Potential Alignment in Tandem Catalysts Enhances CO₂-to-C₂H₄ Conversion Efficiencies

Journal of the American Chemical Society, Год журнала: 2023, Номер 146(1), С. 468 - 475

Опубликована: Дек. 27, 2023

The in-tandem catalyst holds great promise for addressing the limitation of low *CO coverage on Cu-based materials selective C2H4 generation during CO2 electroreduction. However, potential mismatch between CO-formation and favorable C–C coupling Cu represents a bottleneck in these types electrocatalysts, resulting tandem efficiencies. In this study, we propose robust solution to problem by introducing wide-CO generation-potential window nickel single atom (Ni SAC) supported catalyst. selection Ni SAC was based theoretical calculations, its excellent performance further confirmed using situ IR spectroscopy. facilitated carbon dimerization our led ∼370 mA/cm2 partial current density C2H4, corresponding faradic efficiency ∼62%. This remained stable consistent at least ∼14 h high 500 flow-cell reactor, outperforming most catalysts reported so far.

Язык: Английский

---

Tuning Coordination Structures of Zn Sites Through Symmetry‐Breaking Accelerates Electrocatalysis

Advanced Materials, Год журнала: 2023, Номер 36(4)

Опубликована: Авг. 31, 2023

Manipulating the coordination environment of individual active sites in a precise manner remains an important challenge electrocatalytic reactions. Herein, inspired by theoretical predictions, facile procedure to synthesize series symmetry-breaking zinc metal-organic framework (Zn-MOF) catalysts with well-defined structures is presented. Benefiting from optimized microenvironment regulated symmetry-breaking, Zn-N

Язык: Английский

---

Tailoring the coordination environment of double-atom catalysts to boost electrocatalytic nitrogen reduction: a first-principles study

Nanoscale, Год журнала: 2023, Номер 15(39), С. 16056 - 16067

Опубликована: Янв. 1, 2023

Tailoring the coordination environment is an effective strategy to modulate electronic structure and catalytic activity of atomically dispersed transition-metal (TM) catalysts, which has been widely investigated for single-atom catalysts but received less attention emerging double-atom (DACs). Herein, based on first-principles calculations, taking commonly studied N-coordinated graphene-based DACs as references, we explored effect engineering behaviors towards electrocatalytic nitrogen reduction reaction (NRR), realized through replacing one N atom by B or O form B, O, co-coordinated DACs. We found that co-coordination could significantly strengthen N2 adsorption alter pattern TM dimer active center, greatly facilitates activation. Moreover, DACs, linear scaling relationship between binding strengths key intermediates can be attenuated. Consequently, Mn2 exhibiting ultralow limiting potential -0.27 V, climb peak volcano. In addition, experimental feasibility this DAC system was also identified. Overall, benefiting from effect, chemical performance NRR boosted. This phenomena understood adjusted center due changes its microenvironment, affects strength (pattern) pathways, leading enhanced selectivity. work highlights importance in developing other important reactions.

Язык: Английский

---

MOF-based materials for electrochemical reduction of carbon dioxide

Coordination Chemistry Reviews, Год журнала: 2023, Номер 494, С. 215333 - 215333

Опубликована: Июль 28, 2023

Язык: Английский

---

Electron Localization in Rationally Designed Pt₁Pd Single-Atom Alloy Catalyst Enables High-Performance Li–O₂ Batteries

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(4), С. 2339 - 2344

Опубликована: Янв. 18, 2024

Li–O2 batteries (LOBs) are considered as one of the most promising energy storage devices due to their ultrahigh theoretical density, yet they face critical issues sluggish cathode redox kinetics during discharge and charge processes. Here we report a direct synthetic strategy fabricate single-atom alloy catalyst in which Pt is precisely dispersed ultrathin Pd hexagonal nanoplates (Pt1Pd). The LOB with Pt1Pd demonstrates an ultralow overpotential 0.69 V at 0.5 A g–1 negligible activity loss over 600 h. Density functional theory calculations show that can promote activation O2/Li2O2 couple electron localization caused by single atom, thereby lowering barriers for oxygen reduction evolution reactions. Our designing cathodic catalysts address LOBs other storage/conversion devices.

Язык: Английский

---

Surface Engineered Single‐atom Systems for Energy Conversion

Advanced Materials, Год журнала: 2024, Номер 36(16)

Опубликована: Янв. 10, 2024

Abstract Single‐atom catalysts (SACs) are demonstrated to show exceptional reactivity and selectivity in catalytic reactions by effectively utilizing metal species, making them a favorable choice among the different active materials for energy conversion. However, SACs still early stages of conversion, problems like agglomeration low conversion efficiency hampering their practical applications. Substantial research focus on support modifications, which vital SAC stability due intimate relationship between atoms support. In this review, category supports variety surface engineering strategies employed SA systems summarized, including site (heteroatom doping, vacancy introducing, groups grafting, coordination tunning) structure (size/morphology control, cocatalyst deposition, facet engineering, crystallinity control). Also, merits single‐atom systematically introduced. Highlights comprehensive summary discussions utilization surface‐engineered diversified applications photocatalysis, electrocatalysis, thermocatalysis, devices. At end potential obstacles using field discussed. This review aims guide rational design manipulation target‐specific capitalizing characteristic benefits engineering.

Язык: Английский

---

Synergy of Ni Nanoclusters and Single Atom Site: Size Effect on the Performance of Electrochemical CO₂ Reduction Reaction and Rechargeable Zn−CO₂ Batteries

Advanced Functional Materials, Год журнала: 2024, Номер 34(33)

Опубликована: Апрель 18, 2024

Abstract The design of bifunctional electrocatalysts toward reduction reaction carbon dioxide (ECO 2 RR) and oxygen evolution (OER) in aqueous rechargeable Zn─CO batteries (ZABs) still poses a significant challenge. Herein, Ni clusters (Ni x ) 0.5 0.8 nm diameter coupled with single site (Ni−N 4 −C), denoted as Ni−N /Ni 5 8 , respectively, are synthesized the size effect nanoclusters studied. exhibits an ≈100% Faradaic efficiency ( FE CO ECO RR for from −0.4 to −0.8 V versus reversible hydrogen electrode, superior that −C = 55.0%) 80.0%). OER performance or comparable commercial RuO but outperform −C. Theoretical calculation indicates * COOH intermediates bond synergistically atom site, promoting activation reducing energy barrier potential determining step RR. Such is strongly size‐dependent larger result too strong binding intermediates, impede formation CO. As cathode electrocatalyst alkaline ZABs, peak power density 11.7 mW cm −2 cycling durability over 1200 cycles 420 h.

Язык: Английский

---

Recent Design Strategies for M‐N‐C Single‐Atom Catalysts in Oxygen Reduction: An Entropy Increase Perspective

Advanced Functional Materials, Год журнала: 2024, Номер 34(36)

Опубликована: Март 18, 2024

Abstract Recently, a diverse array of novel metal‐nitrogen‐carbon (M‐N‐C) single‐atom catalysts (SACs) have rapidly evolve, particularly in the realm oxygen reduction reaction (ORR). Despite plethora proposed design and improvement strategies for SACs, comprehensive review systematically compiling components M‐N‐C from unified perspective is notably absent. For first time, thorough examination each component conducted, focusing on entropy increase active sites SACs. single M‐N 4 whole system, an implies elevated degree disorder chaos. Broadly, entropy‐increasing modification M (single mental sites) guest groups entails augmentation chaos, with most effective co‐catalytic synergy achieved by establishing multiple through “cocktail effect”. Concerning N (nitrogen other heteroatoms) C (carbon supports), induces heightened disorder, symmetry breaking more likely to drive toward adsorbing molecules attain equilibrium symmetric structure. All these innovative led remarkable ORR activity stability offer guiding criterion future preparation

Язык: Английский

---

Regulating the Electronic Configuration of Ni Sites by Breaking Symmetry of Ni‐Porphyrin to Facilitate CO₂ Photocatalytic Reduction

Advanced Functional Materials, Год журнала: 2024, Номер 34(25)

Опубликована: Фев. 10, 2024

Abstract Adapting the coordination environment to influence electronic configuration of active sites represents an efficient approach for improving photocatalytic performance CO 2 reduction reaction (CO RR) but how execute it precisely remains challenging. Herein, heteroatom‐substitution in Ni‐porphyrin break symmetry Ni center is proposed be effective solution. Based on this, two symmetry‐breaking Ni‐porphyrins, namely Ni(Cl)ON 3 Por and Ni(Cl)SN , are designed successfully prepared. By theoretical calculation, found that efficiently regulates d orbital energy levels center. Furthermore, experimental findings jointly revealed Ni‐porphyrins facilitates generation highly reactive I species during catalytic process, effectively stabilizing reducing barrier formation key * COOH intermediate. As a result, gave production rates 24.7 38.8 mmol g −1 h as well selectivity toward 94.0% 96.4%, respectively, outperforming symmetric NiN 4 rate 6.6 82.8%). These offer microscopic insights into modulate activity by tuning rational design competent catalyst RR photocatalysis.

Язык: Английский

---

Tuning d–p Orbital Hybridization of NiMoO₄@Mo₁₅Se₁₉/NiSe₂ Core‐Shell Nanomaterials via Asymmetric Coordination Interaction Enables the Water Oxidation Process

Advanced Energy Materials, Год журнала: 2024, Номер 14(20)

Опубликована: Апрель 3, 2024

Abstract The electrocatalytic performance of MoNi‐based nanomaterials undergo selenization has garnered significant interest due to their modified electronic structure, while still posses certain challenges for obtained bimetallic selenides. Here, a novel electrocatalyst NiMoO 4 @Mo 15 Se 19 /NiSe 2 core‐shell is constructed promote the desorption OOH * which can facilitate water oxidation process. nanoarrays show that “cores” are mainly nanorods “shells” selenides nanoflakes, super architectures expand more active sites and accelerate electron transfer. Moreover, hybridization interaction between Ni 3d, Mo 4d, 4p orbitals leads an asymmetric distribution electric clouds, decreases adsorption energy transformation oxygen‐containing species. Electrochemical data displays overpotentials only 195 mV, 220 224 mV oxygen evolution reaction (OER) in alkaline freshwater, simulated seawater, natural seawater. current density decay negligible after 100 h stability at about 1.46 V with three‐electrode system low cost unique this work provide constructive solution designing efficient stable OER catalysts future.

Язык: Английский

---