High-Density Cobalt Single-Atom Catalysts for Enhanced Oxygen Evolution Reaction.

Single atom catalysts (SACs) possess unique catalytic properties due to low-coordination and unsaturated active sites. However, the demonstrated performance of SACs is limited by low SAC loading, poor metal-support interactions, and nonstable performance. Herein, we report a macromolecule-assisted SAC synthesis approach that enabled us to demonstrate high-density Co single atoms (10.6 wt % Co SAC) in a pyridinic N-rich graphenic network. The highly porous carbon network (surface area of ∼186 m2 g-1) with increased conjugation and vicinal Co site decoration in Co SACs significantly enhanced the electrocatalytic oxygen evolution reaction (OER) in 1 M KOH (η10 at 351 mV; mass activity of 2209 mA mgCo-1 at 1.65 V) with more than 300 h stability. Operando X-ray absorption near-edge structure demonstrates the formation of electron-deficient Co-O coordination intermediates, accelerating OER kinetics. Density functional theory (DFT) calculations reveal the facile electron transfer from cobalt to oxygen species-accelerated OER.

Catalyst Regeneration via Chemical Oxidation Enables Long-Term Electrochemical Carbon Dioxide Reduction.

Electrochemical CO2 reduction (ECR) with industrially relevant current densities, high product selectivity, and long-term stability has been a long-sought goal. Unfortunately, copper (Cu) catalysts for producing valuable multicarbon (C2+) products undergo structural and morphological changes under ECR conditions, especially at high current densities, resulting in a rapid decrease in product selectivity. Herein, we report a catalyst regeneration strategy, one that employs an electrolysis method comprising alternating "on" and "off" operating regimes, to increase the operating stability of a Cu catalyst. We find that it increases operating lifetime many times, maintaining ethylene selectivity ≥40% for at least 200 h of electrolysis in neutral pH media at a current density of 150 mA cm-2 using a flow cell. We also demonstrate ECR to ethylene at a current density of 1 A cm-2 with ethylene selectivity ≥40% using a three-dimensional Cu gas diffusion electrode, finding that this system under these conditions is rendered stable for greater than 36 h. This work illustrates that Cu-based catalysts, once they have entered into the state conventionally considered to possess degraded catalytic activity, may be recovered to deliver high C2+ selectivity. We present evidence that the combination of short periods of electrolysis, which minimizes the morphological changes during "on" segments, with the progressive chemical oxidation of Cu atoms on the catalyst surface during "off" segments, united with the added effects of washing the accumulated salt and decreasing the catholyte temperature prolong together the catalyst's operating lifetime.

Ligand-modified nanoparticle surfaces influence CO electroreduction selectivity.

Improving the kinetics and selectivity of CO2/CO electroreduction to valuable multi-carbon products is a challenge for science and is a requirement for practical relevance. Here we develop a thiol-modified surface ligand strategy that promotes electrochemical CO-to-acetate. We explore a picture wherein nucleophilic interaction between the lone pairs of sulfur and the empty orbitals of reaction intermediates contributes to making the acetate pathway more energetically accessible. Density functional theory calculations and Raman spectroscopy suggest a mechanism where the nucleophilic interaction increases the sp2 hybridization of CO(ad), facilitating the rate-determining step, CO* to (CHO)*. We find that the ligands stabilize the (HOOC-CH2)* intermediate, a key intermediate in the acetate pathway. In-situ Raman spectroscopy shows shifts in C-O, Cu-C, and C-S vibrational frequencies that agree with a picture of surface ligand-intermediate interactions. A Faradaic efficiency of 70% is obtained on optimized thiol-capped Cu catalysts, with onset potentials 100 mV lower than in the case of reference Cu catalysts.

Early Warning for the Electrolyzer: Monitoring CO2 Reduction via In-Line Electrochemical Impedance Spectroscopy.

The electrochemical CO2 reduction reaction (CO2 RR) to fuels and feedstocks presents an opportunity to decarbonize the chemical industry, and current electrolyzer performance levels approach commercial viability. However, stability remains below that required, in part because of the challenge of probing these electrolyzer systems in real time and the challenge of determining the root cause of failure. Failure can result from initial conditions (e. g., the over- or under-compression of the electrolyzer), gradual degradation of components (e. g., cathode or anode catalysts), the accumulation of products or by-products, or immediate changes such as the development of a hole in the membrane or a short circuit. Identifying and mitigating these assembly-related, gradual, and immediate failure modes would increase both electrolyzer lifetime and economic viability of CO2 RR. We demonstrate the continuous monitoring of CO2 RR electrolyzers during operation via non-disruptive, real-time electrochemical impedance spectroscopy (EIS) analysis. Using this technique, we characterise common failure modes - compression, salt formation, and membrane short circuits - and identify electrochemical parameter signatures for each. We further propose a framework to identify, predict, and prevent failures in CO2 RR electrolyzers. This framework allowed for the prediction of anode degradation ~11 hours before other indicators such as selectivity or voltage.

Bifunctional Gas Diffusion Electrode Enables In Situ Separation and Conversion of CO2 to Ethylene from Dilute Stream.

The requirement of concentrated carbon dioxide (CO2 ) feedstock significantly limits the economic feasibility of electrochemical CO2 reduction (eCO2 R) which often involves multiple intermediate processes, including CO2 capture, energy-intensive regeneration, compression, and transportation. Herein, a bifunctional gas diffusion electrode (BGDE) for separation and eCO2 R from a low-concentration CO2 stream is reported. The BGDE is demonstrated for the selective production of ethylene (C2 H4 ) by combining high-density-polyethylene-derived porous carbon (HPC) as a physisorbent with polycrystalline copper as a conversion catalyst. The BGDE shows substantial tolerance to 10 vol% CO2 exhibiting a Faradaic efficiency of ≈45% toward C2 H4 at a current density of 80 mA cm-2 , outperforming previous reports that utilized such partial pressure (PCO2 = 0.1 atm and above) and unaltered polycrystalline copper. Molecular dynamics simulation and mixed gas permeability assessment reveal that such selective performance is ensured by high CO2 uptake of the microporous HPC as well as continuous desorption owing to the molecular diffusion and concentration gradient created by the binary flow of CO2 and nitrogen (CO2 |N2 ) within the sorbent boundary. Based on detailed techno-economic analysis, it is concluded that this in situ process can be economically compelling by precluding the C2 H4 production cost associated with the energy-intensive intermediate steps of the conventional decoupled process.

Silver Nanowire/MnO2 Nanowire Hybrid Polymer Nanocomposites: Materials with High Dielectric Permittivity and Low Dielectric Loss.

This study reports the fabrication of hybrid nanocomposites based on silver nanowire/manganese dioxide nanowire/poly(methyl methacrylate) (AgNW/MnO2NW/PMMA), using a solution casting technique, with outstanding dielectric permittivity and low dielectric loss. AgNW was synthesized using the hard-template technique, and MnO2NW was synthesized employing a hydrothermal method. The prepared AgNW:MnO2NW (2.0:1.0 vol %) hybrid nanocomposite showed a high dielectric permittivity (64 at 8.2 GHz) and low dielectric loss (0.31 at 8.2 GHz), which are among the best reported values in the literature in the X-band frequency range (8.2-12.4 GHz). The superior dielectric properties of the hybrid nanocomposites were attributed to (i) dimensionality match between the nanofillers, which increased their synergy, (ii) better dispersion state of AgNW in the presence of MnO2NW, (iii) positioning of ferroelectric MnO2NW in between AgNWs, which increased the dielectric permittivity of nanodielectrics, thereby increasing dielectric permittivity of the hybrid nanocomposites, (iv) barrier role of MnO2NW, i.e., cutting off the contact spots of AgNWs and leading to lower dielectric loss, and (v) AgNW aligned structure, which increased the effective surface area of AgNWs, as nanoelectrodes. Comparison of the dielectric properties of the developed hybrid nanocomposites with the literature highlights their great potential for flexible capacitors.