The main impediment to the development of zinc-air batteries is the sluggish kinetics of the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). Transition metal N-doped carbon catalysts offer a promising alternative to noble metal catalysts, with metal-organic framework (MOF)-derived carbon material catalysts being particularly noteworthy. Here, we synthesized MP-Z-C carbon catalysts by combining two-dimensional (2D) metal porphyrin-based MOFs (MPMFs, x = Fe, Co, Ni, Mn) and three-dimensional zeolitic imidazole framework-8 (ZIF-8) through electrostatic interaction, followed by carbonization. ZIF-8 was inserted between the layers of MPMFs to prevent its Π-Π stacking, allowing the active sites to become fully exposed. MP-Z-C demonstrated an impressive catalytic activity for both the ORR and the OER reactions. Among them, FeP-Z-C showed the best catalytic activity. The half-wave potential for ORR was 0.92 V (vs the reversible hydrogen electrode (RHE)), while the overpotential for the OER was 290 mV. In addition, the zinc-air battery assembled by FeP-Z-C exhibited high power density (133.14 mW cm) and significant specific capacity (816 mAh g), indicating considerable potential as a bifunctional catalyst for electronic devices.
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http://dx.doi.org/10.1021/acsami.3c18384 | DOI Listing |
ACS Appl Mater Interfaces
January 2025
Department of Catalysis & Fine Chemicals, CSIR- Indian Institute of Chemical Technology, Uppal Road, Hyderabad, Telangana State 500007, India.
Photoassisted CO reduction employing a metal-free system is both challenging and fascinating. In our study, we present a structural engineering strategy to tune the potential energy barrier, which, in turn, affects the photoreduction ability. A series of porphyrin-based porous organic polymers () were hydrothermally synthesized and the influence of keto-enol tautomerization on the CO photoreduction potential has been rigorously investigated.
View Article and Find Full Text PDFInorg Chem
January 2025
School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, P. R. China.
Porphyrins bearing the unique 18π electron tetrapyrrolic macrocycles exhibit interesting photophysical and photochemical properties and have been considered as promising ligands for the construction of functionalized metal-organic frameworks (MOFs). The combination of porphyrin-type ligands with lanthanide metals featured with diverse coordination environments to realize the novel functions as well as the diversity of the MOF is thus attractive but challenging. Herein, an unprecedented porphyrin-based samarium MOF (Sm-BCPP) composed of a 5,10-bis(4-carboxyphenyl)-10,20-diphenyl porphyrin (HBCPP) ligand and samarium-formed one-dimensional clusters has been constructed via a solvothermal approach, and the synthesized Sm-BCPP has excellent chemical stabilities, exhibiting red luminescence.
View Article and Find Full Text PDFMolecules
December 2024
College of Chemistry and Chemical Engineering, China University of Petroleum, Qingdao 266580, China.
As a key means to solve energy and environmental problems, photocatalytic technology has made remarkable progress in recent years. Organic semiconductor materials offer structural diversity and tunable energy levels and thus attracted great attention. Among them, porphyrin and its derivatives show great potential in photocatalytic reactions and light therapy due to their unique large-π conjugation structure, high apparent quantum efficiency, tailorable functionality, and excellent biocompatibility.
View Article and Find Full Text PDFMaterials (Basel)
December 2024
Department of Chemistry, Morgan State University, 1700 East Cold Spring Lane, Baltimore, MD 21251, USA.
Metal-organic frameworks (MOFs) are hybrid inorganic-organic 3D coordination polymers with metal sites and organic linkers, which are a "hot" topic in the research of sorption, separations, catalysis, sensing, and environmental remediation. In this study, we explore the molecular mechanism and kinetics of interaction of the new copper porphyrin aluminum metal-organic framework (actAl-MOF-TCPPCu) compound with a vapor of the volatile organic sulfur compound (VOSC) diethyl sulfide (DES). First, compound was synthesized by post-synthetic modification (PSM) of Al-MOF-TCPPH compound by inserting Cu ions into the porphyrin ring and characterized by complementary qualitative and quantitative chemical, structural, and spectroscopic analysis.
View Article and Find Full Text PDFSmall Methods
January 2025
College of Environmental Science and Engineering, Hunan University and Key Laboratory of Environmental Biology and Pollution Control (Hunan University), Ministry of Education, Changsha, 410082, P. R. China.
In recent years, porphyrins have been frequently reported as photocatalysts due to their fascinating photochemical properties. However, porphyrins have the same shortcomings as other homogeneous photocatalysts, such as poor stability and difficulty in recovering. To solve this problem, it is a good strategy to form a porphyrin-based metal-organic framework (PMOF) by modifying porphyrin functional groups and adding metals as nodes to connect and control the arrangement of porphyrins.
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