2024 patents
- 7 patent applications
2024 publications
T. Gao, Z. Yan, M. Trentesaux, M. Marinova, V. Ordomsky, S. Paul, Catalysis Today, Submitted.
S. Behloul, O. Gayraud, G. Frapper, F. Guégan, K. Upitak, C. M. Thomas, Z. Yan, K. De Oliveira Vigier, F. Jérôme, ChemSusChem., (2024), 17, e202400289
Abstract
Furfural is an industrially relevant biobased chemical platform. Unlike classical furan, or C-alkylated furans, which have been previously described in the current literature, the =C5H bond of furfural is unreactive. As a result, on a large scale, C=C and C=O bond hydrogenation/hydrogenolysis is mainly performed, with furfuryl alcohol and methyl tetrahydrofuran being the two main downstream chemicals. Here, we show that the derivatization of the -CHO group of furfural restores the reactivity of its =C5H bond, thus permitting its double condensation on various alkyl aldehydes. Overcoming the recalcitrance of the =C5H bond of furfural has opened an access to a biobased monomer, whose potential have been investigated in the fabrication of renewably-sourced poly(silylether). By means of a combined theoretical-experimental study, a reactivity scale for furfural and its protected derivatives against carbonylated compounds has been established using an electrophilicity descriptor, a means to predict the molecular diversity and complexity this pathway may support, and also to de-risk any project related to this topic. Finally, by using performance criteria for industrial operations in the field of fuels and commodities, we discussed the industrial potential of this work in terms of cost, E-factor, reactor productivity and catalyst consumption.
Gongming Peng, Naseeb Ullah, Stéphane Streiff, Karine De Oliveira Vigier, Marc Pera-Titus, Raphael Wischert, François Jérôme, Chem. Eur. J., (2024), 30, e202400601.
Abstract
α,β-Unsaturated aldehydes are important building blocks for the synthesis of a wide range of chemicals, including polymers. The synthesis of these molecules from cheap feedstocks such as alkenes remains a scientific challenge, mainly due to the low reactivity of alkenes. Here we report a selective and metal-free access to α,β-unsaturated aldehydes from alkenes with formaldehyde. This reaction is catalyzed by dimethylamine and affords α,β-unsaturated aldehydes in yields of up to 80 %. By combining Density Functional Theory (DFT) calculations and experiments, we elucidate the reaction mechanism which is based on a cascade of hydride transfer, hydrolysis and aldolization reactions. The reaction can be performed under very mild conditions (30–50 °C), in a theoretically 100 % carbon-economical fashion, with water as the only by-product. The reaction was successfully applied to non-activated linear 1-alkenes, thus opening an access to industrially relevant α,β-unsaturated aldehydes from cheap and widely abundant chemicals at large scale.
J. Zaffran, M. Jiao, R. Wischert, S. Streiff, S. Paul, J. Phys. Chem. C, (2024), 128, 5084-5092.
Abstract
Polyaromatic molecules are compounds of major importance in chemistry. However, simulating their reactivity at the solid catalyst surface with density functional theory (DFT) is very challenging. Indeed, such species require large slab models for their adsorption, hence resulting in a considerable number of atoms and thus significant computational time. In the recent context of increasing use in machine learning (ML), it is clear that such tools are of first interest to speed-up DFT calculations. Considering anthraquinone (AQ) hydrogenation on the surface of metal-doped Pd-based supported catalysts as a model reaction and focusing on the main reaction products, we propose here a method aiming at predicting the energy of the determining states from several descriptors related to a small molecular fragment, benzoquinone (BZQ) adsorbed at different surfaces. We were able to identify two distinct models, both performing with a high efficiency and based on different kinds of descriptors. While the first one involving a single thermodynamic descriptor is more accurate, the second one including a combination of electronic and geometric parameters is still relevant to predict reliable qualitative trends. Interestingly, we showed that simple linear regression tools can compete with other complex ML techniques, providing very accurate models with remarkable stability. Such an approach can be applied to easily assess the effective barriers of formation of several species on catalysts presenting different bimetallic compositions, hence enabling the screening of the catalytic activity and selectivity of various surfaces in a record time. While heavy DFT computations are generally required to optimize each intermediate and transition state, our strategy relies on a single adsorbate relaxation, hence, resulting in a tremendous gain of time. Therefore, our method is crucial for the accelerated computational design of solid catalysts and may have applications in various fields of the chemical industry.
Q. Wang, M.Shamzhy, E. Heuson, M. Trentesaux, M. Marinova, A. Addad, F. Su, V. Ordomsky, Chemical Engineering Journal (2024), 491, 151956.
Abstract
Dihydroxybenzenes, including catechol, resorcinol and hydroquinone, have significant commercial value for a variety of applications such as adhesives, resins, pharmaceuticals, coatings etc. However, selective production of required isomers by phenol hydroxylation represents a considerable challenge. Here, we report a new approach for the synthesis of dihydroxybenzenes by their isomerization using a bifunctional Pt/ZSM-5 catalyst. The catalyst successfully facilitates the transformation of catechol and hydroquinone to each other with a selectivity of up to 74 % and yields up to 50 %. The investigation of the mechanism suggests that isomerization proceeds via a carbonaceous deposit (coke) formed by intermediate quinone condensation with subsequent hydrogenolysis to isomers. The proposed mechanism shows the way for the design of the efficient process for isomerization of dihydroxybenzenes.
K. Zhang, C. Ma, S. Paul, J. Zaffran, Mol. Catal., (2024), 569, 114606.
Abstract
In the present context of environmental concerns, sustainable solutions must be proposed to dispose of waste CO2, a well-known greenhouse gas. Among the various emerging projects, upgrading CO2 molecule into high-value added chemicals appears to be very promising. More particularly, the carboxylation of aromatic compounds to (di-) acid aromatic monomers is of great interest for the high performance polymer industry. Focusing on the direct phenol carboxylation to para-hydroxybenzoic acid as a model reaction, the reactivity of ZrO2 was investigated in this paper, this material being recently reported in various experimental works for its catalytic efficiency. For the first time, we established the phenol carboxylation mechanism at the surface of a metal oxide material, showing that the reaction can only proceed through an Eley-Rideal mechanism. In this mechanism, CO2 is strongly chemisorbed at the surface, whereas phenol is physisorbed close to the CO2 adsorbate. Besides, while the monoclinic and the tetragonal phases often coexist in ZrO2 particles, we demonstrated that only the monoclinic geometry exhibits a substantial activity. However, the selectivity remains a major challenge, the ortho- isomer being the most abundant product, as in the original Kolbe-Schmitt method. While most of the processes generally reported in literature for the direct carboxylation of phenol are achieved in liquid media, a very few theoretical knowledge is available to describe such a process at solid surfaces. Therefore, we expect the present manuscript to be a pioneer work, aiming at providing a better understanding of metal oxide surface reactivity, paving the road to the rational design of efficient solid catalysts for aromatics carboxylation reactions.
Maximilian Koy, Maximilian Fellert, Chuting Deng, Michiel T. Uiterweerd, Alicia Lessentier, Minyan Wu, Mickael Cregut, Jianxia Zheng, Stephane Streiff, Juan J. de Pablo, Ben L. Feringa, Angew. Chem. Int. Ed. , submitted.
2023 patents
- 7 patent applications
2023 publications
F. Jiang, Z. Yan, X. Chen, X. Li, S. Streiff, M. Pera-Titus, Catal. Sci. Technol., (2023), 13, 187-194.
Abstract
Pentamethyldiethylenetriamine is a permethylated polyamine that is widely used to prepare foam polyurethane. The current technology for its synthesis relies on diethylenetriamine methylation with formaldehyde under H2. This route is selective, but the use of formaldehyde raises safety and environmental concerns. Herein we present an alternative non-toxic route using methanol as greener and cheaper methylating reagent. The reaction proceeds fast and selectively over composite copper catalysts with a pentamethyldiethylenetriamine yield of 75% and resistance to sintering.
L. Xue, C. Yuan, S. Wu, Z. Huang, Z. Yan, S. Streiff, H. Xu, W. Shen, Catalysts (2023), 13 (3), 529.
Abstract
Coalbed methane is a significant source of methane in the atmosphere, which is a potent greenhouse gas with a considerable contribution to global warming, thus it is of great importance to remove methane in coalbed gas before the emission. Exploring the economical non-noble metal catalysts for catalytic methane combustion (CMC) has been a wide concern to mitigate the greenhouse effect caused by the emitted low-concentration methane. Herein, a series of Mn-doped Co3O4 catalysts have been synthesized by the environmentally friendly solid-state method. As a result, the Mn0.05Co1 catalyst performed the best CMC activity (T90 = 370 °C) and good moisture tolerance (3 vol% steam). The introduction of an appropriate amount of manganese conduced Co3O4 lattice distortion and transformed Co3+ to Co2+, thus producing more active oxygen vacancies. Mn0.05Co1 exhibited better reducibility and oxygen mobility. In situ studies revealed that methane was adsorbed and oxidized much easier on Mn0.05Co1, which is the crucial reason for its superior catalytic performance.
S. Mathew, Y. Naganawa, F. Jiang, R. Wischert, S. Streiff, P. Métivier, Y. Nakajima, Macromol. Rapid. Commun. (2023), 44 (9), e2200921.
Abstract
Placement of phosphorus in the polymer main chain leads to organophosphorus polymers with potentially unique chemical and physical properties. Herein, it is demonstrated that the Abramov phosphonylation reaction can be extended to the synthesis of such polymers, by reacting di- or tricarbaldehydes with phosphinic acid (PA) in the presence of N,O-bis(trimethylsilyl)acetamide (BSA). This technique affords polymers with main chain PC bonds, wherein phosphorus (V), aromatic rings, and hydroxymethylene moieties are linked by bis(α-hydroxymethylene)phosphinic acid (BHMPA) units. The resulting polymers are water soluble, display resilience against acid- and base-catalyzed hydrolysis, and exhibit superior thermal stability with high char yield in air (≈83%) and nitrogen (≈76%) atmosphere.
M. Ramzan, R. Wischert, S. Steinmann, C. Michel, J. Phys. Chem. Lett. (2023), 14, 18, 4241–4246.
Abstract
Identifying the surface species is critical in developing a realistic understanding of supported metal catalysts working in water. To this end, we have characterized the surface species present at a Ru/water interface by employing a hybrid computational approach involving an explicit description of the liquid water and a possible pressure of H2. On the close-packed, most stable Ru(0001) facet, the solvation tends to favor the full dissociation of water into atomic O and H in contrast with the partially dissociated water layer reported for ultra-high-vacuum conditions. The solvation stabilization was found to reach −0.279 J m2, which results in stable O and H species on Ru(0001) in the presence of liquid water even at room temperature. Conversely, introducing even a small H2 pressure (10–2 bar) results in a monolayer of chemisorbed H at the interface, a general trend found on the three most exposed facets of Ru nanoparticles. While hydroxyls were often hypothesized as possible surface species at the Ru/water interface, this computational study clearly demonstrates that they are not stabilized by liquid water and are not found under realistic reductive catalytic conditions.
K. Silva Vargas, J. Zaffran, M. Araque, M. Sadakane, B. Katryniok, Mol. Catal., (2023), 535, 112856.
Abstract
The Deoxydehydration (DODH) of glycerol to allyl alcohol was studied over ceria-supported rhenium oxide catalyst. Mesoporous ceria materials were synthetized via a nanocasting process using SiO2 and activated carbon as hard templates. The as-obtained ceria supports were impregnated with 2.5-10 wt.% ReOx. and applied in the DODH reaction of glycerol to allyl alcohol at 175°C in batch conditions using 2-hexanol as solvent and hydrogen donor. As the characterisations revealed that the template removal was a critical step in the synthesis of the mesostructured ceria via the nanocasting method, the influence of the presence of the hard template was studied in detail by comparison to commercial ceria supports. The catalyst based on the nanocasting ceria showed higher performance of up to 88% yield in allyl alcohol and was reusable for 3 cycles without reactivation step. No evidence of leaching was observed via hot filtration test. The characterisation of the catalyst by XPS revealed the presence of Re4+ species after test, which led us propose that two redox couples, namely Re7+/Re5+ and Re6+/Re4+, are involved during DODH of glycerol to allyl alcohol, which was further confirmed by DFT calculations.
C. Dong, M. Marinova, K. Ben Tayeb, O. V. Safonova, Y. Zhou, D. Hu, S. Chernyak, M. Corda, J. Zaffran, A. Y. Khodakov, and V. V. Ordomsky, J. Am. Chem. Soc., (2023), 154,2,1185-1193.
Abstract
Direct functionalization of methane selectively to value-added chemicals is still one of the main challenges in modern science. Acetic acid is an important industrial chemical produced nowadays by expensive and environmentally unfriendly carbonylation of methanol using homogeneous catalysts. Here, we report a new photocatalytic reaction route to synthesize acetic acid from CH4 and CO at room temperature using water as the sole external oxygen source. The optimized photocatalyst consists of a TiO2 support and ammonium phosphotungstic polyoxometalate (NPW) clusters anchored with isolated Pt single atoms (Pt1). It enables a stable synthesis of 5.7 mmol·L–1 acetic acid solution in 60 h with the selectivity over 90% and 66% to acetic acid on liquid-phase and carbon basis, respectively, with the production of 99 mol of acetic acid per mol of Pt. Combined isotopic and in situ spectroscopy investigation suggests that synthesis of acetic acid proceeds via a photocatalytic oxidative carbonylation of methane over the Pt1 sites, with the methane activation facilitated by water-derived hydroxyl radicals.
Y. Zhou, M. Trentesaux, M. Marinova, S. Chernyak, J. Morin, M. Dubois, S. Eyley, W. Thielemans, V. Martin-Diaconescu, A. Khodakov, J. Zaffran, and V. Ordomsky, ACS Catal. (2023), 13, 9, 6351–6364.
Abstract
Within conventional bifunctional catalysts, active metal sites are associated with metal components, while acid sites are usually localized over oxide supports. The modification of metal sites by halogens provides an opportunity to generate acidity via the heterolytic dissociation of hydrogen directly over metal sites. Herein, we report the results of high-throughput screening of the combinations of different metals (Co, Ni, Ru, Pt, Pd, Rh) and halogens (Cl, Br, I) for acid site generation from hydrogen in the hydrogenation of furfural and 5-hydroxymethylfurfural. The results demonstrate that only Pd and Pt catalysts demonstrate the formation of acid sites by interaction with Br, Cl, and I. The characterization in combination with density functional theory (DFT) modeling indicates hydrogen heterolytic dissociation over halogens localized at the edges and corners of Pd and Pt nanoparticles with an increase in strength of the acid sites with an increase of electronegativity of the halogen.
H. Hu, M. Ramzan, R. Wischert, F. Jerôme, C. Michel, K. Vigier, and M. Pera-Titus, ACS Sustainable Chemistry & Engineering, (2023), 11, 22, 8229–8241.
Abstract
The direct amination of biomass-derived isohexides with NH3 over a Ru/C catalyst was systematically investigated to understand the role of H2 and NH3 in the production of isohexide diamines vs aminoalcohols, i.e., the transformation of one or both OH-groups in isohexides into NH2 groups. Only aminoalcohols with an exo-OH group were generated starting from isosorbide, which contains both an exo-OH and an endo-OH group, while a moderate yield of diamines was obtained from isomannide with two endo-OH groups due to the higher reactivity of the latter. The main byproducts were identified, including a variety of N- and O-containing cyclic compounds, such as 2,5-dimethylpyrrolidine, that arise from a decomposition path driven by hydrolysis/hydrodeoxygenation of a tricyclic amine intermediate. By combining density functional theory calculations with microkinetics, NH3 was found to adsorb strongly on the catalyst surface and generate adsorbed NH2 and NH species with variable coverage depending on the temperature and the nominal H2/NH3 ratio. Isomerization of isohexides was greatly suppressed by adsorbed NH3. Meanwhile, adsorbed NH3 discouraged the formation of byproducts driven by competing side reactions promoted by H2. The H2/NH3 ratio, which conditions the distribution of NH2 and NH species on the Ru surface, influences drastically the catalytic performance.
R. Schwiedernoch, X. Niu, H. Shu, M. Wu, N. Naghavi, J. Org. Chem. (2023), 88, 15, 10403–10411.
Abstract
β-Lactones are common substructures in a variety of natural products and drugs, and they serve as versatile synthetic intermediates in the production of valuable chemical derivatives. Traditional β-lactone synthesis relies on laborious multi-step synthetic methods that use toxic compounds, sophisticated catalysts, expensive, and/or reactive chemicals. Based on the in situ electrochemical formation of metal-based nanoclusters, this paper describes the development of a one-step, room temperature electrocatalytic method for the formation of stable β-lactone from CO2 and dienes. This one-step “electrosynthesis” method results in the formation of a new class of β-lactone with high selectivity (up to 100%) and activity (up to 80% yields with respect to the reacted diene) by regulating the applied potential and current density. This work paves the way for more sustainable and environmentally friendly reaction pathways based on the in situ formation of nanoclusters as organic electrosynthesis catalysts.
T. Gao, K. S. Kumar, Z. Yan, M. Marinova, M. Trentesaux, M. A. Amin, S. Szunerits, Y. Zhou, V. Martin-Diaconescu, S. Paul, R. Boukherroub, V. Ordomsky, J. Mater. Chem. A, (2023), 11, 19338-19348.
Abstract
The hydrogen and oxygen evolution reactions (HER and OER) are two steps in electrochemical water splitting for conversion of electric power to chemical energy. The main challenge remains the development of efficient, stable and cheap electrocatalysts able to perform both reactions under alkaline conditions. Single atom Ru stabilized by nitrogen-doped carbon and RuO2 are currently the materials of choice for the HER and OER, respectively. Here, we propose a strategy for the preparation of Ru embedded in a carbon nitride matrix for efficient HER and OER in KOH solution. It is based on the preparation of a covalent organic framework 2D CIN-1 structure with coordinated RuII, producing Ru oxide nanoparticles with low valence Ru sites arranged in the form of nanowires between layers of graphitic carbon nitride after pyrolysis. The material demonstrates smaller overpotentials for the HER and OER in comparison with benchmark Pt and RuO2 catalysts, and high catalytic stability.
W. Zhou, P. Métivier, National Science Review, (2023), 10(9)
A. Ratier, R. D. Moulandou-Koumba, M. Anizan, S. Behloul, F. Guegan, G. Frapper, Q. B. Remaury, K. De Oliveira Vigier, J. Zheng, F. Jérôme, RSC Adv. (2023), 13, 30369.
Abstract
Here, we study a sequence Diels–Alder/aromatization reaction between biobased furanic derivatives and alkynes, paving the way to renewable phenols. Guided by DFT calculations, we revealed that, in the case of dimethylfuran, the methyl group can migrate during the aromatization step, making this substrate also eligible to access renewable phenols. This reaction has been then successfully transposed to furfural and furfuryl alcohol, allowing molecular diversity and complexity to be created on phenol ring starting from two cheap biobased furanic derivatives available on large scale.