Homogeneously catalysed reactions can be 'switched on' by activating latent catalysts. Usually, activation is brought about by heat or an external chemical agent. However, activation of homogeneous catalysts with a mechanical trigger has not been demonstrated. Here, we introduce a general method to activate latent catalysts by mechanically breaking bonds between a metal and one of its ligands. We have found that silver(I) complexes of polymer-functionalized N-heterocyclic carbenes, which are latent organocatalysts, catalyse a transesterification reaction when exposed to ultrasound in solution. Furthermore, ultrasonic activation of a ruthenium biscarbene complex with appended polymer chains results in catalysis of olefin metathesis reactions. In each case, the catalytic activity results from ligand dissociation, brought about by transfer of mechanical forces from the polymeric substituents to the coordination bond. Mechanochemical catalyst activation has potential applications in transduction and amplification of mechanical signals, and mechanically initiated polymerizations hold promise as a novel repair mechanism in self-healing materials.
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http://dx.doi.org/10.1038/nchem.167 | DOI Listing |
ACS Appl Mater Interfaces
January 2025
Department of Environmental Engineering, Kwangwoon University, Seoul 01897, Republic of Korea.
The advancement of highly efficient and cost-effective electrocatalysts for electrochemical water splitting, along with the development of triboelectric nanogenerators (TENGs), is crucial for sustainable energy generation and harvesting. In this study, a novel hybrid composite by integrating graphitic carbon nitride (GCN) with an earth-abundant FeMg-layered double hydroxide (LDH) (GCN@FeMg-LDH) was synthesized by the hydrothermal approach. Under controlled conditions, with optimized concentrations of metal ions and GCN, the fabricated electrode, GCN@FeMg-LDH demonstrated remarkably low overpotentials of 0.
View Article and Find Full Text PDFACS Appl Mater Interfaces
January 2025
CEITEC-Central European Institute of Technology, Brno University of Technology, Purkyňova 123, Brno 61200, Czech Republic.
Detailed atomic-scale understanding is a crucial prerequisite for rational design of next-generation single-atom catalysts (SACs). However, the sub-ångström precision needed for systematic studies is challenging to achieve on common SACs. Here, we present a two-dimensional (2D) metal-organic system featuring Fe-N single-atom sites, where the metal-organic structure is modulated by 0.
View Article and Find Full Text PDFChem Soc Rev
January 2025
Department of Applied Physics, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong, P. R. China.
Establishing and regulating the ferroelectric polarization in ferroelectric nano-scale catalysts has been recognized as an emerging strategy to advance water splitting reactions, with the merits of improved surface charge density, high charge transfer rate, increased electronic conductivity, the creation of real active sites, and optimizing the chemisorption energy. As a result, engineering and tailoring the ferroelectric polarization induced internal electric field provides significant opportunities to improve the surface and electronic characteristics of catalysts, thereby enhancing the water splitting reaction kinetics. In this review, an interdisciplinary and comprehensive summary of recent advancements in the construction, characterization, engineering and regulation of the polarization in ferroelectric-based catalysts for water splitting is provided, by exploiting a variety of external stimuli.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Shenzhen University, College of Chemistry and Environmental Engineering, CHINA.
Rationally manipulating the in-situ formed catalytically active surface of catalysts remains a significant challenge for achieving highly efficient water electrolysis. Herein, we present a bias-induced activation strategy to modulate in-situ Ga leaching and trigger the dynamic surface restructuring of lamellar Ir@Ga2O3 for the electrochemical oxygen evolution reaction. The in-situ reconstructed Ga-O-Ir interface sustains high water oxidation rates at OER overpotentials.
View Article and Find Full Text PDFJ Colloid Interface Sci
January 2025
School of Resources and Environmental Engineering, Wuhan University of Technology, Wuhan 430070, China. Electronic address:
Antibiotic organic pollutants not only pose a significant threat to human health but also generate a large amount of carbon dioxide (CO) during the treatment process of advanced oxidation processes (AOPs). Herein, the antibiotics aqueous solution was firstly degraded and mineralized by light-assisted peroxymonosulfate (PMS) activation over hollow manganese dioxide (MnO) catalyst and then the corresponding released CO was effectively captured by calcium oxide (CaO) particles in the same sealed reactor, achieving wastewater treatment with zero carbon releasing. Under simulated light conditions, hollow MnO is excited to generate electron-hole pairs.
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