catalysts. Experimental data demonstrate that the catalyst orchestrates multiple tasks in sequence, involving electrochemical water activation to generate high-valence Co-oxo species, ethylene epoxidation to afford an ethylene oxide intermediate via oxygen transfer, and eventually ring-opening of ethylene oxide to ethylene glycol facilitated by in situ formed Lewis acid site. This work offers a great opportunity for commodity chemicals synthesis based on a one-step, earth-abundant metal-catalyzed, and renewable electricity-driven route.

Pulse Electrolysis Turns on CO2 Methanation through N‐Confused Cupric Porphyrin

AbstractBreaking the D4h symmetry in the square‐planar M−N4 configuration of macrocycle molecular catalysts has witnessed enhanced electrocatalytic activity, but at the expense of electrochemical stability. Herein, we hypothesize that the lability of the active Cu−N3 motifs in the N‐confused copper (II) tetraphenylporphyrin (CuNCP) could be overcome by applying pulsed potential electrolysis (PPE) during electrocatalytic carbon dioxide reduction. We find that applying PPE can indeed enhance the CH4 selectivity on CuNCP by 3 folds to reach the partial current density of 170 mA cm−2 at &gt;60 % Faradaic efficiency (FE) in flow cell. However, combined ex situ X‐ray diffraction (XRD), transmission electron microscope (TEM), and in situ X‐ray absorption spectroscopy (XAS), infrared (IR), Raman, scanning electrochemical microscopy (SECM) characterizations reveal that, in a prolonged time scale, the decomplexation of CuNCP is unavoidable, and the promoted water dissociation under high anodic bias with lowered pH and enriched protons facilitates successive hydrogenation of *CO on the irreversibly reduced Cu nanoparticles, leading to the improved CH4 selectivity. As a key note, this study signifies the adaption of electrolytic protocol to the catalyst structure for tailoring local chemical environment towards efficient CO2 reduction.

Pulse Electrolysis Turns on CO2 Methanation through N-Confused Cupric Porphyrin.

Breaking the D4h symmetry in the square-planar M-N4 configuration of macrocycle molecular catalysts has witnessed enhanced electrocatalytic activity, but at the expense of electrochemical stability. Herein, we hypothesize that the lability of the active Cu-N3 motifs in the N-confused copper (II) tetraphenylporphyrin (CuNCP) could be overcome by applying pulsed potential electrolysis (PPE) during electrocatalytic carbon dioxide reduction. We find that applying PPE can indeed enhance the CH4 selectivity on CuNCP by 3 folds to reach the partial current density of 170 mA cm-2 at >60 % Faradaic efficiency (FE) in flow cell. However, combined ex situ X-ray diffraction (XRD), transmission electron microscope (TEM), and in situ X-ray absorption spectroscopy (XAS), infrared (IR), Raman, scanning electrochemical microscopy (SECM) characterizations reveal that, in a prolonged time scale, the decomplexation of CuNCP is unavoidable, and the promoted water dissociation under high anodic bias with lowered pH and enriched protons facilitates successive hydrogenation of *CO on the irreversibly reduced Cu nanoparticles, leading to the improved CH4 selectivity. As a key note, this study signifies the adaption of electrolytic protocol to the catalyst structure for tailoring local chemical environment towards efficient CO2 reduction.