Generalised analytical method unravels framework-dependent kinetics of adsorption-induced structural transition in flexible metal–organic frameworks

ゲート型吸着剤はガス分子をどう取り込む？ --サブ秒でのX線回折測定が動的過程を紐解く--. 京都大学プレスリリース. 2023-11-08.Flexible metal–organic frameworks (MOFs) exhibiting adsorption-induced structural transition can revolutionise adsorption separation processes, including CO₂ separation, which has become increasingly important in recent years. However, the kinetics of this structural transition remains poorly understood despite being crucial to process design. Here, the CO₂-induced gate opening of ELM-11 ([Cu(BF₄)₂(4, 4’-bipyridine)₂]n) is investigated by time-resolved in situ X-ray powder diffraction, and a theoretical kinetic model of this process is developed to gain atomistic insight into the transition dynamics. The thus-developed model consists of the differential pressure from the gate opening (indicating the ease of structural transition) and reaction model terms (indicating the transition propagation within the crystal). The reaction model of ELM-11 is an autocatalytic reaction with two pathways for CO₂ penetration of the framework. Moreover, gas adsorption analyses of two other flexible MOFs with different flexibilities indicate that the kinetics of the adsorption-induced structural transition is highly dependent on framework structure

Fast Gas‐Adsorption Kinetics in Supraparticle‐Based MOF Packings with Hierarchical Porosity

Metal–organic frameworks (MOFs) are microporous adsorbents for high-throughput gas separation. Such materials exhibit distinct adsorption characteristics owing to the flexibility of the crystal framework in a nanoparticle, which can be different from its bulk crystal. However, for practical applications, such particles need to be compacted into macroscopic pellets, creating mass-transport limitations. In this work, this problem is addressed by forming materials with structural hierarchy, using a supraparticle-based approach. Spherical supraparticles composed of nanosized MOF particles are fabricated by emulsion templating and they are used as the structural component forming a macroscopic material. Zeolitic imidazolate framework-8 (ZIF-8) particles are used as a model system and the gas-adsorption kinetics of the hierarchical material are compared with conventional pellets without structural hierarchy. It is demonstrated that a pellet packed with supraparticles exhibits a 30 times faster adsorption rate compared to an unstructured ZIF-8 powder pellet. These results underline the importance of controlling structural hierarchy to maximize the performance of existing materials. In the hierarchical MOFs, large macropores between the supraparticles, smaller macropores between individual ZIF-8 primary particles, and micropores inherent to the ZIF-8 framework collude to combine large surface area, defined adsorption sites, and efficient mass transport to enhance performance

The K2K SciBar Detector

A new near detector, SciBar, for the K2K long-baseline neutrino oscillation expe riment was installed to improve the measurement of neutrino energy spectrum and to study neutrino interactions in the energy region around 1 GeV. SciBar is a 'fully active' tracking detector with fine segmentation consisting of plastic scintillator bars. The detector was constructed in summer 2003 and is taking data since October 2003. The basic design and initial performance is presented.Comment: 7 pages, 4figures, Contributed to Proceedings of the 10th Vienna Conference on Instrumentation, Vienna, February 16-21, 200

Search for two-neutrino double electron capture on 124^{124}Xe with the XMASS-I detector

Double electron capture is a rare nuclear decay process in which two orbital electrons are captured simultaneously in the same nucleus. Measurement of its two-neutrino mode would provide a new reference for the calculation of nuclear matrix elements whereas observation of its neutrinoless mode would demonstrate lepton number violation. A search for two-neutrino double electron capture on $^{124}$Xe is performed using 165.9 days of data collected with the XMASS-I liquid xenon detector. No significant excess above background was observed and we set a lower limit on the half-life as $4.7 \times 10^{21}$ years at 90% confidence level. The obtained limit has ruled out parts of some theoretical expectations. We obtain a lower limit on the $^{126}$Xe two-neutrino double electron capture half-life of $4.3 \times 10^{21}$ years at 90% confidence level as well.Comment: 6 pages, 3 figures, accepted for publication in Physics Letters

Search for exotic neutrino-electron interactions using solar neutrinos in XMASS-I

We have searched for exotic neutrino-electron interactions that could be produced by a neutrino millicharge, by a neutrino magnetic moment, or by dark photons using solar neutrinos in the XMASS-I liquid xenon detector. We observed no significant signals in 711 days of data. We obtain an upper limit for neutrino millicharge of 5.4$\times$10$^{-12} e$ at 90\% confidence level assuming all three species of neutrino have common millicharge. We also set flavor dependent limits assuming the respective neutrino flavor is the only one carrying a millicharge, $7.3 \times 10^{-12} e$ for $\nu_e$, $1.1 \times 10^{-11} e$ for $\nu_{\mu}$, and $1.1 \times 10^{-11} e$ for $\nu_{\tau}$. These limits are the most stringent yet obtained from direct measurements. We also obtain an upper limit for the neutrino magnetic moment of 1.8$\times$10$^{-10}$ Bohr magnetons. In addition, we obtain upper limits for the coupling constant of dark photons in the $U(1)_{B-L}$ model of 1.3$\times$10$^{-6}$ if the dark photon mass is 1$\times 10^{-3}$ MeV$/c^{2}$, and 8.8$\times$10$^{-5}$ if it is 10 MeV$/c^{2}$

Direct dark matter search by annual modulation in XMASS-I

A search for dark matter was conducted by looking for an annual modulation signal due to the Earth's rotation around the Sun using XMASS, a single phase liquid xenon detector. The data used for this analysis was 359.2 live days times 832 kg of exposure accumulated between November 2013 and March 2015. When we assume Weakly Interacting Massive Particle (WIMP) dark matter elastically scattering on the target nuclei, the exclusion upper limit of the WIMP-nucleon cross section 4.3$\times$10$^{-41}$cm$^2$ at 8 GeV/c$^2$ was obtained and we exclude almost all the DAMA/LIBRA allowed region in the 6 to 16 GeV/c$^2$ range at $\sim$10$^{-40}$cm$^2$. The result of a simple modulation analysis, without assuming any specific dark matter model but including electron/$\gamma$ events, showed a slight negative amplitude. The $p$-values obtained with two independent analyses are 0.014 and 0.068 for null hypothesis, respectively. we obtained 90\% C.L. upper bounds that can be used to test various models. This is the first extensive annual modulation search probing this region with an exposure comparable to DAMA/LIBRA.Comment: 5 pages, 4 figure

Resolving theta_{23} Degeneracy by Accelerator and Reactor Neutrino Oscillation Experiments

If the lepton mixing angle theta_{23} is not maximal, there arises a problem of ambiguity in determining theta_{23} due to the existence of two degenerate solutions, one in the first and the other in the second octant. We discuss an experimental strategy for resolving the theta_{23} octant degeneracy by combining reactor measurement of theta_{13} with accelerator nu_{mu} disappearance and nu_{e} appearance experiments. The robustness of the theta_{23} degeneracy and the difficulty in lifting it only by accelerator experiments with conventional nu_{mu} (and nu_{mu}-bar) beam are demonstrated by analytical and numerical treatments. Our method offers a way to overcome the difficulty and can resolve the degeneracy between solutions sin^2 theta_{23} = 0.4 and sin^2 theta_{23} = 0.6 if sin^2 (2 theta_{13}) \gsim 0.05 at 95% CL by assuming the T2K phase II experiment and a reactor measurement with an exposure of 10 GW.kt.yr. The dependence of the resolving power of the octant degeneracy on the systematic errors of reactor experiments is also examined.Comment: 23 pages, 9 figures, version to appear in PR