Publications

In heterogeneous catalysis, a nanoparticle (NP) system has immediate chemical surroundings with which its interaction needs to be considered, as nanoparticles are typically loaded onto certain supports. Beyond what is known about these interactions, dynamic atomic interactions between the nanoparticle and support could result from the increased energetics at the nanoscale. Here, we show that the dynamic response of atoms in copper nanoparticles to the underlying silica support at room temperature and ambient atmosphere results in the complete disappearance of supported nanoparticles over the course of only a few weeks. A quantitative study of copper nanoparticles at various size regimes (6-17 nm) revealed the significance of size-dependent nanoparticle energetics to the interaction with the support. Extended X-ray absorption fine structure is used to show that copper atoms could readily diffuse into the support to be locally surrounded by oxygen and silicon with structurally disordered outer coordination shells. Increased energetic states at the nanoscale and the energetically favorable configuration of individual copper atoms within silica, identified through EXAFS, are suggested as the cause of nanoparticle disappearance. This unexpected observation opens up new questions as to how nanoparticles interact with surrounding environments that could fundamentally change our conventional view of supported nanoparticle systems.

Luminous red novae (LRNe) are transients characterized by low luminosities and expansion velocities, and are associated with mergers or common envelope ejections in stellar binaries. Intermediate-luminosity red transients (ILRTs) are an observationally similar class with unknown origins, but generally believed to either be electron capture supernovae (ECSN) in super-AGB stars, or outbursts in dusty luminous blue variables (LBVs). In this paper, we present a systematic sample of 8 LRNe and 8 ILRTs detected as part of the Census of the Local Universe (CLU) experiment on the Zwicky Transient Facility (ZTF). The CLU experiment spectroscopically classifies ZTF transients associated with nearby ($<150$ Mpc) galaxies, achieving 80% completeness for m$_{r}<20$\,mag. Using the ZTF-CLU sample, we derive the first systematic LRNe volumetric-rate of 7.8$^{+6.5}_{-3.7}\times10^{-5}$ Mpc$^{-3}$ yr$^{-1}$ in the luminosity range $-16\leq$M$_{\rm{r}}$$\leq -11$ mag. We find that in this luminosity range, the LRN rate scales as dN/dL $\propto L^{-2.5\pm0.3}$ - significantly steeper than the previously derived scaling of $L^{-1.4\pm0.3}$ for lower luminosity LRNe (M$_{V}\geq-10$). The steeper power law for LRNe at high luminosities is consistent with the massive merger rates predicted by binary population synthesis models. We find that the rates of the brightest LRNe (M$_{r}\leq-13$ mag) are consistent with a significant fraction of them being progenitors of double compact objects (DCOs) that merge within a Hubble time. For ILRTs, we derive a volumetric rate of $2.6^{+1.8}_{-1.4}\times10^{-6}$ Mpc$^{-3}$yr$^{-1}$ for M$_{\rm{r}}\leq-13.5$, that scales as dN/dL $\propto L^{-2.5\pm0.5}$. This rate is $\approx1-5\%$ of the local core-collapse supernova rate, and is consistent with theoretical ECSN rate estimates.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

<title>Abstract</title> Global warming increases ecosystem respiration (ER), creating a positive carbon-climate feedback. Thermal acclimation, the direct responses of biological communities to reduce the effects of temperature changes on respiration rates, is a critical mechanism that compensates for warming-induced ER increases and dampens this positive feedback. However, the extent and effects of this mechanism across diverse ecosystems remain unclear. By analyzing CO2 flux data from 93 eddy covariance sites worldwide, we observed thermal acclimation at 84 % of the sites. If sustained, thermal acclimation could reduce projected warming-induced nighttime ER increases by at least 25 % across most climate zones by 2041-2060. Strong thermal acclimation is particularly evident in ecosystems at high elevation, with low-carbon-content soils, and within tundra, semi-arid, and warm-summer Mediterranean climates, supporting the hypothesis that extreme environments favor the evolution of greater acclimation potential. Moreover, ecosystems with dense vegetation and high productivity such as humid tropical and subtropical forests generally exhibit strong thermal acclimation, suggesting that regions with substantial CO2 uptake may continue to serve as strong carbon sinks. Conversely, some ecosystems in cold continental climates show signs of enhancing thermal responses, the opposite of thermal acclimation, which could exacerbate carbon losses as climate warms. Our study underscores the widespread yet climate-specific patterns of thermal acclimation in global terrestrial ER, emphasizing the need to incorporate these patterns into Earth System Models for more accurate carbon-climate feedback projections.

The size-tunable synthesis of poly(vinylpyrrolidone)-stabilized cuboctahedral rhodium nanoparticles with mean diameters ranging between 3-7 nm and multipod structures was accomplished using seeded growth methods. Isotropic PVP-capped 2.9 nm seeds were prepared by ligand exchange on rhodium-triphenylphosphine metal-organic clusters. Quantitative investigation of reaction parameters in ethylene glycol revealed that size and shape could be controlled at a single reaction temperature of 120 degrees C. The rate of rhodium monomer addition was found to be critical for monodispersity and shape control, regardless of thermodynamic factors. Solvent viscosity, varied by changing the polyol solvents, indicated that autocatalytic addition kinetics are responsible for isotropic versus anisotropic growth.