Institut de Recherche de Chimie Paris

While the Born elastic stability criteria are well known for cubic crystals, there is some confusion in the literature about the form they should take for lower-symmetry crystal classes. Here we present closed form necessary and sufficient conditions for elastic stability in all crystal classes, as a concise and pedagogical reference to stability criteria in noncubic materials.

We report on the implementation of a tool for the analysis of second-order elastic stiffness tensors, provided with both an open-source Python module and a standalone online application allowing the visualization of anisotropic mechanical properties. After describing the software features, how we compute the conventional elastic constants and how we represent them graphically, we explain our technical choices for the implementation. In particular, we focus on why a Python module is used to generate the HTML web page with embedded Javascript for dynamical plots.

Mixed-metal MOFs are metal-organic frameworks that contain at least 2 different metal ions as nodes of their frameworks. They are prepared relatively easily by either a one-pot synthesis with a synthesis mixture containing the different metals, or by a post-synthetic ion-exchange method by soaking a monometallic MOF in a concentrated solution of a different (but compatible) metal-ion. More difficult is the accurate characterization of these materials. Is the formed product a mixture of monometallic MOFs or indeed a MOF with different metallic nodes? Are the metals randomly distributed or do they form domains? What is the oxidation state of the metals? How do the metals mutually influence each other, and impact the material's performance? Advanced characterization techniques are required e.g. X-ray absorption spectroscopy, magnetic resonance and electron microscopy. Computational tools at multiple scales are also often applied. In almost every case, a judicious choice of several techniques is required to unambiguously characterize the mixed-metal MOF. Although still in their infancy, several applications are emerging for mixed-metal MOFs, that improve on conventional monometallic MOFs. In the field of gas sorption and storage, especially the stability and affinity towards the target gases can be largely improved by introducing a second metal ion. In the case of flexible MOFs, the breathing behavior, and in particular the pressure at which the MOF opens, can be tailored. In heterogeneous catalysis, new cascade and tandem reactions become possible, with particular focus on reactions where the two metals in close proximity truly form a mixed-metal transition state. The bimetallic MOF should have a clear benefit over a mixture of the respective monometallic MOFs, and bimetallic enzymes can be a huge source of inspiration in this field. Another very promising application lies in the fields of luminescence and sensing. By tuning the lanthanide metals in mixed-metal lanthanide MOFs and by using the organic linkers as antennae, novel smart materials can be developed, acting as sensors and as thermochromic thermometers. Of course there are also still open challenges, as also mixed-metal MOFs do not escape the typical drawbacks of MOFs, such as low stability in moisture and possible metal leaching in liquids. The ease of synthesis of mixed-metal MOFs is a large bonus. In this critical review, we discuss in detail the synthesis, characterization, computational work and applications of mixed-metal MOFs.

A green method for epoxidation of imines using an environmentally benign oxidant system, H2O2/dimethyl carbonate, was developed. N-Alkyloxaziridines were prepared in high yields from N-alkylamines and (hetero)aromatic aldehydes in one-pot fashion, whereas N-sulfonyloxaziridines have been prepared by using the same oxidant system and 5 mol% of Zn(OAc)2·2H2O as catalyst.

Abstract It is generally believed that CO 2 electroreduction to multi‐carbon products such as ethanol or ethylene may be catalyzed with significant yield only on metallic copper surfaces, implying large ensembles of copper atoms. Here, we report on an inexpensive Cu‐N‐C material prepared via a simple pyrolytic route that exclusively feature single copper atoms with a CuN 4 coordination environment, atomically dispersed in a nitrogen‐doped conductive carbon matrix. This material achieves aqueous CO 2 electroreduction to ethanol at a Faradaic yield of 55 % under optimized conditions (electrolyte: 0.1 m CsHCO 3 , potential: −1.2 V vs. RHE and gas‐phase recycling set up), as well as CO electroreduction to C 2 ‐products (ethanol and ethylene) with a Faradaic yield of 80 %. During electrolysis the isolated sites transiently convert into metallic copper nanoparticles, as shown by operando XAS analysis, which are likely to be the catalytically active species. Remarkably, this process is reversible and the initial material is recovered intact after electrolysis.

Abstract By studying the molecular weights of various solutions of cis ‐1,4‐polyisoprene the authors arrived at the formula \documentclass{article}\pagestyle{empty}\begin{document}$$\left[ \eta \right] = \sqrt {2/c} \sqrt {\eta _{sp} - {\rm l}n\eta } _{rel} $$\end{document} which allowed the calculation of the intrinsic viscosity of the polymer solutions by a single viscosity determination. The formula was verified for different systems of polymer–solvent and the values are in accord with those obtained by extrapolation. An operating concentration of about 0.2% is recommended.

Recent years have seen a large increase of the research effort focused on framework materials, including the nowadays-ubiquitous metal-organic frameworks but also dense coordination polymers, covalent organic frameworks, and molecular frameworks. With the quickly increasing number of structures synthesized and characterized, one pattern emerging is the common occurrence of flexibility. More specifically, an important number of framework materials are stimuli-responsive: their structure can undergo changes of large amplitude in response to physical or chemical stimulation. They can display transformations induced by temperature, mechanical pressure, guest adsorption or evacuation, light absorption, etc. and are sometimes referred to as smart materials, sof t crystals, or dynamic materials. This Perspective highlights recent progress in this field, showcasing some of the most novel and unusual responses to stimuli, as well as advances in the fundamental understanding of flexible framework materials.

ZnGa2O4:Cr3+ presents near-infrared long-lasting phosphorescence (LLP) suitable for in vivo bioimaging. It is a bright LLP material showing a main thermally stimulated luminescence (TSL) peak around 318 K. The TSL peak can be excited virtually by all visible wavelengths from 1.8 eV (680 nm) via d–d excitation of Cr3+ to above ZnGa2O4 band gap (4.5 eV–275 nm). The mechanism of LLP induced by visible light excitation is entirely localized around CrN2 ion that is a Cr3+ ion with an antisite defect as first cationic neighbor. The charging process involves trapping of an electron–hole pair at antisite defects of opposite charges, one of them being first cationic neighbor to CrN2. We propose that the driving force for charge separation in the excited states of chromium is the local electric field created by the neighboring pair of antisite defects. The cluster of defects formed by CrN2 ion and the complementary antisite defects is therefore able to store visible light. This unique property enables repeated excitation of LLP through living tissues in ZnGa2O4:Cr3+ biomarkers used for in vivo imaging. Upon excitation of ZnGa2O4:Cr3+ above 3.1 eV, LLP efficiency is amplified by band-assistance because of the position of Cr3+4T1 (4F) state inside ZnGa2O4 conduction band. Additional TSL peaks emitted by all types of Cr3+ including defect-free CrR then appear at low temperature, showing that shallower trapping at defects located far away from Cr3+ occurs through band excitation.

Porous materials contain regions of empty space into which guest molecules can be selectively adsorbed and sometimes chemically transformed. This has made them useful in both industrial and domestic applications, ranging from gas separation, energy storage and ion exchange to heterogeneous catalysis and green chemistry. Porous materials are often ordered (crystalline) solids. Order—or uniformity—is frequently held to be advantageous, or even pivotal, to our ability to engineer useful properties in a rational way. Here we highlight the growing evidence that topological disorder can be useful in creating alternative properties in porous materials. In particular, we highlight here several concepts for the creation of novel porous liquids, rationalize routes to porous glasses and provide perspectives on applications for porous liquids and glasses. Highly ordered crystalline porous solids are useful for many applications. This Perspective explores the evolution of these systems from the ordered state to the glassy and liquid states, discusses the different types of porous liquid and considers possible applications of these disordered systems.

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.

Abstract Graphene oxide is a rising star among 2D materials, yet its interaction with liquid water remains a fundamentally open question: experimental characterization at the atomic scale is difficult, and modeling by classical approaches cannot properly describe chemical reactivity. Here, we bridge the gap between simple computational models and complex experimental systems, by realistic first-principles molecular simulations of graphene oxide (GO) in liquid water. We construct chemically accurate GO models and study their behavior in water, showing that oxygen-bearing functional groups (hydroxyl and epoxides) are preferentially clustered on the graphene oxide layer. We demonstrated the specific properties of GO in water, an unusual combination of both hydrophilicity and fast water dynamics. Finally, we evidence that GO is chemically active in water, acquiring an average negative charge of the order of 10 mC m −2 . The ab initio modeling highlights the uniqueness of GO structures for applications as innovative membranes for desalination and water purification.

The use of photodynamic therapy (PDT) against cancer has received increasing attention over recent years. However, the application of the currently approved photosensitizers (PSs) is limited by their poor aqueous solubility, aggregation, photobleaching and slow clearance from the body. To overcome these limitations, there is a need for the development of new classes of PSs with ruthenium(II) polypyridine complexes currently gaining momentum. However, these compounds generally lack significant absorption in the biological spectral window, limiting their application to treat deep-seated or large tumors. To overcome this drawback, ruthenium(II) polypyridine complexes designed in silico with (E,E')-4,4'-bisstyryl-2,2'-bipyridine ligands show impressive 1- and 2-Photon absorption up to a magnitude higher than the ones published so far. While nontoxic in the dark, these compounds are phototoxic in various 2D monolayer cells, 3D multicellular tumor spheroids and are able to eradicate a multiresistant tumor inside a mouse model upon clinically relevant 1-Photon and 2-Photon excitation.

Biobased production of furfural has been known for decades. Nevertheless, bioeconomy and circular economy concepts is much more recent and has motivated a regain of interest of dedicated research to improve production modes and expand potential uses. Accordingly, this review paper aims essentially at outlining recent breakthroughs obtained in the field of furfural production from sugars and polysaccharides feedstocks. The review discusses advances obtained in major production pathways recently explored splitting in the following categories: (i) non-catalytic routes like use of critical solvents or hot water pretreatment, (ii) use of various homogeneous catalysts like mineral or organic acids, metal salts or ionic liquids, (iii) feedstock dehydration making use of various solid acid catalysts; (iv) feedstock dehydration making use of supported catalysts, (v) other heterogeneous catalytic routes. The paper also briefly overviews current understanding of furfural chemical synthesis and its underpinning mechanism as well as safety issues pertaining to the substance. Eventually, some remaining research topics are put in perspective for further optimization of biobased furfural production.

A new bcc Ti-rich high-entropy alloy (HEA) of composition Ti35Zr27.5Hf27.5Nb5Ta5 was designed using the ‘d-electron alloy design’ approach. The tensile behavior displays a marked transformation-induced plasticity effect resulting in a high normalized work-hardening rate of 0.103 without loss of ductility when compared to the reference composition Ti20Zr20Hf20Nb20Ta20. In this paper, a detailed microstructural analysis was performed to understand the deformation process, revealing architectural-type microstructures and a high volume fraction (65%) of internally twinned stress-induced martensite α″ after mechanical testing. This study opens the way to mechanical properties optimization and enhancement of titanium-based HEAs by combining multiple alloying designs.IMPACT STATEMENTFor the first time, proof is given that transformation-induced plasticity was triggered in a bcc refractory high-entropy alloy, leading to a twofold increase in the normalized work-hardening rate.

We give here a brief overview of the use of machine learning (ML) in our field, for chemists and materials scientists with no experience with these techniques. We illustrate the workflow of ML for computational studies of materials, with a specific interest in the prediction of materials properties. We present concisely the fundamental ideas of ML, and for each stage of the workflow, we give examples of the possibilities and questions to be considered in implementing ML-based modeling.

Vitrimers are covalent polymer networks that can change their topology through thermally activated bond exchange reactions. In this work, fully biobased and recyclable vitrimers were developed from epoxidized soybean oil (ESO) and natural glycyrrhizic acid (GL) as it was without additional chemical modification, which avoided the use of nonrenewable petroleum resources and resolved the disposal problems of materials. Because of the unique rigid skeleton of GL, ESO/GL vitrimers showed good thermal stability and mechanical properties. Driven by the transesterification-induced topological network rearrangements, these ESO/GL vitrimers exhibited high performance of welding, repairing, and shape memory. They were also recyclable and chemically degradable by ethylene glycol. More importantly, these vitrimers could be used as repairable and recyclable adhesives.

Abstract To use water as the source of electrons for proton or CO 2 reduction within electrocatalytic devices, catalysts are required for facilitating the proton‐coupled multi‐electron oxygen evolution reaction (OER, 2 H 2 O→O 2 +4 H + +4 e − ). These catalysts, ideally based on cheap and earth abundant metals, have to display high activity at low overpotential and good stability and selectivity. While numerous examples of Co, Mn, and Ni catalysts were recently reported for water oxidation, only few examples were reported using copper, despite promising efficiencies. A rationally designed nanostructured copper/copper oxide electrocatalyst for OER is presented. This material derives from conductive copper foam passivated by a copper oxide layer and further nanostructured by electrodeposition of CuO nanoparticles. The generated electrodes are highly efficient for catalyzing selective water oxidation to dioxygen with an overpotential of 290 mV at 10 mA cm −2 in 1 m NaOH solution.

A new approach stemming from the adiabatic-connection (AC) formalism is proposed to derive parameter-free double-hybrid (DH) exchange-correlation functionals. It is based on a quadratic form that models the integrand of the coupling parameter, whose components are chosen to satisfy several well-known limiting conditions. Its integration leads to DHs containing a single parameter controlling the amount of exact exchange, which is determined by requiring it to depend on the weight of the MP2 correlation contribution. Two new parameter-free DHs functionals are derived in this way, by incorporating the non-empirical PBE and TPSS functionals in the underlying expression. Their extensive testing using the GMTKN30 benchmark indicates that they are in competition with state-of-the-art DHs, yet providing much better self-interaction errors and opening a new avenue towards the design of accurate double-hybrid exchange-correlation functionals departing from the AC integrand.

In this Letter we report the error analysis of 59 exchange-correlation functionals in evaluating the structural parameters of small- and medium-sized organic molecules. From this analysis, recently developed double hybrids, such as xDH-PBE0, emerge as the most reliable methods, while global hybrids confirm their robustness in reproducing molecular structures. Notably the M06-L density functional is the only semilocal method reaching an accuracy comparable to hybrids'. A comparison with errors obtained on energetic databases (including thermochemistry, reaction barriers, and interaction energies) indicate that most of the functionals have a coherent behavior, showing low (or high) deviations on both energy and structure data sets. Only a few of them are more prone toward one of these two properties.

Abstract Physical eutectogels are appealing materials for technological devices due to their superior ionic conductivity, thermal and electrochemical stability, non‐volatility, and low cost. Nevertheless, current physical eutectogels are suffering from weak mechanical strength and toughness. Here, taking advantage of the distribution difference of polyvinyl alcohol (PVA) in water and deep eutectic solvents (DESs), a simple and universal solvent‐replacement approach is proposed to regulate the spatiotemporal expression of intra/interpolymer interactions to prepare strong and tough physical eutectogels. The exchange of DESs with water can restrengthen the weakened interactions between PVA chains in water, enabling PVA to crystallize to construct a uniform and robust polymer network. Consequently, the resultant PVA eutectogel exhibits record‐high strength (20.2 MPa), toughness (62.7 MJ m –3 ), and tear‐resistance (tearing energy Σ42.4 kJ m –2 ), while possessing excellent stretchability (Σ550% strain), repairability, and adhesive performance. Furthermore, this strategy is proven to be universally applicable to various species of polymers, and even can be utilized to fabricate continuous and conductive eutectogel fibers, demonstrating potential as engineering materials and wearable sensors.