Nanoarchitectonics of Metallene Materials for Electrocatalysis

ACS Nano, Год журнала: 2023, Номер 17(14), С. 13017 - 13043

Опубликована: Июнь 27, 2023

Controlling the synthesis of metal nanostructures is one approach for catalyst engineering and performance optimization in electrocatalysis. As an emerging class unconventional electrocatalysts, two-dimensional (2D) metallene electrocatalysts with ultrathin sheet-like morphology have gained ever-growing attention exhibited superior electrocatalysis owing to their distinctive properties originating from structural anisotropy, rich surface chemistry, efficient mass diffusion capability. Many significant advances synthetic methods electrocatalytic applications 2D metallenes been obtained recent years. Therefore, in-depth review summarizing progress developing electrochemical highly needed. Unlike most reported reviews on metallenes, this starts by introducing preparation based classification metals (e.g., noble metals, non-noble metals) instead methods. Some typical strategies preparing each kind are enumerated detail. Then, utilization applications, especially conversion reactions, including hydrogen evolution reaction, oxygen reduction fuel oxidation CO2 N2 comprehensively discussed. Finally, current challenges opportunities future research energy proposed.

Язык: Английский

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“Ship-in-a-Bottle” Integration of Ditin(IV) Sites into a Metal–Organic Framework for Boosting Electroreduction of CO₂ in Acidic Electrolyte

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(31), С. 16978 - 16982

Опубликована: Авг. 1, 2023

The electrochemical CO2 reduction reaction (eCO2RR) under acidic conditions has become a promising way to achieve high utilization because of the inhibition undesirable carbonate formation that typically occurs neutral and alkaline conditions. Herein, unprecedented highly active ditin(IV) sites were integrated into nanopores metal-organic framework, namely NU-1000-Sn, by "ship-in-a-bottle" strategy. NU-1000-Sn delivers nearly 100% formic acid Faradaic efficiency at an industry current density 260 mA cm-2 with single-pass 95% in solution (pH = 1.67). No obvious degradation was observed over 15 hours continuous operation cm-2, representing remarkable eCO2RR performance electrolyte date. mechanism study shows both oxygen atoms key intermediate *HCOO can coordinate two adjacent Sn site simultaneously. Such bridging coordination is conducive hydrogenation CO2, thus leading performance.

Язык: Английский

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Efficient C–N coupling in the direct synthesis of urea from CO ₂ and N ₂ by amorphous Sb _x Bi _1-x O _y clusters

Proceedings of the National Academy of Sciences, Год журнала: 2023, Номер 120(39)

Опубликована: Сен. 18, 2023

Although direct generation of high-value complex molecules and feedstock by coupling ubiquitous small such as CO 2 N holds great appeal a potential alternative to current fossil-fuel technologies, suitable scalable efficient catalysts this end are not currently available yet be designed developed. To end, here we prepare characterize Sb x Bi 1-x O y clusters for urea synthesis from via C–N coupling. The introduction in the amorphous BiO changes adsorption geometry on catalyst O-connected C-connected, creating possibility formation products urea. modulated Bi(II) sites can effectively inject electrons into , promoting advantageous modification symmetry frontier orbitals involved rate-determining catalytic step. Compared with result lower reaction only −0.3 V vs. RHE, an increased production yield 307.97 μg h −1 mg cat higher Faraday efficiency (10.9%), pointing present system one best aqueous systems among those reported so far. Beyond synthesis, results introduce demonstrate unique strategies modulate electronic states main group p -metals toward their use effective multistep electroreduction reactions requiring

Язык: Английский

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Electrocatalytic Waste-Treating-Waste Strategy for Concurrently Upgrading of Polyethylene Terephthalate Plastic and CO₂ into Value-Added Formic Acid

ACS Catalysis, Год журнала: 2023, Номер 13(21), С. 14163 - 14172

Опубликована: Окт. 20, 2023

Polyethylene terephthalate (PET) plastic and CO2 pollution have seriously threatened the ecological environment caused a huge waste of carbon resources. Herein, we report an electrocatalytic waste-treating-waste strategy for concurrently upgrading PET wastes into value-added formic acid (HCOOH), in which both anode (oxygen-vacancy-rich Ni(OH)2-VO) cathode (Bi/Bi2O3 heterostructure) electrocatalysts were elaborately designed from derivatives. Impressively, as-prepared Ni(OH)2-VO Bi/Bi2O3 achieve high selectivity HCOOH (86 91%, respectively) with industrial-level current densities at ultralow potentials (300 mA cm–2 1.6 V −272 −1.4 V, respectively). Further experimental theoretical results reveal that abundant oxygen vacancies will largely facilitate formation Ni3+ species accelerate subsequent processes dehydrogenation C–C bond breakage during upcycling. Meanwhile, interface electron transfer Bi2O3 to Bi benefits keeping valence sites optimizes adsorption OCHO* intermediate, thereby endowing efficient performance toward reduction HCOOH. As proof concept, solar-powered flow reactor real-time monitoring control functions was designed, realized record Faradaic efficiency 181% This work offers opportunities utilization provides constructive guidance design advanced converting valuable chemicals.

Язык: Английский

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Reaction Environment Regulation for Electrocatalytic CO₂ Reduction in Acids

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(26)

Опубликована: Апрель 19, 2024

The electrocatalytic CO

Язык: Английский

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Enhancing Local CO₂ Adsorption by L‐histidine Incorporation for Selective Formate Production Over the Wide Potential Window

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(49)

Опубликована: Окт. 19, 2023

Electrochemical carbon dioxide reduction reaction (CO2 RR) to produce valuable chemicals is a promising pathway alleviate the energy crisis and global warming issues. However, simultaneously achieving high Faradaic efficiency (FE) current densities of CO2 RR in wide potential range remains as huge challenge for practical implements. Herein, we demonstrate that incorporating bismuth-based (BH) catalysts with L-histidine, common amino acid molecule proteins, an effective strategy overcome inherent trade-off between activity selectivity. Benefiting from significantly enhanced adsorption capability promoted electron-rich nature by L-histidine integrity, BH catalyst exhibits excellent FEformate unprecedented windows (>90 % within -0.1--1.8 V >95 -0.2--1.6 versus reversible hydrogen electrode, RHE). Excellent performance can still be achieved under low-concentration feeding (e.g., 20 vol.%). Besides, extremely low onset -0.05 VRHE (close theoretical thermodynamic -0.02 ) was detected situ ultraviolet-visible (UV-Vis) measurements, together stable operation over 50 h preserved ≈95 partial density 326.2 mA cm-2 at -1.0 .

Язык: Английский

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Efficient and stable acidic CO ₂ electrolysis to formic acid by a reservoir structure design

Proceedings of the National Academy of Sciences, Год журнала: 2023, Номер 120(51)

Опубликована: Дек. 12, 2023

Electrochemical synthesis of valuable chemicals and feedstocks through carbon dioxide (CO 2 ) reduction in acidic electrolytes can surmount the considerable CO loss alkaline neutral conditions. However, achieving high productivity, while operating steadily electrolytes, remains a big challenge owing to severe competing hydrogen evolution reaction. Here, we show that vertically grown bismuth nanosheets on gas-diffusion layer create numerous cavities as electrolyte reservoirs, which confine situ–generated hydroxide potassium ions limit inward proton diffusion, producing locally environments. Based this design, achieve formic acid Faradaic efficiency 96.3% partial current density 471 mA cm −2 at pH 2. When operated slim continuous-flow electrolyzer, system exhibits full-cell energy 40% single pass 79% performs over 50 h. We further demonstrate production pure aqueous solution with concentration 4.2 weight %.

Язык: Английский

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Nanoscale Engineering of P‐Block Metal‐Based Catalysts Toward Industrial‐Scale Electrochemical Reduction of CO₂

Advanced Energy Materials, Год журнала: 2023, Номер 13(34)

Опубликована: Июль 27, 2023

Abstract The efficient conversion of CO 2 to value‐added products represents one the most attractive solutions mitigate climate change and tackle associated environmental issues. In particular, electrochemical reduction fuels chemicals has garnered tremendous interest over last decades. Among all from reduction, formic acid is considered economically vital products. P‐block metals (especially Bi, Sn, In, Pb) have been extensively investigated recognized as catalytic materials for electroreduction formate. Despite remarkable progress, future implementation this technology at industrial‐scale hinges on ability solve remaining roadblocks. review, current research status, challenges, prospects p‐block metal‐based catalysts primarily formate are comprehensively reviewed. rational design nanostructure engineering these metal optimization their performances discussed in detail. Subsequently, recent progress development state‐of‐the‐art operando characterization techniques together with advanced cells uncover intrinsic catalysis mechanism discussed. Lastly, a perspective directions including tackling critical challenges realize its early industrial presented.

Язык: Английский

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A Bismuth‐Based Zeolitic Organic Framework with Coordination‐Linked Metal Cages for Efficient Electrocatalytic CO₂ Reduction to HCOOH

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(45)

Опубликована: Сен. 18, 2023

Zeolitic metal-organic frameworks (ZMOFs) have emerged as one of the most promsing catalysts for energy conversion, but they suffer from either weak bonding between cubes (MOCs) that decrease their stability during catalysis processes or low activity due to inadequate active sites. In this work, through ligand-directing strategy, we successfully obtain an unprecedented bismuth-based ZMOF (Bi-ZMOF) featuring a ACO topological crystal structure with strong coordination Bi-based cages. As result, it enables efficient reduction CO2 formic acid (HCOOH) Faradaic efficiency high 91 %. A combination in situ surface-enhanced infrared absorption spectroscopy and density functional theory calculation reveals Bi-N contributes facilitating charge transfer N Bi atoms, which stabilize intermediate boost HCOOH. This finding highlights importance environment metal sites on electrocatalytic reduction. We believe work will offer new clue rationally design zeolitic MOFs catalytic reaction.

Язык: Английский

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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, Год журнала: 2024, Номер 63(14)

Опубликована: Фев. 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

Язык: Английский

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