Single‐atom catalysis for carbon neutrality

Carbon Energy, Год журнала: 2022, Номер 4(6), С. 1021 - 1079

Опубликована: Июль 14, 2022

Abstract Currently, more than 86% of global energy consumption is still mainly dependent on traditional fossil fuels, which causes resource scarcity and even emission high amounts carbon dioxide (CO 2 ), resulting in a severe “Greenhouse effect.” Considering this situation, the concept “carbon neutrality” has been put forward by 125 countries one after another. To achieve goals neutrality,” two main strategies to reduce CO emissions develop sustainable clean can be adopted. Notably, these are crucial for synthesis advanced single‐atom catalysts (SACs) energy‐related applications. In review, we highlight unique SACs conversion into high‐efficiency energy, example, through photocatalytic, electrocatalytic, thermal catalytic hydrogenation technologies, convert hydrocarbon fuels (CO, CH 4 , HCOOH, 3 OH, multicarbon [C 2+ ] products). addition, introduce technologies devices replace polluting such as photocatalytic electrocatalytic water splitting produce hydrogen oxygen reduction reaction (ORR) fuel cells. Impressively, several representative examples (including d ‐, ds p f ‐blocks) conversion, H ORR discussed describe methods, characterization, corresponding activity. Finally, review concludes with description challenges outlooks future applications contributing toward neutrality.

Язык: Английский

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Tuning the spin state of Fe single atoms by Pd nanoclusters enables robust oxygen reduction with dissociative pathway

Chem, Год журнала: 2022, Номер 9(1), С. 181 - 197

Опубликована: Окт. 27, 2022

Язык: Английский

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Oxygen doping of cobalt-single-atom coordination enhances peroxymonosulfate activation and high-valent cobalt–oxo species formation

Proceedings of the National Academy of Sciences, Год журнала: 2023, Номер 120(16)

Опубликована: Апрель 11, 2023

The high-valent cobalt-oxo species (Co(IV)=O) is being increasingly investigated for water purification because of its high redox potential, long half-life, and antiinterference properties. However, generation Co(IV)=O inefficient unsustainable. Here, a cobalt-single-atom catalyst with N/O dual coordination was synthesized by O-doping engineering. O-doped (Co-OCN) greatly activated peroxymonosulfate (PMS) achieved pollutant degradation kinetic constant 73.12 min-1 g-2, which 4.9 times higher than that Co-CN (catalyst without O-doping) those most reported single-atom catalytic PMS systems. Co-OCN/PMS realized dominant oxidation pollutants increasing the steady-state concentration (1.03 × 10-10 M) 5.9 compared Co-CN/PMS. A competitive kinetics calculation showed contribution to micropollutant 97.5% during process. Density functional theory calculations influenced charge density (increased Bader transfer from 0.68 0.85 e), optimized electron distribution Co center d-band -1.14 -1.06 eV), enhanced adsorption energy -2.46 -3.03 eV, lowered barrier key reaction intermediate (*O*H2O) formation 1.12 0.98 eV. Co-OCN fabricated on carbon felt flow-through device, continuous efficient removal micropollutants (degradation efficiency >85% after 36 h operation). This study provides new protocol activation elimination through heteroatom-doping metal-oxo purification.

Язык: Английский

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Construction of Six‐Oxygen‐Coordinated Single Ni Sites on g‐C₃N₄ with Boron‐Oxo Species for Photocatalytic Water‐Activation‐Induced CO₂ Reduction

Advanced Materials, Год журнала: 2021, Номер 33(48)

Опубликована: Сен. 27, 2021

Abstract The configuration regulation of single‐atom photocatalysts (SAPCs) can significantly influence the interfacial charge transfer and subsequent catalytic process. construction conventional SAPCs for aqueous CO 2 reduction is mainly devoted toward favorable activation photoreduction , however, role water frequently neglected. In this work, single Ni atoms are successfully anchored by boron‐oxo species on g‐C 3 N 4 nanosheets through a facile ion‐exchange method. dative interaction between B atom sp guarantees high dispersion species, where O coordinate with (II) sites to obtain unique six‐oxygen‐coordinated configuration. optimized photocatalyst, rivaling Pt‐modified nanosheets, provides excellent rate CH as products. Quasi‐in‐situ X‐ray photoelectron spectra, transient absorption isotopic labeling, in situ Fourier transform infrared spectra reveal that as‐fabricated effectively capture photoelectrons CN along BO bridges preferentially activate adsorbed produce H eventually induce hydrogen‐assisted reduction. This work diversifies synthetic strategies catalysts insight correlation reaction pathway.

Язык: Английский

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Microenvironment Engineering of Single/Dual‐Atom Catalysts for Electrocatalytic Application

Advanced Materials, Год журнала: 2023, Номер 35(31)

Опубликована: Фев. 23, 2023

Single/dual-metal atoms supported on carbon matrix can be modulated by coordination structure and neighboring active sites. Precisely designing the geometric electronic uncovering structure-property relationships of single/dual-metal confront with grand challenges. Herein, this review summarizes latest progress in microenvironment engineering single/dual-atom sites via a comprehensive comparison single-atom catalyst (SACs) dual-atom catalysts (DACs) term design principles, modulation strategy, theoretical understanding structure-performance correlations. Subsequently, recent advances several typical electrocatalysis process are discussed to get general reaction mechanisms finely-tuned SACs DACs. Finally, full-scaled summaries challenges prospects given for This will provide new inspiration development atomically dispersed electrocatalytic application.

Язык: Английский

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Metal single-site catalyst design for electrocatalytic production of hydrogen peroxide at industrial-relevant currents

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Янв. 12, 2023

Direct hydrogen peroxide (H2O2) electrosynthesis via the two-electron oxygen reduction reaction is a sustainable alternative to traditional energy-intensive anthraquinone technology. However, high-performance and scalable electrocatalysts with industrial-relevant production rates remain be challenging, partially due insufficient atomic level understanding in catalyst design. Here we utilize theoretical approaches identify transition-metal single-site catalysts for using *OOH binding energy as descriptor. The predictions are then used guidance synthesize desired cobalt O-modified Co-(pyrrolic N)4 configuration that can achieve current densities up 300 mA cm-2 96-100% Faradaic efficiencies H2O2 at record rate of 11,527 mmol h-1 gcat-1. Here, show feasibility versatility metal design various commercial carbon phthalocyanine starting materials high applicability acidic, neutral alkaline electrolytes.

Язык: Английский

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Dynamic Stability of Copper Single-Atom Catalysts under Working Conditions

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(37), С. 17140 - 17148

Опубликована: Сен. 12, 2022

The long-term stability of single-atom catalysts is a major factor affecting their large-scale commercial application. How to evaluate the dynamic under working conditions still lacking. Here, taking single copper atom embedded in N-doped graphene as an example, "constant-potential hybrid-solvation model" used reversible transformation between atoms and clusters realistic reaction conditions. It revealed that adsorption H vital driving force for leaching Cu from catalyst surface. more negative electrode potential, stronger H. As result, competitive hydrogen evolution inhibited, Cu-N bonds are weakened, resulting some being tethered on surface dissolved aqueous solution. collision two states forms transient cluster structure true catalytic active site promote CO2 reduction ethanol. applied potential released or switched positive value, hydroxyl radicals (OH•) play dominant role oxidation process cluster, then returns initial atomic dispersion state by redeposition, completing reconstruction cycle catalyst. Our work provides fundamental understanding at level calls reassessment currently reported considering

Язык: Английский

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Graphene‐Supported Atomically Dispersed Metals as Bifunctional Catalysts for Next‐Generation Batteries Based on Conversion Reactions

Advanced Materials, Год журнала: 2021, Номер 34(5)

Опубликована: Окт. 22, 2021

Next-generation batteries based on conversion reactions, including aqueous metal-air batteries, nonaqueous alkali metal-O2 and -CO2 metal-chalcogen metal-ion have attracted great interest. However, their use is restricted by inefficient reversible of active agents. Developing bifunctional catalysts to accelerate the reaction kinetics in both discharge charge processes urgently needed. Graphene-, or graphene-like carbon-supported atomically dispersed metal (G-ADMCs) been demonstrated show excellent activity various electrocatalytic making them promising candidates. Different from G-ADMCs for catalysis, which only require high one direction, rechargeable should provide discharging charging. This review provides guidance design fabrication next-generation reactions. The key challenges that prevent conversion, origin G-ADMCs, current principles highly analyzed highlighted each conversion-type battery. Finally, a summary outlook development G-ADMC materials with energy density efficiency are given.

Язык: Английский

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Manipulating the oxygen reduction reaction pathway on Pt-coordinated motifs

Nature Communications, Год журнала: 2022, Номер 13(1)

Опубликована: Фев. 3, 2022

Electrochemical oxygen reduction could proceed via either 4e

Язык: Английский

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Low‐Coordinated CoNC on Oxygenated Graphene for Efficient Electrocatalytic H₂O₂ Production

Advanced Functional Materials, Год журнала: 2021, Номер 32(5)

Опубликована: Окт. 21, 2021

Abstract Electrochemical H 2 O production through the 2‐electron oxygen reduction reaction (ORR) is a promising alternative to energy‐intensive anthraquinone process. Herein, by simultaneously regulating coordination number of atomically dispersed cobalt sites and nearby functional groups via one‐step microwave thermal shock, highly selective active CoNC electrocatalyst for electrosynthesis that exhibits high selectivity (91.3%), outstanding mass activity (44.4 A g −1 at 0.65 V), large kinetic current density (11.3 mA cm −2 V) in 0.1 m KOH obtained. In strong contrast typical CoN 4 moieties 4‐electron ORR, present catalyst possesses low‐coordinated configuration abundant epoxide groups, which work synergy promoting as demonstrated series control experiments theoretical simulations. This study may provide an effective avenue modulating composition structure electrocatalysts atomic scale, leading development new with unprecedented reactivity.

Язык: Английский

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