Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 4 de 4
Filtrar
Mais filtros










Base de dados
Assunto principal
Intervalo de ano de publicação
1.
Angew Chem Int Ed Engl ; : e202404676, 2024 Jun 16.
Artigo em Inglês | MEDLINE | ID: mdl-38880900

RESUMO

Copper (Cu)-based catalysts have established their unique capability for yielding wide value-added products from CO2. Herein, we demonstrate that the pathways of the electrocatalytic CO2 reduction reaction (CO2RR) can be rationally altered toward C1 or C2+ products by simply optimizing the coordination of Cu with O-containing organic species (squarate (C4O4) and cyclohexanhexanone (C6O6)). It is revealed that the strength of Cu-O bonds can significantly affect the morphologies and electronic structures of derived Cu catalysts, resulting in the distinct behaviors during CO2RR. Specifically, the C6O6-Cu catalysts made up from organized nanodomains shows a dominant C1 pathway with a total Faradaic efficiency (FE) of 63.7% at -1.0 V (versus reversible hydrogen electrode, RHE). In comparison, the C4O4-Cu with an about perfect crystalline structure results in uniformly dispersed Cu-atoms, showing a notable FE of 65.8% for C2+ products with enhanced capability of C-C coupling. The latter system also shows stable operation over at least 10 h with a high current density of 205.1 mA cm-2 at -1.0 VRHE, i.e. is already at the boarder of practical relevance. This study sheds light on the rational design of Cu-based catalysts for directing the CO2RR reaction pathway.

2.
Small ; 20(2): e2305386, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-37668264

RESUMO

The significant attraction toward aqueous proton batteries (APBs) is attributable to their expedited kinetics, elevated safety profile, and economical feasibility. Nevertheless, their practical implement is significantly blocked by the unsatisfactory energy density due to the limited cathode materials. Herein, vanadium hexacyanoferrate Prussian blue analog (VOHCF) is introduced as a potentially favorable cathode material for APBs. The findings demonstrate that this VOHCF electrode exhibits a notable reversible capacity of 102.7 mAh g-1 and exceptional cycling stability, with 95.4% capacity retention over 10 000 cycles at 10 A g-1 . It is noteworthy that this is the detailed instance of VOHCF being proposed as a cathode for APBs. Combining the in situ characterization techniques and theoretical simulations, the origins of excellent proton storage performance are revealed as the multiple redox mechanisms with double active centers of ─C≡N group and V═O bond in VOHCF as well as the robust structure stability. A proton full cell with excellent performance is further achieved by coupling the VOHCF cathode and diquinoxalino[2,3-a:2',3'-c] phenazine (HATN) anode, demonstrating the great potential of VOHCF in practical applications. This work could provide fundamental understanding to the development of feasible cathode materials for proton storage device.

3.
Angew Chem Int Ed Engl ; 62(49): e202313522, 2023 Dec 04.
Artigo em Inglês | MEDLINE | ID: mdl-37855722

RESUMO

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

4.
J Mol Graph Model ; 111: 108101, 2022 03.
Artigo em Inglês | MEDLINE | ID: mdl-34922331

RESUMO

Currently, the oxygen evolution reaction (OER) is constrained by complex four-electron transport, thus it is difficult to understand the catalytic mechanism. In this work, the electronic properties and catalytic performance of M1M2/NC (M = Mn, Fe, Co, Ni, Cu and Zn, random combination in pairs) is studied by density functional theory, the calculated results show that the overpotential of FeCu/NC is 0.88 V, which is used as the optimal catalyst to further study the OER reaction mechanism. Combined with the volcano map and the d-band center position, the low overpotential of FeCu/NC is because it has a more suitable position of d-band center -1.806 eV than other materials. Moreover, the calculation results show that the density of states (DOS) of iron-containing materials is stronger than that of other materials near the Fermi level, which can promote the catalytic reaction. In addition, O∗OH and O∗H, O∗H and O∗ linearly related theoretical equations are proposed, respectively. Furthermore, the analysis of the catalytic mechanism shows that the formation of the catalytic rate-determining step is affected by the movement of the d-band center, the distance of the transition state adsorption and the electric field.


Assuntos
Grafite , Adsorção , Catálise , Eletrônica , Oxigênio
SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA
...