Electrocatalysis for CO₂conversion: from fundamentals to value-added products

Chemical Society Reviews, Год журнала: 2021, Номер 50(8), С. 4993 - 5061

Опубликована: Янв. 1, 2021

This timely and comprehensive review mainly summarizes advances in heterogeneous electroreduction of CO₂: from fundamentals to value-added products.

Язык: Английский

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Rational Design and General Synthesis of Multimetallic Metal–Organic Framework Nano‐Octahedra for Enhanced Li–S Battery

Advanced Materials, Год журнала: 2021, Номер 33(45)

Опубликована: Сен. 23, 2021

Abstract Metal–organic frameworks (MOFs), which consist of central metal nodes and organic linkers, constitute a fast growing class crystalline porous materials with excellent application potential. Herein, series Mn‐based multimetallic MOF (bimetallic trimetallic MIL‐100) nano‐octahedra are prepared by facile one‐pot synthetic strategy. The types proportions the incorporated elements can be tuned while retaining original topological structure. introduction other ions is verified at atomic level combining X‐ray absorption fine structure experiments theoretical calculations. Furthermore, these MIL‐100 utilized as sulfur hosts to prepare cathodes for Li–S batteries. MnNi‐MIL‐100@S cathode exhibits best battery performance among all reported MIL‐100@S composite materials, reversible capacity ≈708.8 mAh g −1 after 200 cycles. strategy described herein incorporate into architecture, parent monometallic cannot directly, thus rationally generating novel MOFs. Importantly, also allows general synthesis study various micro‐/nanoscale MOFs in energy storage field.

Язык: Английский

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Conductive Two‐Dimensional Phthalocyanine‐based Metal–Organic Framework Nanosheets for Efficient Electroreduction of CO₂

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(31), С. 17108 - 17114

Опубликована: Май 25, 2021

Abstract The electrocatalytic conversion of CO 2 into value‐added chemicals is a promising approach to realize carbon‐energy balance. However, low current density still limits the application electroreduction reaction (CO RR). Metal–organic frameworks (MOFs) are one class alternatives for RR due their periodically arranged isolated metal active sites. poor conductivity traditional MOFs usually results in RR. We have prepared conductive two‐dimensional (2D) phthalocyanine‐based MOF (NiPc‐NiO 4 ) nanosheets linked by nickel‐catecholate, which can be employed as highly efficient electrocatalysts CO. obtained NiPc‐NiO has good and exhibited very high selectivity 98.4 % toward production large partial 34.5 mA cm −2 , outperforming reported catalysts. This work highlights potential crystalline electrocatalysis.

Язык: Английский

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Engineering Bismuth–Tin Interface in Bimetallic Aerogel with a 3D Porous Structure for Highly Selective Electrocatalytic CO₂ Reduction to HCOOH

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(22), С. 12554 - 12559

Опубликована: Март 15, 2021

Abstract Electrochemical reduction of CO 2 (CO RR) into valuable hydrocarbons is appealing in alleviating the excessive level. We present very first utilization metallic bismuth–tin (Bi‐Sn) aerogel for RR with selective HCOOH production. A non‐precious bimetallic Bi‐Sn readily prepared at ambient temperature, which exhibits 3D morphology interconnected channels, abundant interfaces and a hydrophilic surface. Superior to Bi Sn, exposes more active sites it has favorable mass transfer properties, endow high FE 93.9 %. Moreover, achieves ca. 90 % that was maintained 10 h flow battery. In situ ATR‐FTIR measurements confirmed formation *HCOO rate‐determining step toward formic acid generation. DFT demonstrated coexistence Sn optimized energy barrier production HCOOH, thereby improving catalytic activity.

Язык: Английский

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The Controllable Reconstruction of Bi‐MOFs for Electrochemical CO₂ Reduction through Electrolyte and Potential Mediation

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(33), С. 18178 - 18184

Опубликована: Июль 9, 2021

Abstract Monitoring and controlling the reconstruction of materials under working conditions is crucial for precise identification active sites, elucidation reaction mechanisms, rational design advanced catalysts. Herein, a Bi‐based metal–organic framework (Bi‐MOF) electrochemical CO 2 reduction selected as case study. In situ Raman spectra combined with ex electron microscopy reveal that intricate Bi‐MOF can be controlled using two steps: 1) electrolyte‐mediated dissociation conversion to Bi O 3 , 2) potential‐mediated Bi. The intentionally reconstructed catalyst exhibits excellent activity, selectivity, durability formate production, unsaturated surface atoms formed during become sites. This work emphasizes significant impact pre‐catalyst provides insight into highly stable electrocatalysts through regulation these processes.

Язык: Английский

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Highly Selective Tandem Electroreduction of CO₂ to Ethylene over Atomically Isolated Nickel–Nitrogen Site/Copper Nanoparticle Catalysts

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(48), С. 25485 - 25492

Опубликована: Сен. 17, 2021

Herein, an effective tandem catalysis strategy is developed to improve the selectivity of CO2 RR towards C2 H4 by multiple distinct catalytic sites in local vicinity. An earth-abundant elements-based electrocatalyst PTF(Ni)/Cu constructed uniformly dispersing Cu nanoparticles (NPs) on porphyrinic triazine framework anchored with atomically isolated nickel-nitrogen (PTF(Ni)) for enhanced produce . The Faradaic efficiency reaches 57.3 % at -1.1 V versus reversible hydrogen electrode (RHE), which about 6 times higher than non-tandem catalyst PTF/Cu, produces CH4 as major carbon product. operando infrared spectroscopy and theoretic density functional theory (DFT) calculations reveal that high concentration CO generated PTF(Ni) can facilitate C-C coupling form nearby NP sites. work offers avenue design electrocatalysts highly selective multicarbon products via a route.

Язык: Английский

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Designing a Built-In Electric Field for Efficient Energy Electrocatalysis

ACS Nano, Год журнала: 2022, Номер 16(12), С. 19959 - 19979

Опубликована: Дек. 15, 2022

To utilize intermittent renewable energy as well achieve the goals of peak carbon dioxide emissions and neutrality, various electrocatalytic devices have been developed. However, reactions, e.g., hydrogen evolution reaction/oxygen reaction in overall water splitting, polysulfide conversion lithium–sulfur batteries, formation/decomposition lithium peroxide lithium–oxygen nitrate reduction to degrade sewage, suffer from sluggish kinetics caused by multielectron transfer processes. Owing merits accelerated charge transport, optimized adsorption/desorption intermediates, raised conductivity, regulation microenvironment, ease combine with geometric characteristics, built-in electric field (BIEF) is expected overcome above problems. Here, we give a Review about very recent progress BIEF for efficient electrocatalysis. First, construction strategies characterization methods (qualitative quantitative analysis) are summarized. Then, up-to-date overviews engineering electrocatalysis, attention on electron structure optimization microenvironment modulation, analyzed discussed detail. In end, challenges perspectives proposed. This gives deep understanding design electrocatalysts next-generation storage devices.

Язык: Английский

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Density Functional Theory for Electrocatalysis

Energy & environment materials, Год журнала: 2021, Номер 5(1), С. 157 - 185

Опубликована: Апрель 27, 2021

It is a considerably promising strategy to produce fuels and high‐value chemicals through an electrochemical conversion process in the green sustainable energy systems. Catalysts for electrocatalytic reactions, including hydrogen evolution reaction (HER), oxygen (OER), reduction (ORR), nitrogen (NRR), carbon dioxide (CO 2 RR), play significant role advanced technologies, such as water splitting devices, fuel cells, rechargeable metal‐air batteries. Developing low‐cost highly efficient electrocatalysts closely related establishing composition–structure–activity relationships fundamental understanding of catalytic mechanisms. Density functional theory (DFT) emerging important computational tool that can provide insights into relationship between performances physical/chemical properties catalysts. This article presents review on progress DFT, simulations, within framework processes, well designs virtual screenings new electrocatalysts. Some useful descriptors analysis tools evaluating are highlighted, formation energies, d ‐band model, scaling relation, e g orbital occupation, free energies adsorption. Furthermore, remaining questions perspectives development DFT electrocatalysis also proposed.

Язык: Английский

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Divergent Paths, Same Goal: A Pair‐Electrosynthesis Tactic for Cost‐Efficient and Exclusive Formate Production by Metal–Organic‐Framework‐Derived 2D Electrocatalysts

Advanced Materials, Год журнала: 2021, Номер 33(25)

Опубликована: Май 14, 2021

Abstract Electrosynthesis of formic acid/formate is a promising alternative protocol to industrial processes. Herein, pioneering pair‐electrosynthesis tactic reported for exclusively producing formate via coupling selectively electrocatalytic methanol oxidation reaction (MOR) and CO 2 reduction (CO RR), in which the electrode derived from Ni‐based metal–organic framework (Ni‐MOF) nanosheet arrays (Ni‐NF‐Af), as well Bi‐MOF‐derived ultrathin bismuthenes (Bi‐enes), both obtained through an situ electrochemical conversion process, are used efficient anodic cathodic electrocatalysts, respectively, achieving concurrent yielding same high‐value product at electrodes with greatly reduced energy input. The as‐prepared Ni‐NF‐Af only needs quite low potentials reach large current densities (e.g., 100 mA cm −2 @1.345 V) ≈100% selectivity methanol‐to‐formate conversion. Meanwhile, RR cathode, Bi‐enes can simultaneously exhibit near‐unity selectivity, densities, good stability wide potential window toward production. Consequently, coupled MOR//CO system based on distinctive MOF‐derived catalysts displays excellent performance formate, delivering high nearly 100% production anode cathode. This work provides novel way design advanced electrocatalysts innovative electrolytic systems value‐added feedstocks.

Язык: Английский

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Engineering a conductive network of atomically thin bismuthene with rich defects enables CO₂ reduction to formate with industry-compatible current densities and stability

Energy & Environmental Science, Год журнала: 2021, Номер 14(9), С. 4998 - 5008

Опубликована: Янв. 1, 2021

An electrocatalytic membrane featuring a 3D porous conductive network of atomically thin and defect-rich bismuthene nanolayers is assembled, which affords an unparalleled catalytic performance for CO 2 electroreduction to formate.

Язык: Английский

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