Stability Issues in Electrochemical CO₂ Reduction: Recent Advances in Fundamental Understanding and Design Strategies

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(51)

Published: Aug. 11, 2023

Electrochemical CO2 reduction reaction (CO2 RR) offers a promising approach to close the anthropogenic carbon cycle and store intermittent renewable energy in fuels or chemicals. On path commercializing this technology, achieving long-term operation stability is central requirement but still confronts challenges. This motivates organize present review systematically discuss issue of RR. starts from fundamental understanding on destabilization mechanisms RR, with focus degradation electrocatalyst change microenvironment during continuous electrolysis. Subsequently, recent efforts catalyst design stabilize active sites are summarized, where increasing atomic binding strength resist surface reconstruction highlighted. Next, optimization electrolysis system enhance by maintaining especially mitigating flooding carbonate problems demonstrated. The manipulation conditions also enables prolong RR lifespan through recovering catalytically mass transport process. finally ends up indicating challenges future opportunities.

Language: Английский

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Boosting CO₂ Electroreduction to C₂H₄ via Unconventional Hybridization: High-Order Ce⁴⁺ 4f and O 2p Interaction in Ce-Cu₂O for Stabilizing Cu⁺

ACS Nano, Journal Year: 2023, Volume and Issue: 17(14), P. 13974 - 13984

Published: July 6, 2023

Efficient conversion of carbon dioxide (CO2) into value-added materials and feedstocks, powered by renewable electricity, presents a promising strategy to reduce greenhouse gas emissions close the anthropogenic loop. Recently, there has been intense interest in Cu2O-based catalysts for CO2 reduction reaction (CO2RR), owing their capabilities enhancing C–C coupling. However, electrochemical instability Cu+ Cu2O leads its inevitable Cu0, resulting poor selectivity C2+ products. Herein, we propose an unconventional feasible stabilizing through construction Ce4+ 4f–O 2p–Cu+ 3d network structure Ce-Cu2O. Experimental results theoretical calculations confirm that orbital hybridization near Ef based on high-order 4f 2p can more effectively inhibit leaching lattice oxygen, thereby Ce-Cu2O, compared with traditional d–p hybridization. Compared pure Cu2O, Ce-Cu2O catalyst increased ratio C2H4/CO 1.69-fold during CO2RR at −1.3 V. Furthermore, situ ex spectroscopic techniques were utilized track oxidation valency copper under conditions time resolution, identifying well-maintained species catalyst. This work not only avenue design involving but also provides deep insights metal-oxidation-state-dependent catalysts.

Language: Английский

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Surface engineering for stable electrocatalysis

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(5), P. 2693 - 2737

Published: Jan. 1, 2024

Unprecedented insights into electrochemical surface dynamics from operando studies inspire electronic and topographical strategies, paving the way for sustained electrocatalytic performance across HER, OER, ORR, CO 2 RR applications.

Language: 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, Journal Year: 2023, Volume and Issue: 145(31), P. 16978 - 16982

Published: Aug. 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.

Language: Английский

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Metalation of metal–organic frameworks: fundamentals and applications

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(11), P. 5626 - 5676

Published: Jan. 1, 2024

Metalation of metal-organic frameworks (MOFs) has been developed as a prominent strategy for materials functionalization pore chemistry modulation and property optimization. By introducing exotic metal ions/complexes/nanoparticles onto/into the parent framework, many metallized MOFs have exhibited significantly improved performance in wide range applications. In this review, we focus on research progress metalation during last five years, spanning design principles, synthetic strategies, potential Based crystal engineering minor change MOF composition through would lead to leveraged variation properties. This review starts from general strategies established incorporation species within MOFs, followed by principles graft desired functionality while maintaining porosity frameworks. Facile contributed great number bespoke with excellent performance, summarize their applications gas adsorption separation, heterogeneous catalysis, detection sensing, energy storage conversion. The underlying mechanisms are also investigated state-of-the-art techniques analyzed gaining insight into structure-property relationships, which turn facilitate further development principles. Finally, current challenges opportunities discussed, promising future directions customizing next-generation advanced outlined well.

Language: Английский

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Strong Electronic Coupling Effects at the Heterojunction Interface of SnO₂ Nanodots and g-C₃N₄ for Enhanced CO₂ Electroreduction

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(10), P. 7055 - 7066

Published: May 9, 2023

Constructing abundant surface/interface structures has significant impacts on improving the performance of electrochemical CO2 reduction reaction (CO2RR) catalysts. For developing high-performance CO2RR catalysts, herein we report a 0D/2D heterojunction structure SnO2 nanodots (∼2 nm) confined graphitic carbon nitride (g-C3N4) nanosheets for promoting conversion to formate. Experimental and theoretical studies demonstrate that N-coordinating sites g-C3N4 highly distributed synergistically lead strong metal oxide–support interactions, substantial interface in SnO2/g-C3N4 induced efficient electron transfer from electron-rich mainly through p–p orbital couplings. As result, provides superior activity stability formate, with Faradic efficiency 91.7% at −0.88 V vs RHE. Moreover, proposed strategy was extended In2O3/g-C3N4, supplying universal achieve hybrid catalysts production high-value chemicals.

Language: Английский

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Recent Advances in Electrocatalytic Hydrogenation Reactions on Copper‐Based Catalysts

Advanced Materials, Journal Year: 2023, Volume and Issue: 36(14)

Published: Sept. 27, 2023

Hydrogenation reactions play a critical role in the synthesis of value-added products within chemical industry. Electrocatalytic hydrogenation (ECH) using water as hydrogen source has emerged an alternative to conventional thermocatalytic processes for sustainable and decentralized under mild conditions. Among various ECH catalysts, copper-based (Cu-based) nanomaterials are promising candidates due their earth-abundance, unique electronic structure, versatility, high activity/selectivity. Herein, recent advances application Cu-based catalysts upgrading valuable chemicals systematically analyzed. The properties initially introduced, followed by design strategies enhance activity selectivity. Then, typical on presented detail, including carbon dioxide reduction multicarbon generation, alkyne-to-alkene conversion, selective aldehyde ammonia production from nitrogen-containing substances, amine organic nitrogen compounds. In these catalyst composition nanostructures toward different is focused. co-hydrogenation two substrates (e.g., CO

Language: 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, Journal Year: 2023, Volume and Issue: 62(49)

Published: Oct. 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 .

Language: Английский

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Tuning C1/C2 Selectivity of CO2 Electrochemical Reduction over in‐Situ Evolved CuO/SnO2 Heterostructure

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(40)

Published: July 24, 2023

Abstract Heterostructured oxides with versatile active sites, as a class of efficient catalysts for CO 2 electrochemical reduction (CO ER), are prone to undergo structure reconstruction under working conditions, thus bringing challenges understanding the reaction mechanism and rationally designing catalysts. Herein, we first time elucidate structural CuO/SnO potentials reveal intrinsic relationship between ER product selectivity in situ evolved heterostructures. At −0.85 V RHE , evolves Cu O/SnO high HCOOH (Faradaic efficiency 54.81 %). Mostly interestingly, it is reconstructed Cu/SnO 2‐x at −1.05 significantly improved Faradaic ethanol 39.8 %. In Raman spectra density functional theory (DFT) calculations that synergetic absorption *COOH *CHOCO intermediates interface favors formation *CO decreases energy barrier C−C coupling, leading ethanol.

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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