MXenes are a recently discovered family of two-dimensional (2D) early transition metal carbides and carbonitrides, which have already shown many attractive properties and great promise in energy storage and many other applications. However, a complex surface chemistry and small coherence length have been obstacles in some applications of MXenes, also limiting the accuracy of predictions of their properties. In this study, we describe and benchmark a novel way of modeling layered materials with real interfaces (diverse surface functional groups and stacking order between the adjacent monolayers) against experimental data. The structures of three kinds of Ti3C2T x MXenes (T stands for surface terminating species, including O, OH, and F) produced under different synthesis conditions were resolved for the first time using atomic pair distribution function obtained by high-quality neutron total scattering. The true nature of the material can be easily captured with the sensitivity of neutron scattering to the surface species of interest and the detailed “third-generation” structure model we present. The modeling approach leads to new understanding of MXene structural properties and can replace the currently used idealized models in predictions of a variety of physical, chemical, and functional properties of Ti3C2-based MXenes. The developed models can be employed to guide the design of new MXene materials with selected surface termination and controlled contact angle, catalytic, optical, electrochemical, and other properties. We suggest that the multilevel structural modeling should form the basis for a generalized methodology on modeling diffraction and pair distribution function data for 2D and layered materials.

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Understanding of structural, electrical, and gravimetric peculiarities of water vapor interaction with ion-intercalated MXenes led to design of a multimodal humidity sensor. Neutron scattering coupled to molecular dynamics and ab initio calculations showed that a small amount of hydration results in a significant increase in the spacing between MXene layers in the presence of K and Mg intercalants between the layers. Films of K- and Mg-intercalated MXenes exhibited relative humidity (RH) detection thresholds of ∼0.8% RH and showed monotonic RH response in the 0-85% RH range. We found that MXene gravimetric response to water is 10 times faster than their electrical response, suggesting that HO-induced swelling/contraction of channels between MXene sheets results in trapping of HO molecules that act as charge-depleting dopants. The results demonstrate the use of MXenes as humidity sensors and infer potential impact of water on structural and electrical performance of MXene-based devices.

Boehmite (γ-AlOOH) and gibbsite (α-Al(OH) 3 ) are important archetype (oxy)hydroxides of aluminum in nature that also play diverse roles across a plethora of industrial applications. Developing the ability to understand and predict the properties and characteristics of these materials, on the basis of their natural growth or synthesis pathways, is an important 1 fundamental science enterprise with wide ranging impacts. The present study describes bulk and surface characteristics of these novel materials in comprehensive detail, using a collectively-sophisticated set of experimental capabilities, including a range of conventional laboratory solids analyses and national user facility analyses such as synchrotron X-ray absorption and scattering spectroscopies, as well as small angle neutron scattering. Their thermal stability is investigated using in situ temperature-dependent Raman spectroscopy. These pure and effectively defect-free materials are ideal for synthesis of advanced alumina products.

The structure of SnO2 nanoparticles (avg. 5 nm) with a few layers of water on the surface has been elucidated by atomic pair distribution function (PDF) methods using in situ neutron total scattering data and molecular dynamics (MD) simulations. Analysis of PDF, neutron prompt gamma, and thermogravimetric data, coupled with MD-generated surface D2O/OD configurations demonstrates that the minimum concentration of OD groups required to prevent rapid growth of nanoparticles during thermal dehydration corresponds to ~0.7 monolayer coverage. Surface hydration layers not only stabilize the SnO2 nanoparticles but also induce particle-size-dependent structural modifications and are likely to promote interfacial reactions through hydrogen bonds between adjacent particles. Upon heating/dehydration under vacuum above 250 °C, nanoparticles start to grow with low activation energies, rapid increase of nanoparticle size, and a reduction in the a lattice dimension. This study underscores the value of neutron diffraction and prompt-gamma analysis, coupled with molecular modeling, in elucidating the influence of surface hydration on the structure and metastable persistence of oxide nanomaterials.

It is generally believed that HO and OH are the key species stabilizing and controlling amorphous calcium carbonate "polyamorph" forms, and may in turn control the ultimate crystallization products during synthesis and in natural systems. Yet, the locations and hydrogen-bonding network of these species in ACC have never been measured directly using neutron diffraction. We report a synthesis route that overcomes the existing challenges with respect to yield quantities and deuteration, both of which are critically necessary for high quality neutron studies.

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