Connecting chemical worlds for a sustainable future.

Chemistry plays a central role in science and is the basis of one of the major, more impactful, and diverse industries. However, to address the most pressing global challenges, we must learn to create connections in an effective and meaningful way, with other disciplines, industries, and society at large. Here, we present the IUPAC Top Ten Emerging Technologies in Chemistry as an example of an initiative that highlights the value of the most promising advances in chemistry and contributes to creating connections to accelerate sustainable solutions for our society and our planet.

Language of Chemistry: Making IUPAC Nomenclature Available in Spanish.

Science, including mathematics, physics, and, of course, chemistry, has its own language and symbols and names we learn in school. However, to teach it, communicate it, and use it, we use our own native languages. Most of the scientific literature, including this article, is in English, as are the texts published by the various scientific unions, including the International Union of Pure and Applied Chemistry (IUPAC), to define scientific nomenclature, terminology, and presentation. However, it is essential that these fundamental texts are available in as many languages as possible to facilitate their teaching, learning, and use throughout the world. It should be noted, however, that the translation of these texts into different languages is a complex task that requires some choices due to the lack of obvious alternatives or the cacophony of some terms. In this paper, we provide some details on the challenges, compromises, and difficult decisions involved in translating the IUPAC Nomenclature Brief Guides into Spanish.

Blue-LED activated photocatalytic hydrogenation of nitroarenes with Cu2O/CuO heterojunctions.

This study describes how the optimization of Cu2O/CuO heterostructures can enhance their (photo)catalytic performance. More specifically, the evaluation of catalysts with different Cu2O/CuO molar ratios was used to optimize their performance for the hydrogenation of 4-nitrophenol under both blue-LED light and dark conditions. For the first time, we analyzed the effect of blue LED irradiation on this reaction and found that when blue LEDs are used as the light source, a Cu2O/CuO ratio of 0.15 results in rate constants 7 to 3 times higher than those of catalysts with either lower (0.01) or higher (0.42) ratios. Furthermore, this photocatalyst shows good stability, >70% after 5 cycles, and excellent chemoselectivity in the selective reduction of the nitro group in the presence of other functionalities, i.e. -COOH, -CONH2 and -OH.

Chemical Solutions to the Current Polycrisis.

In the past 15 years, we've experienced an unprecedented series of crises, including financial (2008), health (2020), and most recently the supply chain disruptions and the energy emergency in Europe, caused by the war in Ukraine (2022). On top of that, climate change still poses a serious threat to our lives and our planet. These interconnected challenges create tremendous societal problems and compromise the viability of the chemical industry in an environment of price volatility and high inflation. Thus, the International Union of Pure and Applied Chemistry (IUPAC) has launched a series of actions to tackle this and raise awareness of the role of chemistry in solving our major threats. Since 2019, IUPAC has identified the "Top Ten Emerging Technologies in Chemistry" to connect chemical researchers with industry, bridging the gap between science and innovation, maintaining the current competitiveness of the chemical industry, as well as tackling our most pressing global challenges.

Tunable hybrid zeolites prepared by partial interconversion.

Zeolite interconversion is a widely used strategy due to its unique advantages in the synthesis of some zeolites. By using a long-chain quaternary amine as both a structure-directing agent and porogen, we have produced superior catalysts, which we named Hybrid Zeolites, as their structures are made of building units of different zeolite types. The properties of these materials can be conveniently tuned, and their catalytic performance can be optimized simply by stopping the interconversion at different times. For cracking the 1,3,5-triisopropylbenzene, Hybrid Zeolites made of FAU and MFI units show a 5-fold increase in selectivity towards the desired product, that is, 1,3-diisopropylbenzene, compared to the commercial FAU, and a 7-fold increase in conversion at constant selectivity compared to MFI zeolite.

Cooperative Surface Passivation and Hierarchical Structuring of Zeolite Beta Catalysts.

We report a method to prepare core-shell zeolite beta (*BEA) with an aluminous core and an epitaxial Si-rich shell. This method capitalizes on the inherent defects in *BEA crystals to simultaneously passivate acid sites on external surfaces and increase intracrystalline mesoporosity through facile post-hydrothermal synthesis modification in alkaline media. This process creates more hydrophobic materials by reducing silanol defects and enriching the shell in silica via a combination of dealumination and the relocation of silica from the core to the shell during intracrystalline mesopore formation. The catalytic consequences of *BEA core-shells relative to conventional analogues were tested using the biomass conversion of levulinic acid and n-butanol to n-butyl levulinate as a benchmark reaction. Our findings reveal that siliceous shells and intracrystalline mesopores synergistically enhance the performance of *BEA catalysts.

Hierarchical Catalysts Prepared by Interzeolite Transformation.

Interzeolite transformation has been used to produce a novel family of hierarchical catalysts featuring excellent textural properties, strong acidity, and superior catalytic performance for the Friedel-Crafts alkylation of indole with benzhydrol, the Claisen-Schmidt condensation of benzaldehyde and hydroxyacetophenone, and the cracking of polystyrene. Intermediate solids of the FAU interzeolite transformation into BEA display both increased accessibility─due to the development of mesoporosity─and strong acidity─caused by the presence of ultrasmall crystals or zeolitic fragments in their structure. The use of surfactants allows for the development of the hierarchical catalysts with very narrow pore size distribution. The properties of interzeolite transformation intermediates (ITIs) can be fine-tuned simply by stopping the interconversion at different times.

Accelerating the Crystallization of Zeolite SSZ-13 with Polyamines.

Tailoring processes of nucleation and growth to achieve desired material properties is a pervasive challenge in synthetic crystallization. In systems where crystals form via nonclassical pathways, engineering materials often requires the controlled assembly and structural evolution of colloidal precursors. In this study, we examine zeolite SSZ-13 crystallization and show that several polyquaternary amines function as efficient accelerants of nucleation, and, in selected cases, tune crystal size by orders of magnitude. Among the additives tested, polydiallyldimethylammonium (PDDA) was found to have the most pronounced impact on the kinetics of SSZ-13 formation, leading to a 4-fold reduction in crystallization time. Our findings also reveal that enhanced nucleation occurs at an optimal PDDA concentration where a combination of light-scattering techniques demonstrate these conditions lead to polymer-induced aggregation of amorphous precursors and the promotion of (alumino)silicate precipitation from the growth solution. Here, we show that relatively low concentrations of polymer additives can be used in unique ways to dramatically enhance SSZ-13 crystallization rates, thereby improving the overall efficiency of zeolite synthesis.

Micelle Formation inside Zeolites: A Critical Step in Zeolite Surfactant-Templating Observed by Raman Microspectroscopy.

Micelle formation inside faujasite (FAU) zeolite, a critical step in the introduction of mesoporosity in zeolites by surfactant templating, has been confirmed by both 13C NMR and Raman spectroscopy. Here we provide unambiguous evidence of the incorporation of surfactant molecules inside zeolites during the first step of the surfactant-templating process followed by their self-assembly into micelles after hydrothermal treatment. The homogeneous presence of these micelles throughout zeolite crystals has been directly observed by Raman microspectroscopy, confirming the uniform incorporation of mesoporosity in zeolites by surfactant templating.

Standing on the Shoulders of Giants - Your Mentors and Role Models Will Shape Your Career.

Choosing the right mentors and role models has a profound impact in both our lives and professional careers; however, most often, not enough time or thought is given to this important decision. Because of that, we may miss some great opportunities and limit the potential benefits. In this invited contribution, I share my personal experience on nurturing the relationship with mentors and on choosing role models with my same values and a strong sense of service.

Spontaneous Pillaring of Pentasil Zeolites.

Conventional methods to prepare hierarchical zeolites depend upon the use of organic structure-directing agents and often require multiple synthesis steps with limited product yield and Brønsted acid concentration. Here, it is shown that the use of MEL- or MFI-type zeolites as crystalline seeds induces the spontaneous formation of self-pillared pentasil zeolites, thus avoiding the use of any organic or branching template for the crystallization of these hierarchical structures. The mechanism of formation is evaluated by time-resolved electron microscopy to provide evidence for the heterogeneous nucleation and growth of sequentially branched nanosheets from amorphous precursors. The resulting hierarchical zeolites have large external surface area and high percentages of external acid sites, which markedly improves their catalytic performance in the Friedel-Crafts alkylation and methanol to hydrocarbons reactions. These findings highlight a facile, commercially viable synthesis method to reduce mass-transport limitations and improve the performance of zeolite catalysts.

Thermochemistry of Surfactant-Templating of USY Zeolite.

With the aim of understanding the thermochemistry of the introduction of mesoporosity in zeolites by using surfactants, high temperature oxide melt solution calorimetry was used to determine the change in the enthalpy of formation of USY zeolite before and after the introduction of mesoporosity. Our results confirm that this process only slightly destabilizes the zeolite by the additional surface area. However, this can be overcome by the stabilizing effect of the interactions between the surfactant and the zeolite framework.

Ultrasmall Zeolite†L Crystals Prepared from Highly Interdispersed Alkali-Silicate Precursors.

The preparation of nanosized zeolites is critical for applications where mass-transport limitations within microporous networks hinder their performance. Often the ability to generate ultrasmall zeolite crystals is dependent upon the use of expensive organics with limited commercial relevance. Herein, we report the generation of zeolite L crystals with uniform sizes less than 30 nm using a facile, organic-free method. Time-resolved analysis of precursor assembly and evolution during nonclassical crystallization highlights key differences among silicon sources. Our findings reveal that a homogenous dispersion of potassium ions throughout silicate precursors leads to the formation of a metastable nonporous phase, which undergoes an intercrystalline transformation to zeolite L. The generation of highly interdispersed alkali-silicate precursors is seemingly critical to enhancing the rate of nucleation and facilitating the formation of ultrasmall crystal.

The Energetics of Surfactant-Templating of Zeolites.

Mesoporosity can be conveniently introduced into zeolites by treating them in basic surfactant solutions. The apparent activation energy involved in the formation of mesopores in USY by surfactant-templating was determined using a combination of in situ synchrotron X-ray diffraction and ex situ gas adsorption. Additionally, techniques such as pH measurement and thermogravimetry/differential thermal analysis were employed to determine OH- evolution and cetyltrimethylammonium ion (CTA+ ) uptake during the development of mesoporosity, thereby providing information about the different steps involved. The combination of both in situ and ex situ techniques has allowed determination of the apparent activation energies of the different processes involved in the mesostructuring of USY zeolites for the first time. Apparent activation energies are of the same order of magnitude (30-65 kJ mol-1 ) as those involved in the crystallization of zeolites. Hence, important mechanistic insight into the surfactant-templating method was obtained.

Visible-Light-Activated Black Organotitanias: How Synthetic Conditions Influence Their Structure and Photocatalytic Activity.

A series of low-temperature, visible-light-activated black organotitanias were synthesised through a sol-gel strategy that allowed the in situ incorporation of p-phenylenediamine (PPD) into the framework of anatase nanoparticles. The effect of the synthetic conditions on the crystalline structure and photocatalytic activity of these materials was assessed by several characterisation techniques, which revealed a small crystalline domain size (4.6-5.5 nm), effective incorporation of PPD inside the nanoparticles, and a significant reduction in the band gap of these materials (from 3.2 to 2.7-2.9 eV). A systematic study of the synthetic parameters also allowed a significant reduction of the solvent used for the preparation of these black organotitanias (20-fold), as well as the crystallisation time, without compromising the structural properties and photocatalytic activity of these materials. The organotitanias with the highest PPD content and high crystallinity result in the best performing materials in the photocatalytic degradation of rhodamine 6G under both UV- and visible-light irradiation.

Recent advances in the textural characterization of hierarchically structured nanoporous materials.

This review focuses on important aspects of applying physisorption for the pore structural characterization of hierarchical materials such as mesoporous zeolites. During the last decades major advances in understanding the adsorption and phase behavior of fluids confined in ordered nanoporous materials have been made, which led to major progress in the physisorption characterization methodology (summarized in the 2015 IUPAC report on physisorption characterization). Here we discuss progress and challenges for the physisorption characterization of nanoporous solids exhibiting various levels of porosity from micro- to macropores. While physisorption allows one to assess micro- and mesopores, a widely employed method for textural analysis of macroporous materials is mercury porosimetry and we also review important insights associated with the underlying mechanisms governing mercury intrusion/extrusion experiments. Hence, although the main focus of this review is on physical adsorption, we strongly emphasize the importance of combining advanced physical adsorption with other complementary experimental techniques for obtaining a reliable and comprehensive understanding of the texture of hierarchically structured materials.