In this work, we report for the first time a comprehensive investigation of the intricate correlation between dynamic phase evolution and glycerol electrooxidation reaction (GEOR) performance across three primary MnO crystallographic phases (α-, β-, and γ-MnO). The results showed that all three electrocatalysts exhibited comparable selectivity toward three-carbon products (∼90%), but γ-MnO exhibited superior performance, with a low onset potential of ∼1.45 V, the highest current density of ∼1.9 mA cm at 1.85 V, and reasonable stability. Raman spectroscopy revealed the potential-induced surface reconstruction of different MnO structures from which a correlation among the applied potential, electrocatalytic activity, and product distribution was identified. The higher the applied potential, the greater conversion from the original structure to δ-MnO, resulting in lower C-C cleavage and higher 3C product selectivity. This study not only provides a systematic understanding of structure-controlled electrocatalytic activity for high selectivity toward 3C products of MnO but also contributes to the development of a non-noble and environmentally friendly catalyst for valorizing glycerol.
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http://dx.doi.org/10.1021/acsami.3c00857 | DOI Listing |
ACS Appl Mater Interfaces
December 2024
Faculty of Metallurgical and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, Yunnan, PR China.
The exploration and rational design of high-performance, durable, and non-precious-metal bifunctional oxygen electrocatalysts are highly desired for the large-scale application of overall water splitting. Herein, an effective and straightforward coupling approach was developed to fabricate high-performance bifunctional OER/HER electrocatalysts based on core-shell nanostructure comprising a Ni/NiN core and a NiFe(OH) shell. The as-prepared Ni/NiN@NiFe(OH)-4 catalyst exhibited low overpotentials of 57 and 243 mV at 10 mA cm for the HER and OER in 1.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
Shenzhen University, Chemistry, Nanhai Ave 3688, 518060, Shenzhen, CHINA.
The high entropy alloy (HEA) possesses distinctive thermal stability and electronic characteristics, which exhibits substantial potential for diverse applications in electrocatalytic reactions. However, accurately controlling the size of HEA still remains a challenge, especially for the ultrasmall HEA nanoparticles. Herein, we firstly calculate and illustrate the size impact on the electronic structure of HEA and the adsorption energies of crucial intermediates in typical electrocatalytic reactions, such as the hydrogen evolution reaction (HER), oxygen reduction reaction (ORR), CO2 electroreduction (CO2RR) and NO3- electroreduction (NO3RR).
View Article and Find Full Text PDFJ Inorg Biochem
December 2024
Departamento de Química Inorgánica, Analítica y Química Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Buenos Aires C1428EGA, Argentina; Instituto de Química Física de Los Materiales, Medio Ambiente y Energía (INQUIMAE), CONICET-Universidad de Buenos Aires, Buenos Aires C1428EGA, Argentina. Electronic address:
Here, we show that the replacement of the distal residues Asp and/or Arg of the DyP peroxidases from Bacillus subtilis and Pseudomonas putida results in functional enzymes, albeit with spectroscopically perturbed active sites. All the enzymes can be activated either by the addition of exogenous HO or by in situ electrochemical generation of the reactive oxygen species (ROS) OH, O and HO. The latter method leads to broader and upshifted pH-activity profiles.
View Article and Find Full Text PDFACS Appl Mater Interfaces
December 2024
Key Laboratory of Near-Net Forming of Light Metals of Liaoning Province, Dalian Jiaotong University, Dalian 116028, China.
Porous CuNi films are promising candidates for electrocatalytic water splitting, with their catalytic performance largely influenced by the crystallographic structure and chemical state. In this study, by employing a magnetic field-controlled bubble template-assisted electrodeposition method, CuNi films with a preferred Ni(111) crystal orientation were synthesized. Moreover, adjusting the magnetic field direction during deposition can affect the degree of preferred orientation and, consequently, the electrochemical activity of the films.
View Article and Find Full Text PDFChemphyschem
December 2024
Jilin University, Jilin University, Renmin Street, 130022, ChangChun, CHINA.
Electrochemical reduction of nitrate to ammonia (NO3RR) offers a promising strategy for renewable ammonia (NH3) synthesis and wastewater treatment, but still suffers from limited activity and NH3 selectivity due to the lack of effective electrocatalyst. Here, we perform a four-steps screening strategy to screen high performance NO3RR catalyst by density functional theory calculations using 23 single transition metals atom doped on 1T-WS2/graphene (TM@1T-WS2/graphene) as candidates. The results show that Cu@1T-WS2/graphene exhibits the highest NO3RR activity among 23 candidates with a low rate determining step energy barrier of 0.
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