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1.
J Am Chem Soc ; 146(15): 10599-10607, 2024 Apr 17.
Artículo en Inglés | MEDLINE | ID: mdl-38567740

RESUMEN

The success of electrochemical CO2 reduction at high current densities hinges on precise interfacial transportation and the local concentration of gaseous CO2. However, the creation of efficient CO2 transportation channels remains an unexplored frontier. In this study, we design and synthesize hydrophobic porous Cu2O spheres with varying pore sizes to unveil the nanoporous channel's impact on gas transfer and triple-phase interfaces. The hydrophobic channels not only facilitate rapid CO2 transportation but also trap compressed CO2 bubbles to form abundant and stable triple-phase interfaces, which are crucial for high-current-density electrocatalysis. In CO2 electrolysis, in situ spectroscopy and density functional theory results reveal that atomic edges of concave surfaces promote C-C coupling via an energetically favorable OC-COH pathway, leading to overwhelming CO2-to-C2+ conversion. Leveraging optimal gas transportation and active site exposure, the hydrophobic porous Cu2O with a 240 nm pore size (P-Cu2O-240) stands out among all the samples and exhibits the best CO2-to-C2+ productivity with remarkable Faradaic efficiency and formation rate up to 75.3 ± 3.1% and 2518.2 ± 8.1 µmol h-1 cm-2, respectively. This study introduces a novel paradigm for efficient electrocatalysts that concurrently addresses active site design and gas-transfer challenges.

2.
Chem Sci ; 14(47): 13851-13859, 2023 Dec 06.
Artículo en Inglés | MEDLINE | ID: mdl-38075663

RESUMEN

Selective conversion of carbon dioxide (CO2) to multi-carbon products (CO2-to-C2+) at high current densities is in essential demand for the practical application of the resultant valuable products, yet it remains challenging to conduct due to the lack of efficient electrocatalysts. Herein, three-dimensional ordered porous cuprous oxide cuboctahedra (3DOP Cu2O-CO) were designed and synthesized by a molecular fence-assisted hard templating approach. Capitalizing on the merits of interconnected and uniformly distributed pore channels, 3DOP Cu2O-CO exhibited outstanding electrochemical CO2-to-C2+ conversion, achieving faradaic efficiency and partial current density for C2+ products of up to 81.7% and -0.89 A cm-2, respectively, with an optimal formation rate of 2.92 mmol h-1 cm-2 under an applied current density of -1.2 A cm-2. In situ spectroscopy and simulation results demonstrated that the ordered pores of 3DOP Cu2O-CO can effectively confine and accumulate sufficient *CO adsorption during electrochemical CO2 reduction, which facilitates efficient dimerization for the formation of C2+ products. Furthermore, the 3DOP structure induces a higher local pH value, which not only enhances the C-C coupling reaction, but also suppresses competing H2 evolution.

3.
Chem Sci ; 13(13): 3819-3825, 2022 Mar 30.
Artículo en Inglés | MEDLINE | ID: mdl-35432914

RESUMEN

An effective yet simple approach was developed to synthesize mesoporous PdBi nanocages for electrochemical applications. This technique relies on the subtle utilization of the hydrolysis of a metal salt to generate precipitate cores in situ as templates for navigating the growth of mesoporous shells with the assistance of polymeric micelles. The mesoporous PdBi nanocages are then obtained by excavating vulnerable cores and regulating the crystals of mesoporous metallic skeletons. The resultant mesoporous PdBi nanocages exhibited excellent electrocatalytic performance toward the ethanol oxidation reaction with a mass activity of 3.56 A mg-1_Pd, specific activity of 17.82 mA cm-2 and faradaic efficiency of up to 55.69% for C1 products.

4.
New Phytol ; 229(5): 2957-2969, 2021 03.
Artículo en Inglés | MEDLINE | ID: mdl-33188641

RESUMEN

Despite widespread anthropogenic nutrient enrichment, it remains unclear how nutrient enrichment influences plant-arbuscular mycorrhizal fungi (AMF) symbiosis and ecosystem multifunctionality at the global scale. Here, we conducted a meta-analysis to examine the worldwide effects of nutrient enrichment on AMF and plant diversity and ecosystem multifunctionality using data of field experiments from 136 papers. Our analyses showed that nutrient addition simultaneously decreased AMF diversity and abundance belowground and plant diversity aboveground at the global scale. The decreases in AMF diversity and abundance associated with nutrient addition were more pronounced with increasing experimental duration, mean annual temperature (MAT) and mean annual precipitation (MAP). Nutrient addition-induced changes in soil pH and available phosphorus (P) predominantly regulated the responses of AMF diversity and abundance. Furthermore, AMF diversity correlated with ecosystem multifunctionality under nutrient addition worldwide. Our findings identify the negative effects of nutrient enrichment on AMF and plant diversity and suggest that AMF diversity is closely linked with ecosystem function. This study offers an important advancement in our understanding of plant-AMF interactions and their likely responses to ongoing global change.


Asunto(s)
Micorrizas , Ecosistema , Hongos , Nitrógeno/análisis , Nutrientes , Raíces de Plantas/química , Suelo , Microbiología del Suelo
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