Intrinsic Electrocatalytic Activity Regulation of M–N–C Single‐Atom Catalysts for the Oxygen Reduction Reaction

Angewandte Chemie International Edition, Год журнала: 2020, Номер 60(9), С. 4448 - 4463

Опубликована: Апрель 21, 2020

Abstract Single‐atom catalysts (SACs) with highly active sites atomically dispersed on substrates exhibit unique advantages regarding maximum atomic efficiency, abundant chemical structures, and extraordinary catalytic performances for multiple important reactions. In particular, M–N–C SACs (M=transition metal atom) demonstrate optimal electrocatalytic activity the oxygen reduction reaction (ORR) have attracted extensive attention recently. Despite substantial efforts in fabricating various SACs, principles regulating intrinsic of their not been sufficiently studied. this Review, we summarize regulation strategies promoting ORR by modulation center atoms, coordinated environmental guest groups. Theoretical calculations experimental investigations are both included to afford a comprehensive understanding structure–performance relationship. Finally, future directions developing advanced other analogous reactions proposed.

Язык: Английский

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Simultaneously Achieving High Activity and Selectivity toward Two-Electron O₂ Electroreduction: The Power of Single-Atom Catalysts

ACS Catalysis, Год журнала: 2019, Номер 9(12), С. 11042 - 11054

Опубликована: Сен. 23, 2019

On-site production of hydrogen peroxide (H2O2) using electrochemical methods could be more efficient than the current industrial process. However, due to existence scaling relations for adsorption reaction intermediates, there is a long established trade-off between activity and selectivity catalysts, as enhancement catalytic typically accompanied by four-electron O2 reduction (ORR), leading reduced H2O2 production. Herein, means density functional theory (DFT) computations, we reported feasibility several classes important representative experimentally achievable single-atom catalysts (SACs) toward two-electron ORR, paying attention their stability, selectivity, at acidic medium. Starting from 210 two-dimensional (2D) SACs, demonstrated that 31 SACs have potential break metal-based simultaneously achieve high screened out 7 with higher PtHg4 in media. Especially, noble metal-free SAC, namely, single Zn atom centered phthalocyanine (Zn@Pc-N4), has remarkable improvement small overpotential 0.15 V. Moreover, multivariable analysis machine-learning techniques, provided comprehensive understanding underlying origin unveiled intrinsic correlations structure performance. This work may pave way design discovery promising materials

Язык: Английский

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Tailoring Selectivity of Electrochemical Hydrogen Peroxide Generation by Tunable Pyrrolic‐Nitrogen‐Carbon

Advanced Energy Materials, Год журнала: 2020, Номер 10(21)

Опубликована: Апрель 17, 2020

Abstract The electrochemical reduction of O 2 via a two‐electron reaction pathway to H provides possibility for replacing the current anthraquinone process, enabling sustainable and decentralized production. Here, nitrogen‐rich few‐layered graphene (N‐FLG) with tunable nitrogen configuration is developed generation. A positive correlation between content pyrrolic‐N selectivity experimentally observed. critical role elucidated by variable intermediate adsorption profiles as well dependent negative shifts peak on X‐ray near edge structure spectra. By virtue optimized N doping unique porous structure, as‐fabricated N‐FLG electrocatalyst exhibits high toward synthesis superior long‐term stability. To achieve high‐value products both anode cathode energy efficiency, practical device coupling generation furfural oxidation assembled, simultaneously yield rate at (9.66 mol h −1 g cat ) 2‐furoic acid (2.076 m −2 under small cell voltage 1.8 V.

Язык: Английский

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Theory-oriented screening and discovery of advanced energy transformation materials in electrocatalysis

Advanced Powder Materials, Год журнала: 2021, Номер 1(1), С. 100013 - 100013

Опубликована: Ноя. 15, 2021

Various metal-based electrocatalysts from nanocrystals, to clusters and single-atoms, have been well-discovered towards high-efficient power devices electrocatalytic conversion. To accelerate energy transformation materials discovery, developing high-throughput DFT calculations machine-learning techniques is of great necessity. This review comprehensively outlines the latest progress theory-guided design advanced materials. Especially, we focus on study single atoms in various devices, such as fuel cell (oxygen reduction reaction, ORR; acid oxidation reaction; alcohol reaction), other reactions for energy-related conversion small molecules, H2O2 evolution (2e− ORR), water splitting (H2 reaction/O2 HER/OER), N2 reaction (NRR), CO2 (CO2RR). Firstly, electronic structure, interaction mechanism, activation path are discussed provide an overall blueprint electrocatalysis batteries mentioned above. Thereafter, experimental synthesis strategies, structural recognition, performance figured out. Finally, some viewpoints into current issues future concept provided.

Язык: Английский

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A Review on Challenges and Successes in Atomic-Scale Design of Catalysts for Electrochemical Synthesis of Hydrogen Peroxide

ACS Catalysis, Год журнала: 2020, Номер 10(14), С. 7495 - 7511

Опубликована: Июнь 10, 2020

Hydrogen peroxide is a valuable chemical oxidant with wide range of applications in variety industrial processes, especially water sanitization. Electrochemical synthesis hydrogen (H2O2) through two-electron oxygen reduction reaction (2e-ORR) or oxidation (2e-WOR) has emerged as an appealing process for onsite production this chemically oxidant. On-site produced H2O2 can be applied wastewater treatment remote locations any where needed oxidizing agent. This Review studies the theoretical efforts understanding challenges catalysis electrochemical well providing design principles more efficient catalyst materials.

Язык: Английский

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Confined local oxygen gas promotes electrochemical water oxidation to hydrogen peroxide

Nature Catalysis, Год журнала: 2020, Номер 3(2), С. 125 - 134

Опубликована: Янв. 6, 2020

Язык: Английский

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Highly active and selective oxygen reduction to H2O2 on boron-doped carbon for high production rates

Nature Communications, Год журнала: 2021, Номер 12(1)

Опубликована: Июль 9, 2021

Abstract Oxygen reduction reaction towards hydrogen peroxide (H 2 O ) provides a green alternative route for H production, but it lacks efficient catalysts to achieve high selectivity and activity simultaneously under industrial-relevant production rates. Here we report boron-doped carbon (B-C) catalyst which can overcome this activity-selectivity dilemma. Compared the state-of-the-art oxidized catalyst, B-C presents enhanced (saving more than 210 mV overpotential) currents (up 300 mA cm −2 while maintaining (85–90%). Density-functional theory calculations reveal that boron dopant site is responsible due low thermodynamic kinetic barriers. Employed in our porous solid electrolyte reactor, demonstrates direct continuous generation of pure solutions with 95%) partial ~400 ), illustrating catalyst’s great potential practical applications future.

Язык: Английский

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High-Concentration Single Atomic Pt Sites on Hollow CuSx for Selective O2 Reduction to H2O2 in Acid Solution

Chem, Год журнала: 2019, Номер 5(8), С. 2099 - 2110

Опубликована: Май 23, 2019

Язык: Английский

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Recent Progress of Electrochemical Production of Hydrogen Peroxide by Two‐Electron Oxygen Reduction Reaction

Advanced Science, Год журнала: 2021, Номер 8(15)

Опубликована: Май 27, 2021

Shifting electrochemical oxygen reduction reaction (ORR) via two-electron pathway becomes increasingly crucial as an alternative/green method for hydrogen peroxide (H2 O2 ) generation. Here, the development of 2e- ORR catalysts in recent years is reviewed, aspects mechanism exploration, types high-performance catalysts, factors to influence catalytic performance, and potential applications ORR. Based on previous theoretical experimental studies, underlying firstly unveiled, aspect pathway, thermodynamic free energy diagram, limiting potential, volcano plots. Then, various efficient producing H2 are summarized. Additionally, active sites catalysts' such electronic structure, carbon defect, functional groups (O, N, B, S, F etc.), synergistic effect, others (pH, pore steric hindrance etc.) discussed. The electrogeneration also has wastewater treatment, disinfection, organics degradation, storage. Finally, future directions prospects electrochemically examined. These insights may help develop highly active/selective shape application this method.

Язык: Английский

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Promoting H2O2 production via 2-electron oxygen reduction by coordinating partially oxidized Pd with defect carbon

Nature Communications, Год журнала: 2020, Номер 11(1)

Опубликована: Май 1, 2020

Abstract Electrochemical synthesis of H 2 O through a selective two-electron (2e − ) oxygen reduction reaction (ORR) is an attractive alternative to the industrial anthraquinone oxidation method, as it allows decentralized production. Herein, we report that synergistic interaction between partially oxidized palladium (Pd δ+ and oxygen-functionalized carbon can promote 2e ORR in acidic electrolytes. An electrocatalyst synthesized by solution deposition amorphous Pd clusters 3 4 onto mildly nanotubes -OCNT) shows nearly 100% selectivity toward positive shift onset potential ~320 mV compared with OCNT substrate. A high mass activity (1.946 mg −1 at 0.45 V) -OCNT achieved. Extended X-ray absorption fine structure characterization density functional theory calculations suggest nearby oxygen-containing groups key for ORR.

Язык: Английский

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