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

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(21), P. 14163 - 14172

Published: Oct. 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.

Language: Английский

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Stabilizing the oxidation state of catalysts for effective electrochemical carbon dioxide conversion

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(12), P. 6295 - 6321

Published: Jan. 1, 2024

Developing sophisticated strategies to stabilize oxidative metal catalysts based on the correlation between dynamic oxidation state and product profile is favorable for efficient electrochemical CO 2 conversion.

Language: Английский

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Efficient Capture and Electroreduction of Dilute CO₂ into Highly Pure and Concentrated Formic Acid Aqueous Solution

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(20), P. 14349 - 14356

Published: May 14, 2024

High-purity CO2 rather than dilute (15 vol %, CO2/N2/O2 = 15:80:5, v/v/v) similar to the flue gas is currently used as feedstock for electroreduction of CO2, and liquid products are usually mixed up with cathode electrolyte, resulting in high product separation costs. In this work, we showed that a microporous conductive Bi-based metal–organic framework (Bi-HHTP, HHTP 2,3,6,7,10,11-hexahydroxytriphenylene) can not only efficiently capture from under humidity but also catalyze adsorbed into formic acid current density 80 mA cm–2 Faradaic efficiency 90% at very low cell voltage 2.6 V. Importantly, performance atmosphere was close high-purity atmosphere. This first catalyst maintain exceptional eCO2RR presence both O2 N2. Moreover, by using feedstock, 1 working electrode coating Bi-HHTP continuously produce 200 mM aqueous solution relative purity 100% least 30 h membrane assembly (MEA) electrolyzer. The does contain electrolytes, such highly concentrated pure be directly an electrolyte fuel cells. Comprehensive studies revealed might ascribed ability micropores on lower Gibbs free energy formation key intermediate *OCHO open Bi sites.

Language: Английский

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Concentrated Formic Acid from CO₂ Electrolysis for Directly Driving Fuel Cell

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(13)

Published: Feb. 2, 2024

Abstract The production of formic acid via electrochemical CO 2 reduction may serve as a key link for the carbon cycle in economy, yet its practical feasibility is largely limited by quantity and concentration product. Here we demonstrate continuous at M an industrial‐level current densities (i.e., 200 mA cm −2 ) 300 h on membrane electrode assembly using scalable lattice‐distorted bismuth catalysts. optimized catalysts also enable Faradaic efficiency formate 94.2 % highest partial density 1.16 A , reaching rate 21.7 mmol −1 . To assess practicality this system, perform comprehensive techno‐economic analysis life assessment, showing that our approach can potentially substitute conventional methyl hydrolysis industrial production. Furthermore, resultant serves direct fuel air‐breathing cells, boasting power 55 mW exceptional thermal 20.1 %.

Language: Английский

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pH‐Universal Electrocatalytic CO₂ Reduction with Ampere‐Level Current Density on Doping‐Engineered Bismuth Sulfide

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(32)

Published: May 27, 2024

Abstract The practical application of the electrocatalytic CO 2 reduction reaction (CO RR) to form formic acid fuel is hindered by limited activation molecules and lack universal feasibility across different pH levels. Herein, we report a doping‐engineered bismuth sulfide pre‐catalyst (BiS‐1) that S partially retained after electrochemical reconstruction into metallic Bi for RR formate/formic with ultrahigh performance wide range. best BiS‐1 maintains Faraday efficiency (FE) ~95 % at 2000 mA cm −2 in flow cell under neutral alkaline solutions. Furthermore, catalyst shows unprecedentedly high FE (~95 %) current densities from 100 1300 acidic Notably, density can reach 700 while maintaining above 90 membrane electrode assembly electrolyzer operate stably 150 h 200 . In situ spectra functional theory calculations reveals doping modulates electronic structure effectively promotes formation HCOO* intermediate generation. This work develops efficient stable electrocatalysts sustainable production.

Language: Английский

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A Copper–Zinc Cyanamide Solid-Solution Catalyst with Tailored Surface Electrostatic Potentials Promotes Asymmetric N-Intermediate Adsorption in Nitrite Electroreduction

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: 147(9), P. 8012 - 8023

Published: Feb. 18, 2025

The electrocatalytic nitrite reduction (NO2RR) converts nitrogen-containing pollutants to high-value ammonia (NH3) under ambient conditions. However, its multiple intermediates and multielectron coupled proton transfer process lead low activity NH3 selectivity for the existing electrocatalysts. Herein, we synthesize a solid-solution copper-zinc cyanamide (Cu0.8Zn0.2NCN) with localized structure distortion tailored surface electrostatic potential, allowing asymmetric binding of NO2-. It exhibits outstanding NO2RR performance Faradaic efficiency ∼100% an yield 22 mg h-1 cm-2, among best such process. Theoretical calculations in situ spectroscopic measurements demonstrate that Cu-Zn sites coordinated linear polarized [NCN]2- could transform symmetric [Cu-O-N-O-Cu] CuNCN-NO2- [Cu-N-O-Zn] configuration Cu0.8Zn0.2NCN-NO2-, thus enhancing adsorption bond cleavage. A paired electro-refinery Cu0.8Zn0.2NCN cathode reaches 2000 mA cm-2 at 2.36 V remains fully operational industrial-level 400 >140 h production rate ∼30 mgNH3 cm-2. Our work opens new avenue tailoring potentials using strategy advanced electrocatalysis.

Language: Английский

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Unveiling the role of heteroatom doping and strain in Core-Shell catalysts for CO2RR

Chemical Engineering Journal, Journal Year: 2025, Volume and Issue: unknown, P. 160155 - 160155

Published: Feb. 1, 2025

Language: Английский

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Restraining Interfacial Cu²⁺ by using Amorphous SnO₂ as Sacrificial Protection Boosts CO₂ Electroreduction

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(40)

Published: Aug. 7, 2023

The electrochemical carbon dioxide reduction reaction (CO2 RR) to formate is of great interest in the field energy. Cu-based material an appealing electrocatalyst for CO2 RR. However, retaining Cu2+ under high cathodic potential RR remains a challenge, leading low electrocatalytic selectivity, activity, and stability. Herein, inspired by corrosion science, sacrificial protection strategy stabilize interfacial crystalline CuO through embedding active amorphous SnO2 (c-CuO/a-SnO2 ) reported, which greatly boosts sensitivity, stability formate. as-made hybrid catalyst can achieve superior selectivity with remarkable Faradaic efficiency (FE) 96.7%, superhigh current density over 1 A cm-2 that far outperforms industrial benchmarks (FE > 90%, 300 mA ). In situ X-ray absorption spectroscopy (XAS) diffractionexperimental theoretical calculation results reveal broadened s-orbital a-SnO2 offers lower orbital extra electrons than , effectively retain nearby interface significantly lowers energy barrier limited step (* → * HCOO) enhances activity

Language: Английский

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Application of MOF-derived materials as electrocatalysts for CO₂ conversion

Materials Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 7(23), P. 6107 - 6129

Published: Jan. 1, 2023

This review summarizes the four main synthesis strategies of MOF-derived materials, and feasibility challenges materials in ECO 2 RR are discussed.

Language: Английский

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A comparative study on carbon neutral hydrogen carrier production: Formic acid from CO2 vs. ammonia

Journal of CO2 Utilization, Journal Year: 2024, Volume and Issue: 82, P. 102756 - 102756

Published: April 1, 2024

Hydrogen (H2) is increasingly recognized as a key player in the journey towards carbon neutrality, with ammonia (NH3) and formic acid (FA) emerging significant hydrogen vectors. This review highlights advancements catalyst efficiency for FA synthesis from CO2, particularly bismuth (Bi) tin (Sn) catalysts. It investigates diverse NH3 production methodologies, such electrochemical, thermochemical, photochemical processes, underscores integration of renewables to address their energy demands. The study also reviews novel materials like metal-organic frameworks (MOFs) carbon-based catalysts that could enhance catalytic effectiveness. Transitioning lab-scale models industrial-scale applications requires addressing longevity process enhancement, it suggests investigating hybrid systems might offer improved yields. Concluding directive future research, advocates scalable, economically viable, environmentally sustainable CO2 conversion technologies, underscoring essential roles reduced emissions.

Language: Английский

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