Kinetics of the deposition process of k -mers in the presence of desorption or/and diffusional relaxation of particles is studied by Monte Carlo method on a one-dimensional lattice. For reversible deposition of k-mers, we find that after the initial "jamming," a stretched exponential growth of the coverage theta(t) toward the steady-state value theta(eq) occurs, i.e., theta(eq)-theta(t) is proportional to exp[-(t/tau)(beta)]. The characteristic time scale tau is found to decrease with desorption probability P(des) according to a power law, tau is proportional to P(des)(-gamma), with the same exponent gamma=1.22+/-0.04 for all k-mers. For irreversible deposition with diffusional relaxation, the growth of the coverage theta(t) above the jamming limit to the closest packing limit (CPL) theta(CPL) is described by the pattern theta(CPL)-theta(t) is proportional to E(beta)[-(t/tau)(beta)], where E(beta) denotes the Mittag-Leffler function of order beta(0,1) . Similarly to the reversible case, we found that the dependence of the relaxation time tau on the diffusion probability P(dif) is consistent again with a simple power-law, i.e., tau is proportional to P(dif)(-delta). When adsorption, desorption, and diffusion occur simultaneously, coverage always reaches an equilibrium value theta(eq), which depends only on the desorption/adsorption probability ratio. The presence of diffusion only hastens the approach to the equilibrium state, so that the stretched exponential function gives a very accurate description of the deposition kinetics of these processes in the whole range above the jamming limit.
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http://dx.doi.org/10.1103/PhysRevE.80.021115 | DOI Listing |
ACS Nano
January 2025
Creative Research Initiative Center for Nanospace-confined Chemical Reactions (NCCR), Pohang University of Science and Technology (POSTECH), Pohang 37673, Korea.
Unlike homogeneous metal complexes, achieving absolute control over reaction selectivity in heterogeneous catalysts remains a formidable challenge due to the unguided molecular adsorption/desorption on metal-surface sites. Conventional organic surface modifiers or ligands and rigid inorganic and metal-organic porous shells are not fully effective. Here, we introduce the concept of "ligand-porous shell cooperativity" to desirably reaction selectivity in heterogeneous catalysis.
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January 2025
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012, P. R. China.
Orbital structures are strongly correlated with catalytic performance, whereas their regulation strategy is still in pursuit. Herein, the Fe 3 and O 2 orbital hybridization was optimized by controlling the content of amorphous NiFe(OH) (a-NiFe(OH)), which was grown in situ on crystalline NiFeO (c-NiFeO) using an ultrasonic reduction method. The results of electron energy loss spectroscopy (EELS) and X-ray absorption spectra (XAS) revealed that the Fe-O orbital hybridization in a-NiFe(OH) is effectively strengthened by jointing with the adjacent oxygen (O) in c-NiFeO, which is further confirmed by the higher antibonding orbital energies based on density functional theory (DFT) calculations.
View Article and Find Full Text PDFAdv Mater
January 2025
School of Materials Science and Engineering, Peking University, Beijing, 100871, P. R. China.
Innovating nanocatalysts with both high intrinsic catalytic activity and high selectivity is crucial for multi-electron reactions, however, their low mass/electron transport at industrial-level currents is often overlooked, which usually leads to low comprehensive performance at the device level. Herein, a Cl/O etching-assisted self-assembly strategy is reported for synthesizing a self-assembled gap-rich PdMn nanofibers with high mass/electron transport highway for greatly enhancing the electrocatalytic reforming of waste plastics at industrial-level currents. The self-assembled PdMn nanofiber shows excellent catalytic activity in upcycling waste plastics into glycolic acid, with a high current density of 223 mA cm@0.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Shanghai Institute of Ceramics Chinese Academy of Sciences, State Key Laboratory of High Performance Ceramics and Superfine Microstructure, CHINA.
Pairing photocatalytic 1,2,3,4-tetrahydroisoquinoline semi-dehydrogenation reaction (THIQ-SDR) with two-electron oxygen reduction reaction (2e- ORR) is a green solar to chemical strategy by simultaneously utilizing the photo-excited electrons and holes. However, it is still short of high-efficiency photocatalyst to drive two reactions above. In the present work, crystalline pyrene-thiourea/urea covalent organic frameworks (COF-Py-S and -O) were synthesized and demonstrated as high-performance metal-free photocatalysts.
View Article and Find Full Text PDFChem Asian J
January 2025
Fudan University, Department of Environmental Science and Engineering, Shanghai Handan Road 220, 200433, Shanghai, CHINA.
Novel Ce1-xMnxVO4 catalysts prepared via modified hydrothermal synthesis were used in selective catalytic reduction of NO using NH3 (NH3-SCR). The Ce1-xMnxVO4 catalysts displayed optimum NO removal efficiency at 250 oC. Physicochemical properties including crystal type, morphology, particle size, elemental composition, BET surface area, chemical bond, and valence state were studied by XRD, TEM, EDS, N2 adsorption-desorption, Raman spectroscopy, and XPS.
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