Importing Antibonding‐Orbital Occupancy through Pd−O−Gd Bridge Promotes Electrocatalytic Oxygen Reduction

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(52)

Опубликована: Ноя. 9, 2023

The active-site density, intrinsic activity, and durability of Pd-based materials for oxygen reduction reaction (ORR) are critical to their application in industrial energy devices. This work constructs a series carbon-based rare-earth (RE) oxides (Gd2 O3 , Sm2 Eu2 CeO2 ) by using RE metal-organic frameworks tune the ORR performance Pd sites through Pd-REx Oy interface interaction. Taking Pd-Gd2 /C as representative, it is identified that strong coupling between Gd2 induces formation Pd-O-Gd bridge, which triggers charge redistribution . screened exhibits impressive with high onset potential (0.986 VRHE ), half-wave (0.877 excellent stability. Similar results also found Pd-Sm2 /C, Pd-Eu2 Pd-CeO2 catalysts. Theoretical analyses reveal promotes electron transfer antibonding-orbital occupancy Pd-*OH optimization *OH adsorption rate-determining step ORR. pH-dependent microkinetic modeling shows close theoretical optimal activity ORR, outperforming Pt under same conditions. By its ascendancy superior Zn-air battery an air cathode, implying practicability.

Язык: Английский

---

In-situ reconstructed Cu/Cu2O heterogeneous nanorods with oxygen vacancies for enhanced electrocatalytic nitrate reduction to ammonia

Chemical Engineering Journal, Год журнала: 2023, Номер 479, С. 147574 - 147574

Опубликована: Ноя. 20, 2023

Язык: Английский

---

Electronic Structure Design of Transition Metal-Based Catalysts for Electrochemical Carbon Dioxide Reduction

ACS Nano, Год журнала: 2024, Номер 18(14), С. 9823 - 9851

Опубликована: Март 28, 2024

With the increasingly serious greenhouse effect, electrochemical carbon dioxide reduction reaction (CO2RR) has garnered widespread attention as it is capable of leveraging renewable energy to convert CO2 into value-added chemicals and fuels. However, performance CO2RR can hardly meet expectations because diverse intermediates complicated processes, necessitating exploitation highly efficient catalysts. In recent years, with advanced characterization technologies theoretical simulations, exploration catalytic mechanisms gradually deepened electronic structure catalysts their interactions intermediates, which serve a bridge facilitate deeper comprehension structure-performance relationships. Transition metal-based (TMCs), extensively applied in CO2RR, demonstrate substantial potential for further modulation, given abundance d electrons. Herein, we discuss representative feasible strategies modulate catalysts, including doping, vacancy, alloying, heterostructure, strain, phase engineering. These approaches profoundly alter inherent properties TMCs interaction thereby greatly affecting rate pathway CO2RR. It believed that rational design modulation fundamentally provide viable directions development toward conversion many other small molecules.

Язык: Английский

---

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

Chemical Society Reviews, Год журнала: 2024, Номер 53(12), С. 6295 - 6321

Опубликована: Янв. 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.

Язык: Английский

---

Bottom‐up Growth of Convex Sphere with Adjustable Cu(0)/Cu(I) Interfaces for Effective C₂ Production from CO₂ Electroreduction

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(28)

Опубликована: Май 4, 2024

Abstract One challenge confronting the Cu 2 O catalysts in electrocatalysis of carbon dioxide reduction reaction (CO RR) is active Cu(I) species, resulting low selectivity and quick deactivation. In this study, we for first time introduce a bottom‐up growth convex sphere with adjustable Cu(0)/Cu(I) interfaces (Cu x @Cu spheres). Interestingly, are dynamically modulated by varying hydrothermal time, thus regulating conversion C 1 products. particular, 4 h treatment applied to 0.25 favorable interface results highest products (90.5 %). situ Fourier‐transform infrared spectroscopy measurements density functional theory calculations reveal that lowers energy barrier production ethylene ethanol while increasing coverage localized *CO adsorbate increased dimerization. This work establishes novel approach transforming state valence‐sensitive electrocatalysts into high‐value energy‐related engineering

Язык: Английский

---

Deciphering the Stability Mechanism of Cu Active Sites in CO₂ Electroreduction via Suppression of Antibonding Orbital Occupancy in the O 2p-Cu 3d Hybridization

ACS Catalysis, Год журнала: 2024, Номер 14(3), С. 1351 - 1362

Опубликована: Янв. 11, 2024

Copper-based catalysts, hallmarked by their ideal C–C coupling energy facilitated the symbiotic presence of Cu+ and Cu0 active sites, are poised to revolutionize selective electrochemical reduction CO2 C2H4. Regrettably, these catalysts beleaguered unavoidable diminution during reaction process, resulting in suboptimal C2H4 yields. To circumvent this limitation, we have judiciously mitigated antibonding orbital occupancy O 2p 3d hybridization introducing Cu defects into Cu2O, thereby augmenting Cu–O bond strength stabilize sites further decipher stabilization mechanism Cu+. This structural refinement, illuminated meticulous DFT calculations, fosters a heightened free threshold for hydrogen evolution (HER), while orchestrating thermodynamically favorable milieu enhanced within Cu-deficient Cu2O (Cuv-Cu2O). Empirically, Cuv-Cu2O has outperformed its pure counterpart, exhibiting prominent C2H4/CO ratio 1.69 as opposed 1.01, without conceding significant ground production over an 8 h span at −1.3 V vs RHE. endeavor not only delineates critical influence on reveals deep about but also charts pioneering pathway realm advanced materials design.

Язык: Английский

---

Targeted C-O bond cleavage of *CH2CHO at copper active sites for efficient electrosynthesis of ethylene from CO2 reduction

Applied Catalysis B Environment and Energy, Год журнала: 2024, Номер 351, С. 123992 - 123992

Опубликована: Апрель 24, 2024

Язык: Английский

---

Electronic metal-support interaction modulates Cu electronic structures for CO2 electroreduction to desired products

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Фев. 25, 2025

In this work, the Cu single-atom catalysts (SACs) supported by metal-oxides (Al2O3-CuSAC, CeO2-CuSAC, and TiO2-CuSAC) are used as theoretical models to explore correlations between electronic structures CO2RR performances. For these catalysts, metal-support interaction (EMSI) induced charge transfer sites supports subtly modulates structure form different highest occupied-orbital. The occupied 3dyz orbital of Al2O3-CuSAC enhances adsorption strength CO weakens C-O bonds through 3dyz-π* electron back-donation. This reduces energy barrier for C-C coupling, thereby promoting multicarbon formation on Al2O3-CuSAC. 3dz2 TiO2-CuSAC accelerates H2O activation, lowers reaction forming CH4. over activated H2O, in turn, intensifies competing hydrogen evolution (HER), which hinders high-selectivity production CH4 TiO2-CuSAC. CeO2-CuSAC with 3dx2-y2 promotes CO2 activation its localized state inhibits coupling. moderate water activity facilitates *CO deep hydrogenation without excessively activating HER. Hence, exhibits Faradaic efficiency 70.3% at 400 mA cm−2. Rational regulation control electroreduction pathways is challenging. Here, authors report modulating single-sites via interaction, enabling switchable selectivity multicarbons methane.

Язык: Английский

---

Asymmetric Cu(I)─W Dual‐Atomic Sites Enable C─C Coupling for Selective Photocatalytic CO₂ Reduction to C₂H₄

Advanced Science, Год журнала: 2024, Номер 11(28)

Опубликована: Апрель 26, 2024

Abstract Solar‐driven CO 2 reduction into value‐added C 2+ chemical fuels, such as H 4 , is promising in meeting the carbon‐neutral future, yet performance usually hindered by high energy barrier of C─C coupling process. Here, an efficient and stabilized Cu(I) single atoms‐modified W 18 O 49 nanowires (Cu 1 /W ) photocatalyst with asymmetric Cu─W dual sites reported for selective photocatalytic to . The interconversion between W(V) W(VI) ensures stability during Under light irradiation, optimal Cu (3.6‐Cu catalyst exhibits concurrent activity selectivity toward production, reaching a corresponding yield rate 4.9 µmol g −1 h 72.8%, respectively. Combined situ spectroscopies computational calculations reveal that atoms stabilize *CO intermediate, effectively reduce two neighboring intermediates, enabling highly generation from photoreduction. This work demonstrates leveraging atomically‐dispersed dual‐sites ‐to‐C conversion can provide new insight other targeted products through rational construction active coupling.

Язык: Английский

---

Engineering stable Cu+-Cu0 sites and oxygen defects in boron-doped copper oxide for electrocatalytic reduction of CO2 to C2+ products

Chemical Engineering Journal, Год журнала: 2024, Номер 484, С. 149710 - 149710

Опубликована: Фев. 15, 2024

Язык: Английский

---