The role of electrocatalysts in energy storage/conversion, biomedical and environmental sectors, green chemistry, and much more has generated enormous interest in comprehending their structure-activity relations. While targeting the surface-to-volume ratio, exposing reactive crystal planes and interfacial modifications are time-tested considerations for activating metallic catalysts; it is primarily by substitution in molecular electrocatalysts. This account draws the distinction between a substituent's chemical identity and isomerism, when regioisomerism of the -NO substituent is conferred at the "α" and "β" positions on the macrocycle of cobalt phthalocyanines. Spectroscopic analysis and theoretical calculations establish that the β isomer accumulates catalytically active intermediates via a cumulative influence of inductive and resonance effects. However, the field effect in the α isomer restricts this activation due to a vanishing resonance effect. The demonstration of the distinct role of isomerism in substituted molecular electrocatalysts for reactions ranging from energy conversion to biosensing highlights that isomerism of the substituents makes an independent contribution to electrocatalysis over its chemical identity.
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http://dx.doi.org/10.1021/acs.jpclett.9b02689 | DOI Listing |
Angew Chem Int Ed Engl
December 2024
Xiamen University, College of Chemistry and Chemical Engineering, 402 Siming Road, 361005, Xiamen, CHINA.
PtRu-based catalysts toward hydrogen oxidation reaction (HOR) suffer from low efficiency, CO poisoning and over-oxidation at high potentials. In this work, an amorphization strategy is adopted for preparation of amorphous SrRuPtOxHy nanobelts (a-SrRuPtOxHy NBs). The a-SrRuPtOxHy NBs have optimized adsorption of intermediates (H and OH), increased number of active sites, highly weakened CO poisoning and enhanced anti-oxidation ability owing to the special amorphous structure.
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December 2024
State Key Laboratory of Bio-fibers and Eco-textiles, Collaborative Innovation Center of Shandong Marine Biobased Fibers and Ecological Textiles, Institute of Marine Biobased Materials, College of Materials Science and Engineering, Qingdao University, Qingdao, 266071, P. R. China.
Organic small molecules (OSMs) with well-defined structures are crucial integral components of cathode catalysts for fuel cells. Despite the acknowledged potential of heteroatom doping to enhance the catalytic performance of metal-free carbon-based catalysts, there exists a notable gap in conducting molecular structure and catalytic activity, particularly under the premise of maintaining a constant molecular skeleton and with a clear molecular structure. Herein, the charge distribution is modulated by introducing different chalcogens into the same molecular skeleton through main-group engineering.
View Article and Find Full Text PDFJ Colloid Interface Sci
December 2024
Key Laboratory of Eco-chemical Engineering, International Science and Technology Cooperation Base of Eco-chemical Engineering and Green Manufacturing, College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, Qingdao 266042, PR China. Electronic address:
Despite the ultrahigh theoretical energy density and cost-effectiveness, aprotic lithium-oxygen (Li-O) batteries suffer from slow oxygen redox kinetics at cathodes and large voltage hysteresis. Here, we well-design ultrafine Co nanoparticles supported by N-doped mesoporous hollow carbon nanospindles (Co@HCNs) to serve as efficient electrocatalysts for Li-O battery. Benefiting from strong metal-support interactions, the obtained Co@HCNs manifest high affinity for the LiO intermediate, promoting formation of ultrathin nanosheet-like LiO with low-impedance contact interface on the Co@HCNs cathode surface, which facilitates the reversible decomposition upon charging.
View Article and Find Full Text PDFJ Colloid Interface Sci
December 2024
Key Laboratory of Eco-chemical Engineering, Ministry of Education, International Science and Technology Cooperation Base of Eco-chemical Engineering and Green Manufacturing, College of Chemistry and Molecular Engineering, Qingdao University of Science & Technology, 53 Zhengzhou Road, 266042 Qingdao, PR China. Electronic address:
The development of suitable support to maximize the atomic utilization efficiency of platinum is of great significance for the hydrogen evolution reaction (HER). Herein, we report a simple and fast nonequilibrium-corrosive approach to prepare oxygen defect-enriched FeO decorated with trace Pt onto nickel-iron foam (Pt/FeO-O/NIF). The Pt/FeO-O/NIF electrode is superhydrophilic with intimate contact with the electrolyte.
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December 2024
State Key Laboratory of Bio-fibers and Eco-textiles, Collaborative Innovation Center of Shandong Marine Biobased Fibers and Ecological Textiles, Institute of Marine Biobased Materials, College of Materials Science and Engineering, Qingdao University, Qingdao, 266071, P. R. China.
Polymer gels, renowned for unparalleled chemical stability and self-sustaining properties, have garnered significant attention in electrocatalysis. Notably, organic polymer gels that exhibit temperature sensitivity and incorporate suitable polar nonvolatile liquids, enhance electronic conductivity, and impart distinct morphological features, but remain largely unexplored as electrocatalysts for oxygen reduction reaction (ORR). To address this issue, an innovative strategy is proposed for synergistic modulation of the rigidity of mainchain molecular skeleton and length of alkyl sidechains, enabling the development of organogel polymers with a sol-gel temperature-sensitive phase transition that promises high selectivity and enhanced activity in electrocatalytic processes.
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