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1. Proton switching molecular magnetoelectricity

   https://doi.org/10.1038/s41467-021-24941-9  

   Hu, Yong ; Broderick, Scott ; Guo, Zipeng ; N’Diaye, Alpha T. ; Bola, Jaspal S. ; Malissa, Hans ; Li, Cheng ; Zhang, Qiang ; Huang, Yulong ; Jia, Quanxi ; et al ( December 2021 , Nature Communications)

   Abstract The convergence of proton conduction and multiferroics is generating a compelling opportunity to achieve strong magnetoelectric coupling and magneto-ionics, offering a versatile platform to realize molecular magnetoelectrics. Here we describe machine learning coupled with additive manufacturing to accelerate the design strategy for hydrogen-bonded multiferroic macromolecules accompanied by strong proton dependence of magnetic properties. The proton switching magnetoelectricity occurs in three-dimensional molecular heterogeneous solids. It consists of a molecular magnet network as proton reservoir to modulate ferroelectric polarization, while molecular ferroelectrics charging proton transfer to reversibly manipulate magnetism. The magnetoelectric coupling induces a reversible 29% magnetization control at ferroelectric phase transition with a broad thermal hysteresis width of 160 K (192 K to 352 K), while a room-temperature reversible magnetic modulation is realized at a low electric field stimulus of 1 kV cm −1 . The findings of electrostatic proton transfer provide a pathway of proton mediated magnetization control in hierarchical molecular multiferroics.
2. PHIP hyperpolarized [1-13C]pyruvate and [1-13C]acetate esters via PH-INEPT polarization transfer monitored by 13C NMR and MRI

   https://doi.org/10.1038/s41598-021-85136-2  

   Svyatova, Alexandra ; Kozinenko, Vitaly P. ; Chukanov, Nikita V. ; Burueva, Dudari B. ; Chekmenev, Eduard Y. ; Chen, Yu-Wen ; Hwang, Dennis W. ; Kovtunov, Kirill V. ; Koptyug, Igor V. ( March 2021 , Scientific Reports)

   Parahydrogen-induced polarization of¹³C nuclei by side-arm hydrogenation (PHIP-SAH) for [1-¹³C]acetate and [1-¹³C]pyruvate esters with application of PH-INEPT-type pulse sequences for¹H to¹³C polarization transfer is reported, and its efficiency is compared with that of polarization transfer based on magnetic field cycling (MFC). The pulse-sequence transfer approach may have its merits in some applications because the entire hyperpolarization procedure is implemented directly in an NMR or MRI instrument, whereas MFC requires a controlled field variation at low magnetic fields. Optimization of the PH-INEPT-type transfer sequences resulted in¹³C polarization values of 0.66 ± 0.04% and 0.19 ± 0.02% for allyl [1-¹³C]pyruvate and ethyl [1-¹³C]acetate, respectively, which is lower than the corresponding polarization levels obtained with MFC for¹H to¹³C polarization transfer (3.95 ± 0.05% and 0.65 ± 0.05% for allyl [1-¹³C]pyruvate and ethyl [1-¹³C]acetate, respectively). Nevertheless, a significant¹³C NMR signal enhancement with respect to thermal polarization allowed us to perform¹³C MR imaging of both biologically relevant hyperpolarized molecules which can be used to produce useful contrast agents for the in vivo imaging applications.
3. pH swing cycle for CO ₂ capture electrochemically driven through proton-coupled electron transfer

   https://doi.org/10.1039/D0EE01834A  

   Jin, Shijian ; Wu, Min ; Gordon, Roy G. ; Aziz, Michael J. ; Kwabi, David G. ( October 2020 , Energy & Environmental Science)

   We perform a thermodynamic analysis of the energetic cost of CO 2 separation from flue gas (0.1 bar CO 2 (g)) and air (400 ppm CO 2 ) using a pH swing created by electrochemical redox reactions involving proton-coupled electron transfer from molecular species in aqueous electrolyte. In this scheme, electrochemical reduction of these molecules results in the formation of alkaline solution, into which CO 2 is absorbed; subsequent electrochemical oxidation of the reduced molecules results in the acidification of the solution, triggering the release of pure CO 2 gas. We examined the effect of buffering from the CO 2 –carbonate system on the solution pH during the cycle, and thereby on the open-circuit potential of an electrochemical cell in an idealized four-process CO 2 capture-release cycle. The minimum work input varies from 16 to 75 kJ mol CO2 −1 as throughput increases, for both flue gas and direct air capture, with the potential to go substantially lower if CO 2 capture or release is performed simultaneously with electrochemical reduction or oxidation. We discuss the properties required of molecules that would be suitable for such a cycle. We also demonstrate multiple experimental cycles of an electrochemical CO 2 capture andmore »release system using 0.078 M sodium 3,3′-(phenazine-2,3-diylbis(oxy))bis(propane-1-sulfonate) as the proton carrier in an aqueous flow cell. CO 2 capture and release are both performed at 0.465 bar at a variety of current densities. When extrapolated to infinitesimal current density we obtain an experimental cycle work of 47.0 kJ mol CO2 −1 . This result suggests that, in the presence of a 0.465 bar/1.0 bar inlet/outlet pressure ratio, a 1.9 kJ mol CO2 −1 thermodynamic penalty should add to the measured value, yielding an energy cost of 48.9 kJ mol CO2 −1 in the low-current-density limit. This result is within a factor of two of the ideal cycle work of 34 kJ mol CO2 −1 for capturing at 0.465 bar and releasing at 1.0 bar. The ideal cycle work and experimental cycle work values are compared with those for other electrochemical and thermal CO 2 separation methods.« less
4. Fracture toughness of a metal–organic framework glass

   https://doi.org/10.1038/s41467-020-16382-7  

   To, Theany ; Sørensen, Søren S. ; Stepniewska, Malwina ; Qiao, Ang ; Jensen, Lars R. ; Bauchy, Mathieu ; Yue, Yuanzheng ; Smedskjaer, Morten M. ( May 2020 , Nature Communications)

   Metal-organic framework glasses feature unique thermal, structural, and chemical properties compared to traditional metallic, organic, and oxide glasses. So far, there is a lack of knowledge of their mechanical properties, especially toughness and strength, owing to the challenge in preparing large bulk glass samples for mechanical testing. However, a recently developed melting method enables fabrication of large bulk glass samples (>25 mm³) from zeolitic imidazolate frameworks. Here, fracture toughness (K_Ic) of a representative glass, namely ZIF-62 glass (Zn(C₃H₃N₂)_1.75(C₇H₅N₂)_0.25), is measured using single-edge precracked beam method and simulated using reactive molecular dynamics.K_Icis determined to be ~0.1 MPa m^0.5, which is even lower than that of brittle oxide glasses due to the preferential breakage of the weak coordinative bonds (Zn-N). The glass is found to exhibit an anomalous brittle-to-ductile transition behavior, considering its low fracture surface energy despite similar Poisson’s ratio to that of many ductile metallic and organic glasses.
5. Micron-gap spacers with ultrahigh thermal resistance and mechanical robustness for direct energy conversion

   https://doi.org/10.1038/s41378-019-0071-4  

   Nicaise, Samuel M. ; Lin, Chen ; Azadi, Mohsen ; Bozorg-Grayeli, Tara ; Adebayo-Ige, Promise ; Lilley, Drew E. ; Pfitzer, Yann ; Cha, Wujoon ; Van Houten, Kyana ; Melosh, Nicholas A. ; et al ( July 2019 , Microsystems & Nanoengineering)

   In thermionic energy converters, the absolute efficiency can be increased up to 40% if space-charge losses are eliminated by using a sub-10-µm gap between the electrodes. One practical way to achieve such small gaps over large device areas is to use a stiff and thermally insulating spacer between the two electrodes. We report on the design, fabrication and characterization of thin-film alumina-based spacers that provided robust 3–8 μm gaps between planar substrates and had effective thermal conductivities less than those of aerogels. The spacers were fabricated on silicon molds and, after release, could be manually transferred onto any substrate. In large-scale compression testing, they sustained compressive stresses of 0.4–4 MPa without fracture. Experimentally, the thermal conductance was 10–30 mWcm⁻²K⁻¹and, surprisingly, independent of film thickness (100–800 nm) and spacer height. To explain this independence, we developed a model that includes the pressure-dependent conductance of locally distributed asperities and sparse contact points throughout the spacer structure, indicating that only 0.1–0.5% of the spacer-electrode interface was conducting heat. Our spacers show remarkable functionality over multiple length scales, providing insulating micrometer gaps over centimeter areas using nanoscale films. These innovations can be applied to other technologies requiring high thermal resistance in small spaces, such as thermophotovoltaic converters,more »insulation for spacecraft and cryogenic devices.

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