Quantum tunneling rotor as a sensitive atomistic probe of guests in a metal-organic framework

Quantum tunneling rotors in a zeolitic imidazolate framework ZIF-8 can provide insights into local gas adsorption sites and local dynamics of porous structure, which are inaccessible to standard physisorption or x-ray diffraction sensitive primarily to long-range order. Using in situ high-resolution inelastic neutron scattering at 3 K, we follow the evolution of methyl tunneling with respect to the number of dosed gas molecules. While nitrogen adsorption decreases the energy of the tunneling peak, and ultimately hinders it completely (0.33 meV to zero), argon substantially increases the energy to 0.42 meV. Ab initio calculations of the rotational barrier of ZIF-8 show an exception to the reported adsorption sites hierarchy, resulting in anomalous adsorption behavior and linker dynamics at subatmospheric pressure. The findings reveal quantum tunneling rotors in metal-organic frameworks as a sensitive atomistic probe of local physicochemical phenomena.MMC Laboratory is supported by the ERC Consolidator Grant (PROMOFS Grant Agreement No. 771575) and EPSRC Awards (Grants No. EP/N014960/1 and No. EP/R511742/1). We thank ISIS Facility for the awarded OSIRIS beamtime (Grants No. RB1410426, No. RB1510529, and No. RB1610180), DOIs 10.5286/ISIS.E.RB1410426, 10.5286/ISIS.E.RB1510529, and 10.5286/ISIS.E.RB1610180, as well as the Cryogenics, and Pressure & Furnaces teams for their exemplary support. M.R.R. acknowledges the U.S. DOE Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division (Separation Sciences). This work is further supported by the Fund for Scientific Research Flanders (FWO) through a Ph.D. fellowship for A.L. (Grant No. 11D2220N) and a postdoctoral fellowship for S.M.J.R. (Grant No. 12T3522N). Financial support for F.F.-A. from the Spanish Ministry of Science and Innovation (Grant No. PID2020-114506GBI00 funded by MCIN/AEI/10.13039/501100011033 and Grant No. TED2021-129457B-I00 funded by MCIN/AEI/10.13039/501100011033 and the European Union NextGenerationEU/PRTR) as well as the Basque Government (Grant No. PIBA-2021-0026) is gratefully acknowledged. We also acknowledge the financial support received from the IKUR Strategy under the collaboration agreement between Ikerbasque Foundation and the Materials Physics Center on behalf of the Department of Education of the Basque Government.Peer reviewe

How reproducible are surface areas calculated from the BET equation?

Porosity and surface area analysis play a prominent role in modern materials science. At the heart of this sits the Brunauer-Emmett-Teller (BET) theory, which has been a remarkably successful contribution to the field of materials science. The BET method was developed in the 1930s for open surfaces but is now the most widely used metric for the estimation of surface areas of micro- and mesoporous materials. Despite its widespread use, the calculation of BET surface areas causes a spread in reported areas, resulting in reproducibility problems in both academia and industry. To prove this, for this analysis, 18 already-measured raw adsorption isotherms were provided to sixty-one labs, who were asked to calculate the corresponding BET areas. This round-robin exercise resulted in a wide range of values. Here, the reproducibility of BET area determination from identical isotherms is demonstrated to be a largely ignored issue, raising critical concerns over the reliability of reported BET areas. To solve this major issue, a new computational approach to accurately and systematically determine the BET area of nanoporous materials is developed. The software, called "BET surface identification" (BETSI), expands on the well-known Rouquerol criteria and makes an unambiguous BET area assignment possible

Velocity-jump instabilities in Hele-Shaw flow of associating polymer solutions

We study fracturelike flow instabilities that arise when water is injected into a Hele-Shaw cell filled with aqueous solutions of associating polymers. We explore various polymer architectures, molecular weights, and solution concentrations. Simultaneous measurements of the finger tip velocity and of the pressure at the injection point allow us to describe the dynamics of the finger in terms of the finger mobility, which relates the velocity to the pressure gradient. The flow discontinuities, characterized by jumps in the finger tip velocity, which are observed in experiments with some of the polymer solutions, can be modeled by using a nonmonotonic dependence between a characteristic shear stress and the shear rate at the tip of the finger. A simple model, which is based on a viscosity function containing both a Newtonian and a non-Newtonian component, and which predicts nonmonotonic regions when the non-Newtonian component of the viscosity dominates, is shown to agree with the experimental data