Unveiling pH‐Dependent Adsorption Strength of *CO₂⁻ Intermediate over High‐Density Sn Single Atom Catalyst for Acidic CO₂‐to‐HCOOH Electroreduction

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(14)

Published: Feb. 16, 2024

Abstract The acidic electrochemical CO 2 reduction reaction (CO RR) for direct formic acid (HCOOH) production holds promise in meeting the carbon‐neutral target, yet its performance is hindered by competing hydrogen evolution (HER). Understanding adsorption strength of key intermediates electrolyte indispensable to favor RR over HER. In this work, high‐density Sn single atom catalysts (SACs) were prepared and used as catalyst, reveal pH‐dependent coverage *CO − intermediatethat enables enhanced towards HCOOH production. At pH=3, SACs could deliver a high Faradaic efficiency (90.8 %) formation corresponding partial current density up −178.5 mA cm −2 . detailed situ attenuated total reflection Fourier transform infrared (ATR‐FTIR) spectroscopic studies that favorable alkaline microenvironment formed near surface SACs, even electrolyte. More importantly, intermediate unravelled which turn affects competition between HER

Language: Английский

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Immobilized Tetraalkylammonium Cations Enable Metal‐free CO₂ Electroreduction in Acid and Pure Water

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(9)

Published: Jan. 2, 2024

Abstract Carbon dioxide reduction reaction (CO 2 RR) provides an efficient pathway to convert CO into desirable products, yet its commercialization is greatly hindered by the huge energy cost due loss and regeneration. Performing RR under acidic conditions containing alkali cations can potentially address issue, but still causes (bi)carbonate deposition at high current densities, compromising product Faradaic efficiencies (FEs) in present‐day acid‐fed membrane electrode assemblies. Herein, we present a strategy using positively charged polyelectrolyte—poly(diallyldimethylammonium) immobilized on graphene oxide via electrostatic interactions displace cations. This enables FE of 85 %, carbon efficiency 93 (EE) 35 % for 100 mA cm −2 modified Ag catalysts acid. In pure‐water‐fed reactor, obtained 78 with 30 EE 40 °C. All performance metrics are comparable or even exceed those attained presence metal

Language: Английский

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A covalent molecular design enabling efficient CO2 reduction in strong acids

Nature Synthesis, Journal Year: 2024, Volume and Issue: 3(10), P. 1231 - 1242

Published: June 25, 2024

Language: Английский

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Addressing the Carbonate Issue: Electrocatalysts for Acidic CO₂ Reduction Reaction

Advanced Materials, Journal Year: 2024, Volume and Issue: unknown

Published: May 9, 2024

Abstract Electrochemical CO 2 reduction reaction (CO RR) powered by renewable energy provides a promising route to conversion and utilization. However, the widely used neutral/alkaline electrolyte consumes large amount of produce (bi)carbonate byproducts, leading significant challenges at device level, thereby impeding further deployment this reaction. Conducting RR in acidic electrolytes offers solution address “carbonate issue”; however, it presents inherent difficulties due competitive hydrogen evolution reaction, necessitating concerted efforts toward advanced catalyst electrode designs achieve high selectivity activity. This review encompasses recent developments RR, from mechanism elucidation design engineering. begins discussing mechanistic understanding pathway, laying foundation for RR. Subsequently, an in‐depth analysis advancements catalysts is provided, highlighting heterogeneous catalysts, surface immobilized molecular enhancement. Furthermore, progress made device‐level applications summarized, aiming develop high‐performance systems. Finally, existing future directions are outlined, emphasizing need improved selectivity, activity, stability, scalability.

Language: Английский

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High‐Throughput Screening and General Synthesis Strategy of Single‐Atom Nanozymes for Oral Squamous Cell Carcinoma Therapy

Advanced Materials, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 5, 2025

Abstract Single‐atom nanozymes (SAzymes), with their superior enzyme‐like catalytic activity, have emerged as promising candidates for oncology therapeutics. The well‐defined structures of SAzymes make them well predictable by experiences and theoretical calculation. However, the effects metal center species coordination environments on activity are variable, screening artificial experiments is challenging. High‐throughput can rapidly select optimal thus better application in tumor therapy highly desirable. Herein, a “high‐throughput screening‐SAzymes structures” system established efficient drug preparation density functional theory oxidase‐like processes screened differences brought about different metals environments. Through this process, transition (Mn, Fe, Co, Ni) active centers synthesized then tested multi‐enzyme activities. It found that SAzyme Co exhibited best further showed good anti‐oral squamous cell carcinoma properties both vitro vivo. This study opens up new avenue rational design oral cancer combining computational experimental validation.

Language: Английский

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Stabilizing Ni Single-Atom Sites through Introducing Low-Valence Ni Species for Durably Efficient Electrochemical CO2 Reduction

Applied Catalysis B Environment and Energy, Journal Year: 2025, Volume and Issue: unknown, P. 125151 - 125151

Published: Feb. 1, 2025

Language: Английский

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Lanthanide single-atom catalysts for efficient CO2-to-CO electroreduction

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: March 27, 2025

Abstract Single-atom catalysts (SACs) have received increasing attention due to their 100% atomic utilization efficiency. The electrochemical CO 2 reduction reaction (CO RR) using SAC offers a promising approach for utilization, but achieving facile adsorption and desorption remains challenging traditional SACs. Instead of singling out specific atoms, we propose strategy utilizing atoms from the entire lanthanide (Ln) group facilitate RR. Density functional theory calculations, operando spectroscopy, X-ray absorption spectroscopy elucidate bridging mechanism representative erbium (Er) single-atom catalyst. As result, realize series Ln SACs spanning 14 elements that exhibit Faradaic efficiencies exceeding 90%. Er catalyst achieves high turnover frequency ~130,000 h − 1 at 500 mA cm . Moreover, 34.7% full-cell energy efficiency 70.4% single-pass conversion are obtained 200 with acidic electrolyte. This catalytic platform leverages collective potential group, introducing new possibilities efficient -to-CO beyond through exploration unique bonding motifs in catalysts.

Language: Английский

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Hydrophobized electrospun nanofibers of hierarchical porosity as the integral gas diffusion electrode for full-pH CO₂ electroreduction in membrane electrode assemblies

Energy & Environmental Science, Journal Year: 2023, Volume and Issue: 16(10), P. 4423 - 4431

Published: Jan. 1, 2023

Hydrophobized nanofibers of hierarchical porosity as the integral gas diffusion electrode are demonstrated. The GDE showcases stable operation for >273 hours in neutral MEA and a single-pass CO 2 conversion 78% acidic MEA.

Language: Английский

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Advanced Catalyst Design and Reactor Configuration Upgrade in Electrochemical Carbon Dioxide Conversion

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(52)

Published: Aug. 20, 2023

Abstract Electrochemical carbon dioxide reduction reaction (CO 2 RR) driven by renewable energy shows great promise in mitigating and potentially reversing the devastating effects of anthropogenic climate change environmental degradation. The simultaneous synthesis energy‐dense chemicals can meet global demand while decoupling emissions from economic growth. However, development CO RR technology faces challenges catalyst discovery device optimization that hinder their industrial implementation. In this contribution, a comprehensive overview current state research is provided, starting with background motivation for technology, followed fundamentals evaluated metrics. Then underlying design principles electrocatalysts are discussed, emphasizing structure–performance correlations advanced electrochemical assembly cells increase selectivity throughput. Finally, review looks to future identifies opportunities innovation mechanism discovery, material screening strategies, assemblies move toward carbon‐neutral society.

Language: Английский

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Toward Unifying the Mechanistic Concepts in Electrochemical CO₂ Reduction from an Integrated Material Design and Catalytic Perspective

Advanced Functional Materials, Journal Year: 2022, Volume and Issue: 32(51)

Published: Oct. 17, 2022

Electrocatalytic CO2 reduction (eCO2RR) is one of the avenues with most potential toward achieving sustainable energy economy and global climate change targets by harvesting renewable into value-added fuels chemicals. From an industrial standpoint, eCO2RR provides specific advantages over thermochemical photochemical pathways in terms much broader product scope, high specificity, easy adaptability to electricity infrastructure. However, unlike water electrolyzers, lack suitable cathode materials for impedes its commercialization due material design challenges. The current state-of-the-art catalysts suffer largely from low reaction rates, insufficient C2+ selectivity, overpotentials, industrial-scale stability. Overcoming scientific applied technical hurdles commercial realization demands a holistic integration catalytic designs, deep mechanistic understanding, efficient process engineering. Special emphasis on understanding performance outcome sought guide future that can play significant role closing anthropogenic carbon loop. This article integrative approach understand principles robust catalyst superimposed underlying projections which strongly depend experimental conditions viz. choice electrolyte, reactor membrane design, pH solvent, partial pressure CO2.

Language: Английский

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