Single‐atom materials: The application in energy conversion

Interdisciplinary materials, Journal Year: 2024, Volume and Issue: 3(1), P. 74 - 86

Published: Jan. 1, 2024

Abstract Single‐atom materials (SAMs) have become one of the most important power sources to push field energy conversion forward. Among main types energy, including thermal electrical solar and biomass SAMs realized ultra‐high efficiency show an appealing future in practical application. More than high activity, uniform active sites also provide a convincible model for chemists design comprehend mechanism behind phenomenon. Therefore, we presented insightful review application single‐atom material conversion. The challenges (e.g., accurate synthesis application) directions machine learning efficient design) applications are included, aiming guidance research next step.

Language: Английский

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The solvation environment of molecularly dispersed cobalt phthalocyanine determines methanol selectivity during electrocatalytic CO2 reduction

Nature Catalysis, Journal Year: 2024, Volume and Issue: 7(9), P. 987 - 999

Published: July 8, 2024

Language: Английский

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Downsizing Porphyrin Covalent Organic Framework Particles Using Protected Precursors for Electrocatalytic CO₂ Reduction

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(19)

Published: Feb. 1, 2024

Abstract Covalent organic frameworks (COFs) are promising electrocatalyst platforms owing to their designability, porosity, and stability. Recently, COFs with various chemical structures developed as efficient electrochemical CO 2 reduction catalysts. However, controlling the morphology of COF catalysts remains a challenge, which can limit electrocatalytic performance. Especially, while porphyrin show catalytic properties, particle size is mostly large uncontrolled because severe aggregation crystallites. In this work, new synthetic methodology for rationally downsized catalyst particles reported, where tritylated amine employed novel protected precursor synthesis. Trityl protection provides high solubility precursor, its deprotection proceeds in situ under typical synthesis conditions. Subsequent homogeneous nucleation colloidal growth yield smaller than conventional synthesis, suppressed crystallite aggregation. The exhibit superior performance reduction, higher production rate faradaic efficiency compared particles. improved attributed contact area conductive agent. This study reveals an important factor evaluation electrocatalysts strategy control it.

Language: Английский

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Best practices for in-situ and operando techniques within electrocatalytic systems

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

Published: March 16, 2025

In-situ and operando techniques in heterogeneous electrocatalysis are a powerful tool used to elucidate reaction mechanisms. Ultimately, they key determining concrete links between catalyst's physical/electronic structure its activity en route designing next-generation systems. To this end, the exact execution interpretation of these lines experiments is critical as determines strength conclusions that can be drawn what uncertainties remain. Instead focusing on how were understand systems, case with most reviews topic, work instead initiates nuanced discussion 1) best carry out each technique 2) initiate analysis which level insights from set in-situ or experiments/controls carried out. We focus several commonly techniques, including vibrational (IR, Raman) spectroscopy, X-ray absorption spectroscopy electrochemical mass spectrometry. In addition this, we include sections reactor design link theoretical modelling applicable across all techniques. While electrocatalysis, make when appropriate areas photo- thermo-catalytic highlight common pitfalls field, avoid them, sets complementary may strengthen analysis. end an overview gaps remain innovations must made overcome them. situ useful towards mechanistic investigations electrocatalytic systems but interpreted properly. Here, authors provide guidelines for practices use methods.

Language: Английский

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Advances and challenges in single-site catalysts towards electrochemical CO₂ methanation

Energy & Environmental Science, Journal Year: 2023, Volume and Issue: 16(11), P. 4812 - 4833

Published: Jan. 1, 2023

In this review, we systematically summarizes the activity descriptors of CO 2 methanation, recent advances SSCs for electrocatalytic and in situ characterizations used tracking structure change during RR.

Language: Английский

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电催化CO2还原的稳定性问题: 评论性综述

Science China Materials, Journal Year: 2024, Volume and Issue: 67(6), P. 1721 - 1739

Published: May 16, 2024

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Role of Mass Transport in Electrochemical CO₂ Reduction to Methanol Using Immobilized Cobalt Phthalocyanine

ACS Applied Energy Materials, Journal Year: 2024, Volume and Issue: 7(8), P. 3091 - 3098

Published: April 4, 2024

Electrochemical CO2 reduction (CO2R) using heterogenized molecular catalysts usually yields 2-electron products (CO, formate). Recently, it has been reported that certain preparations of immobilized cobalt phthalocyanine (CoPc) produce methanol (MeOH), a 6-electron product. Here, we demonstrate the significant role intermediate mass transport in CoPc selectivity to methanol. We first developed simple, physically mixed, polymer (and polyfluoroalkyl, PFAS)-free preparation on multiwalled carbon nanotubes (MWCNTs) which can be integrated onto Au electrodes poly(3,4-ethylenedioxythiophene) polystyrenesulfonate (PEDOT:PSS) adhesion layer. After optimization catalyst and loading, Faradaic efficiencies partial current densities 36% (±3%) 3.8 (±0.5) mA cm–2, respectively, are achieved CO2-saturated aqueous electrolyte. The electrolyte flow rate large effect. A linear velocity 8.5 cm/min produces highest MeOH selectivity, with higher rates increasing CO lower hydrogen evolution reaction, suggesting is an unbound intermediate. Using continuum multiphysics model assuming intermediate, show qualitative agreement optimal inlet rate. Polymer binders were not required achieve high efficiency for MWCNTs. also investigated formaldehyde as strain, but definitive conclusions could established.

Language: Английский

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Molecular architectures of iron complexes for oxygen reduction catalysis—Activity enhancement by hydroxide ions coupling

Proceedings of the National Academy of Sciences, Journal Year: 2024, Volume and Issue: 121(11)

Published: March 4, 2024

Developing cost-effective and high-performance electrocatalysts for oxygen reduction reaction (ORR) is critical clean energy generation. Here, we propose an approach to the synthesis of iron phthalocyanine nanotubes (FePc NTs) as a highly active selective electrocatalyst ORR. The performance significantly superior FePc in randomly aggregated molecularly dispersed states, well commercial Pt/C catalyst. When NTs are anchored on graphene, resulting architecture shifts ORR potentials above redox Fe 2+/3+ sites. This does not obey redox-mediated mechanism operative conventional with 2+ –N moiety serving Pourbaix analysis shows that sites couples HO − ions transfer, forming HO–Fe 3+ under turnover condition. chemisorption intermediates appropriately weakened compared state thus intrinsically more active.

Language: Английский

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Impact of the Surface Microenvironment on the Redox Properties of a Co-Based Molecular Cathode for Selective Aqueous Electrochemical CO₂-to-CO Reduction

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(22), P. 15345 - 15355

Published: May 20, 2024

Electrode-confined molecular catalysts are promising systems to enable the efficient conversion of CO2 useful products. Here, we describe development an original cathode for reduction CO based on noncovalent integration a tetraazamacrocyclic Co complex carbon nanotube-based matrix. Aqueous electrochemical characterization modified electrode allowed clear observation change redox behavior center as surface concentration was tuned, highlighting impact catalyst microenvironment its properties. The enabled CO2-to-CO in fully aqueous conditions, giving rise turnover number (TONCO) up 20 × 103 after 2 h constant electrolysis at mild overpotential (η = 450 mV) and with faradaic efficiency about 95%. Post operando measurements using techniques, inductively coupled plasma, X-ray photoelectron spectroscopy absorption films demonstrated that catalysis remained nature, making this Co-based new alternative electrocatalytic media.

Language: Английский

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Potential Dependence and Substituent Effect in CO₂ Electroreduction on a Cobalt Phthalocyanine Catalyst

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(12), P. 9575 - 9585

Published: June 11, 2024

Cobalt phthalocyanine molecules combined with carbon materials (CoPc@NC) have been reported to exhibit prominent electrocatalytic performance toward the CO2 reduction reaction (CO2RR). However, molecular-scale insights into mechanisms regarding its high activity or Faraday efficiency remain limited due great challenge in modeling electrochemical interface. Herein, an explicit computational model inclusion of solvation and electrode potential was employed explore mechanistic nature CO2RR at graphene-supported CoPc It is suggested that on molecular catalyst can be remarkably affected by potential. The DFT-based constrained ab initio dynamics simulations thermodynamic integration method support notion frontier orbitals easily modulated potentials thus influence redox during CO2RR. adsorption step involving partial charge transfer from strongly potential-dependent. Once absorbed, subsequent protonation, as rate-determining step, not significantly Moreover, overall catalytic enhanced introducing electron-donating substituent such a cyano group (−CN), which attributed redistribution between substrate catalyst. Our work only provides deep electronic structure CoPc@NC system but also illustrates critical role substituents catalyst, paving promising way for advancing efficient transformation.

Language: Английский

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