Molecular Sieving Properties of Nanoporous Mixed-Linker ZIF-62: Associated Structural Changes upon Gas Adsorption Application

The evaluation of the flexibility in zeolitic imidazolate frameworks (ZIFs) has been very useful to understand their performance in gas adsorption and separation applications. Here, we have evaluated the adsorption properties of a nanoporous mixed-linker ZIF-62 using a combination of gas adsorption measurements, grand canonical Monte Carlo simulations, and synchrotron X-ray powder diffraction under operando conditions. While adsorption studies in nanoporous ZIF-62 at 77 K and atmospheric pressure predict a large O2/N2 separation ability, computational studies anticipate that the observed differences must be attributed to kinetic restrictions of N2 to access the internal porosity at cryogenic temperatures. Interestingly, upon a small increase in the adsorption temperature (90 K vs 77 K), both N2 and O2 are able to access the inner porous structure through the promotion of a phase transition (ca. 3.8% volume expansion) upon gas adsorption. This narrow phase (np) to expanded phase (ep) structural transition in ZIF-62 is completely suppressed above 150 K. Based on the excellent molecular sieve properties of nanoporous ZIF-62 for O2/N2 at cryogenic temperatures, we extended our study to the adsorption of linear and branched hydrocarbons. This study predicts the preferential adsorption of alkanes over alkenes in ZIF-62 for small hydrocarbons (C2), while in the case of C3 hydrocarbons and above, the adsorption process is mainly defined by kinetic restrictions.J.S.-A. acknowledges financial support from the MINECO (Projects MAT2016-80285-p and PID2019-108453GB-C21). The authors acknowledge ALBA for providing beamtime (Project No. 2019023264). Computational work was supported by the Cambridge High-Performance Computing Service, the Cambridge Service for Data-Driven Discovery (CSD3)

Freezing/melting of water in the confined nanospace of carbon materials: Effect of an external stimulus

Freezing/melting behavior of water confined in the nanopores of activated carbon materials has been evaluated using differential scanning calorimetry (DSC) at different water loadings, and after the application of an external stimulus. Under atmospheric pressure conditions, the DSC scans show a depression in the freezing/melting point of confined water compared to the bulk system. Interestingly, water confined in narrow micropores (pores below 0.7 nm) does not exhibit any phase transition, i.e. it is non-freezable water. Inelastic neutron scattering (INS) data confirm the presence of a distorted molecular assembly in narrow micropores, whereas synchrotron X-ray powder diffraction data (SXRPD) demonstrate the non-freezable nature of the water confined in these narrow-constrictions. Similar experiments under high-pressure CH4 give rise to a completely different scenario. Under high-pressure conditions methane hydrates are formed with a water-to-hydrate yield of 100% for the under-saturated and saturated samples, i.e. in the presence of an external stimulus even water in narrow micropores is prone to experience a liquid-to-solid phase transition. These results confirm the beneficial role of carbon as a host structure to promote nucleation and growth of methane hydrates with faster kinetics and a higher yield compared to the bulk system and to other porous materials.The authors would like to acknowledge financial support from the MINECO (MAT2016-80285-p), Generalitat Valenciana (PROMETEOII/2014/004), H2020 (MSCA-RISE-2016/NanoMed Project), Spanish ALBA synchrotron (Projects 2018022707 & 2019023322) and Oak Ridge beam time availability (Project IPTS-20843.1)

Electrochemical Investigation of Calcium Substituted Monoclinic Li3_3 V2_2(PO4_4)3_3 Negative Electrode Materials for Sodium‐ and Potassium‐Ion Batteries

Herein, the electrochemical properties and reaction mechanism of Li$_{3‒2x}$Ca$_x$V$_2$(PO$_4$)$_3$/C (x = 0, 0.5, 1, and 1.5) as negative electrode materials for sodium-ion/potassium-ion batteries (SIBs/PIBs) are investigated. All samples undergo a mixed contribution of diffusion-controlled and pseudocapacitive-type processes in SIBs and PIBs via Trasatti Differentiation Method, while the latter increases with Ca content increase. Among them, Li$_3$V$_2$(PO$_4$)$_3$/C exhibits the highest reversible capacity in SIBs and PIBs, while Ca$_{1.5}$V$_2$(PO$_4$)$_3$/C shows the best rate performance with a capacity retention of 46% at 20 C in SIBs and 47% at 10 C in PIBs. This study demonstrates that the specific capacity of this type of material in SIBs and PIBs does not increase with the Ca-content as previously observed in lithium-ion system, but the stability and performance at a high C-rate can be improved by replacing Li$^+$ with Ca$^{2+}$. This indicates that the insertion of different monovalent cations (Na$^+$/K$^+$) can strongly influence the redox reaction and structure evolution of the host materials, due to the larger ion size of Na$^+$ and K$^+$ and their different kinetic properties with respect to Li$^+$. Furthermore, the working mechanism of both LVP/C and Ca$_{1.5}$V$_2$(PO$_4$)$_3$/C in SIBs are elucidated via in operando synchrotron diffraction and in operando X-ray absorption spectroscopy

Electrochemical performance and reaction mechanism investigation of V₂O₅ positive electrode material for aqueous rechargeable zinc batteries

The electrochemical performance and reaction mechanism of orthorhombic V$_2$O$_5$ in 1 M ZnSO$_4$ aqueous electrolyte are investigated. V$_2$O$_5$ nanowires exhibit an initial discharge and charge capacity of 277 and 432 mA h g$^{−1}$, respectively, at a current density of 50 mA g$^{−1}$. The material undergoes quick capacity fading during cycling under both low (50 mA g$^{−1}$) and high (200 mA g$^{−1}$) currents. V$_2$O$_5$ can deliver a higher discharge capacity at 200 mA g$^{−1}$ than that at 50 mA g$^{−1}$ after 10 cycles, which could be attributed to a different type of activation process under both current densities and distinct degrees of side reactions (parasitic reactions). Cyclic voltammetry shows several successive redox peaks during Zn ion insertion and deinsertion. In operando synchrotron diffraction reveals that V$_2$O$_5$ undergoes a solid solution and two-phase reaction during the 1st cycle, accompanied by the formation/decomposition of byproducts Zn$_3$(OH)$_2$V$_2$O$_7$·2(H$_2$O) and ZnSO$_4$Zn$_3$(OH)$_6$·5H$_2$O. In the 2nd insertion process, V$_2$O$_5$ goes through the same two-phase reaction as that in the 1st cycle, with the formation of the byproduct ZnSO$_4$Zn$_3$(OH)$_6$·5H$_2$O. The reduction/oxidation of vanadium is confirmed by in operando X-ray absorption spectroscopy. Furthermore, Raman, TEM, and X-ray photoelectron spectroscopy (XPS) confirm the byproduct formation and the reversible Zn ion insertion/deinsertion in the V$_2$O$_5$

Structural Origin of Suppressed Voltage Decay in Single‐Crystalline Li‐Rich Layered Li[Li0.2_{0.2}Ni0.2_{0.2}Mn0.6_{0.6}]O2_{2} Cathodes

Lithium- and manganese-rich layered oxides (LMLOs, ≥ 250 mAh g$^{−1}$) with polycrystalline morphology always suffer from severe voltage decay upon cycling because of the anisotropic lattice strain and oxygen release induced chemo-mechanical breakdown. Herein, a Co-free single-crystalline LMLO, that is, Li[Li$_{0.2}$Ni$_{0.2}$Mn$_{0.6}$]O$_{2}$ (LLNMO-SC), is prepared via a Li$^+$/Na$^+$ ion-exchange reaction. In situ synchrotron-based X-ray diffraction (sXRD) results demonstrate that relatively small changes in lattice parameters and reduced average micro-strain are observed in LLNMO-SC compared to its polycrystalline counterpart (LLNMO-PC) during the charge–discharge process. Specifically, the as-synthesized LLNMO-SC exhibits a unit cell volume change as low as 1.1% during electrochemical cycling. Such low strain characteristics ensure a stable framework for Li-ion insertion/extraction, which considerably enhances the structural stability of LLNMO during long-term cycling. Due to these peculiar benefits, the average discharge voltage of LLNMO-SC decreases by only ≈0.2 V after 100 cycles at 28 mA g$^{-1}$ between 2.0 and 4.8 V, which is much lower than that of LLNMO-PC (≈0.5 V). Such a single-crystalline strategy offers a promising solution to constructing stable high-energy lithium-ion batteries (LIBs)

New insights into the breathing phenomenon in ZIF-4

Structural changes in ZIFs upon adsorption remain a paradigm due to the sensitivity of the adsorption mechanism to the nature of the organic ligands and gas probe molecules. Synchrotron X-ray diffraction under operando conditions clearly demonstrates for the first time that ZIF-4 exhibits a structural reorientation from a narrow-pore (np) to a new expanded-pore (ep) structure upon N2 adsorption, while it does not do so for CO2 adsorption. The existence of an expanded-pore structure of ZIF-4 has also been predicted by molecular simulations. In simulations the expanded structure was stabilized by entropy at high temperatures and by strong adsorption of N2 at low temperatures. These results are in perfect agreement with manometric adsorption measurements for N2 at 77 K that show the threshold pressure for breathing at ∼30 kPa. Inelastic neutron scattering (INS) measurements show that CO2 is also able to promote structural changes but, in this specific case, only at cryogenic temperatures (5 K).The authors would like to acknowledge financial support from the MINECO (MAT2016-80285-p), Generalitat Valenciana (PROMETEOII/2014/004), H2020 (MSCA-RISE-2016/NanoMed Project), Spanish ALBA synchrotron (Projects AV-2017021985 and IH-2018012591) and Oak Ridge beam time availability (Project IPTS-20843.1). JSA and JGL acknowledge financial support from UA (ACIE17-15) to cover all the expenses for INS measurements at Oak Ridge. JGL acknowledges GV (GRISOLIAP/2016/089) for the research contract

Low-oxidation-state Ru sites stabilized in carbon-doped RuO2 with low-temperature CO2 activation to yield methane

The generation of methane fuel using surplus renewable energy with CO as the carbon source enables both the decarbonization and substitution of fossil fuel feedstocks. However, high temperatures are usually required for the efficient activation of CO. Here we present a solid catalyst synthesized using a mild, green hydrothermal synthesis that involves interstitial carbon doped into ruthenium oxide, which enables the stabilization of Ru cations in a low oxidation state and a ruthenium oxycarbonate phase to form. The catalyst shows an activity and selectivity for the conversion of CO into methane at lower temperatures than those of conventional catalysts, with an excellent long-term stability. Furthermore, this catalyst is able to operate under intermittent power supply conditions, which couples very well with electricity production systems based on renewable energies. The structure of the catalyst and the nature of the ruthenium species were acutely characterized by combining advanced imaging and spectroscopic tools at the macro and atomic scales, which highlighted the low-oxidation-state Ru sites (Ru, 0 < n < 4) as responsible for the high catalytic activity. This catalyst suggests alternative perspectives for materials design using interstitial dopants.We thank the support of C. Cerdá and M. D. Soriano in the catalyst preparation and testing. This research was funded by the Ministerio de Ciencia, Innovación y Universidades (grant nos. PID2021-1262350B-C31, PID2020-113006-RB-I00, PID2019-110018GA-I00 and MCIN/AEI/10.13039/501100011033), Generalitat Valenciana (grant no. CIAICO/2021/2138), the Department of Economy, Knowledge, Business and the University of the Regional Government of Andalusia (project reference FEDER-UCA18-107139). This study forms part of the Advanced Materials programme and was supported by MCIN with funding from the European Union Next Generation (EU PRTR-C17.11) and by Generalitad Valenciana (ref. MFA/2022/016). C.T.-S. acknowledges the Polytechnical University of Valencia for the economic support through an FPI scholarship associated with the PAID programme ‘Programa de Ayudas de Investigación y Desarrollo’. XAS, XPS and XRD experiments were performed at the ALBA Synchrotron with the collaboration of ALBA staff. Infrared experiments were performed at the SOLEIL Synchrotron with the collaboration of SOLEIL staff