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Instruments / Technical Area	Publication Details	Published
B21-High Throughput SAXS	Concentrated rhamnolipid formulations: bridging chemodiversity to structure, flow behavior, and functionality Matilde Tancredi , Carlo Carandente Coscia , Michela Buonocore , Alessandro Cangiano , Maria Michela Salvatore , Lorenzo Veronico , Delia Picone , Anna Maria D'Ursi , Manuela Grimaldi , Maria Francesca Ottaviani , Stefano Guido , Luigi Paduano , Luigi Gentile , Gerardino D'Errico Acs Sustainable Chemistry & Engineering DOI: 10.1021/acssuschemeng.5c09437 Diamond Proposal Number(s): [34244] Open Access Show Abstract ▼ Abstract: The development of ultraconcentrated biobased formulations is one of the latest frontiers in sustainable product design. This study demonstrates that biosurfactants are well suited to the scope with their natural chemodiversity being a key factor in optimizing formulation structure and function. The composition of a low-cost commercial rhamnolipid sample was investigated by using nuclear magnetic resonance and mass spectrometry. The results revealed a complex mixture of congeners with a predominance of dirhamnolipids and double-tailed species and the presence of long-chain free fatty acids. Polarized optical microscopy, small-angle X-ray scattering, and electron paramagnetic resonance show that this rhamnolipid sample, in aqueous solution, forms ellipsoidal micelles with a highly hydrophobic core, whose dimensions are almost insensitive to concentration (up to 65 wt %) and temperature (up to 50 °C). Analysis of the results hints that a fundamental role in tuning the system behavior is played by the specific rhamnolipid congener composition and by the free fatty acids acting as cosurfactants. At concentrations exceeding 65 wt %, small domains with different supramolecular ordered structures form, suggesting congener segregation. This aggregation behavior explains the preserved low viscosity and good cleaning efficiency. Thus, rhamnolipids are established as valuable candidates for the design of innovative, sustainable formulations.	Dec 2025
B18-Core EXAFS	Green one-pot synthesis of benzimidazoles from dinitroarenes in water using a Ru-doped Co-based heterogeneous catalyst José Luis Del Río-Rodríguez , Silvia Gutiérrez-Tarriño , Maria Asuncion Molina , Lucy Costley-Wood , Chiara Falcini , Andrew M. Beale , Pascual Oña-Burgos Acs Sustainable Chemistry & Engineering 49 DOI: 10.1021/acssuschemeng.5c05806 Diamond Proposal Number(s): [42561] Open Access Show Abstract ▼ Abstract: A novel methodology is presented for preparing non-noble metal-based heterogeneous catalysts doped with low amounts of noble metals, yielding highly active and reusable materials for sustainable organic transformations. A new Co–Ru@C catalyst was developed by incorporating small ruthenium nanoparticles (1 wt %) and cobalt nanoparticles (10 wt %) on Vulcan carbon via pyrolysis of a ruthenium-doped cobalt metal–organic framework supported on carbon (2D-Co(Ru)MOF/C). Advanced characterization (in situ PXRD and XAS, HAADF-STEM, HRTEM) confirmed strong Co–Ru interactions, enhancing catalytic activity. The catalyst was evaluated in the one-pot reductive amination of dinitrobenzenes to benzimidazoles using molecular hydrogen and water, which is in line with green chemistry. The synergistic effect between Co and Ru enabled quantitative product yields under significantly milder reaction conditions than the existing ones. In addition, ruthenium was found to facilitate hydrogen activation in the bimetallic material compared with its undoped Co@C counterpart. Regarding stability, the Co–Ru@C catalyst retained its activity over at least five consecutive cycles without metal leaching or structural degradation. This material demonstrated a broad substrate scope, affording over 20 functionalized benzimidazoles in high yields. Half-gram-scale syntheses of commercial Diabazole and Fuberidazole further validated the scalability of this approach.	Sep 2025
E01-JEM ARM 200CF E02-JEM ARM 300CF	Nanoceria as an efficient and cost-effective metal-free catalyst for the oxidation of alcohols Claire Squarzoni , Nicolas Kania , Malcolm Dearg , Max Quayle , Hang Hu , Thomas J. A. Slater , Andrea Folli , Alberto Roldan , Marc Pera-Titus , Anne Ponchel Acs Sustainable Chemistry & Engineering 178 DOI: 10.1021/acssuschemeng.5c05061 Diamond Proposal Number(s): [30463] Open Access Show Abstract ▼ Abstract: This study investigates the catalytic properties of nanoceria for the liquid-phase oxidation of aromatic and aliphatic alcohols using t-butyl hydroperoxide as an oxidant without the need for base or supported noble metals. The morphology, reducibility, and reversible H2 adsorption characteristics of ceria were comprehensively studied using X-ray diffraction, BET, HAADF-STEM, H2-TPR, H2-TPD, and X-ray photoelectron spectroscopy. Radical formation was interrogated by electron paramagnetic resonance (EPR) using dimethyl pyrrolidine N-oxide (DMPO) and N-tert-butyl-α-phenylnitrone (PBN) as spin traps, complemented by atomistic simulations to elucidate the influence of trap and radical adduct adsorption on the catalysts on radical abundance. The solvent played a critical role in enhancing the catalytic performance and carbon balance. The catalyst retained its structural integrity during the reaction in acetonitrile and could be reused for at least five consecutive runs. EPR analysis revealed that peroxyl radicals (tBu-OO•) were the predominant reactive species with no detectable formation of oxyl (tBu-O•) radicals, ruling out a Fenton-like catalytic mechanism in solution. Incorporating small amounts of Au (0.5–1.0 wt %) as Au(I) single atoms or clusters reduced the catalytic activity due to a decreased surface reducibility and reversible H2 adsorption despite an increased peroxyl radical formation. However, Au doping did not alter the product distribution. Compared to a benchmark 0.3 wt % Au/TS-1 catalyst, nanoceria achieved a 60% cost reduction and an E-factor of 0.08 (vs 0.2–1.3 for 0.3 wt % Au/TS-1) at equivalent acid production rates, highlighting the economic and environmental benefits.	Aug 2025
I20-Scanning-X-ray spectroscopy (XAS/XES)	Robust and recyclable single-atom and cluster-like Cu-based catalysts for methanol oxidative carbonylation to dimethyl carbonate Wenjie Li , Shanlin Gao , Chunbo Lai , Xinling Li , Wanjing Xiao , Xinyu Wang , Huibo Lin , Yang Zhang , Haijun Liu , Gan Yang , Chenghua Xu , Luke J. R. Higgins , Andrew M. Beale , Marc Pera-Titus , Zhiyong Deng Acs Sustainable Chemistry & Engineering 31 DOI: 10.1021/acssuschemeng.5c04760 Diamond Proposal Number(s): [40509] Open Access Show Abstract ▼ Abstract: Methanol oxidative carbonylation is a highly desired reaction for the industrial production of dimethyl carbonate (DMC), offering a more sustainable alternative to the conventional, environmentally unfriendly phosgene-methanol process. Although supported copper nanoparticle catalysts can facilitate this reaction, their rapid deactivation due to Cu sintering and overoxidation limits their industrial applicability. In this study, we present robust and reusable single-atoms and cluster-like Cu catalysts (catalyst loading up to 6.5 wt %) supported on N-doped carbon, synthesized via pyrolysis of Cu-doped ZIF-8 precursors. The formation and stability of highly dispersed Cu species during the reaction was confirmed using a comprehensive suite of characterization techniques, including X-ray diffraction (XRD), Fourier transform infrared (FT-IR), high-resolution transmission electron microscopy (HR-TEM), aberration corrected high angle annular dark field-scanning transmission electron microscopy (AC-HAADF-STEM), X-ray photoelectron spectroscopy (XPS), NH3-TPD, H2-TPR, and X-ray absorption spectroscopy (XAS). This unique copper architecture achieved an exceptional DMC selectivity of 99.4% and a space-time yield of 3249 mg DMC·g–1·h–1 (TOFDMC,B = 34.4 h–1; TOFDMC,S = 294 h–1) at 120 °C for 2 h. The catalysts demonstrated excellent reusability, maintaining their performance over at least seven consecutive runs without deactivation. Postreaction analysis of the spent catalyst after seven runs revealed that Cu was largely free of leaching, sintering, and overoxidation.	Jul 2025
B18-Core EXAFS	Influence of surface functionalities on Au/C catalysts for oxidative homocoupling of phenylboronic acid Tanja E. Parmentier , Anna Lazaridou , Joseph Cartwright , Ben Davies , Simon Dawson , Grazia Malta , Simon Freakley , Thomas E. Davies , David J. Morgan , Simon Kondrat , Christopher J. Kiely , Samuel Pattisson , Nicholas F. Dummer , Graham J. Hutchings Acs Sustainable Chemistry & Engineering 55 DOI: 10.1021/acssuschemeng.5c02262 Diamond Proposal Number(s): [15151] Open Access Show Abstract ▼ Abstract: The formation of C–C bonds through coupling reactions is an important industrial process. The ability of Au to catalyze such reactions has been reported, with both homogeneous and heterogeneous catalyst examples. Previous work has shown that carbon-supported cationic and nanoparticulate Au are active for the homocoupling of phenylboronic acid to biphenyl. However, the stability of supported cationic Au is short-lived, and the formed nanoparticles were suggested to be the active species. Through the synthesis of two types of supported cationic Au catalysts, utilizing either aqua regia or acetone solvents, we show that both catalysts develop nanoparticulate Au species early in the reaction; however, only the aqua regia prepared catalyst is active. We ascribe the activity of the aqua regia prepared Au catalyst to excess Cl and the presence of C–Cl surface species in combination with Au. Carbon treated with aqua regia was inactive; however, when used as a support for Au deposited with acetone or via a sol immobilization method, activity was comparable to the aqua regia prepared catalyst. The role of C–Cl and Au nanoparticles is discussed with respect to their correlation to the biphenyl yield, which is shown to be significant only when the C–Cl species are present on the catalyst.	Jun 2025
I03-Macromolecular Crystallography	Functional and structural characterization of PETase SM14 from marine-sponge Streptomyces sp. active on polyethylene terephthalate Alan Carletti , Shapla Bhattacharya , Sara Pedroni , Marcello Berto , Riccardo Bonettini , Rossella Castagna , Emilio Parisini , Giulia Di Rocco Acs Sustainable Chemistry & Engineering DOI: 10.1021/acssuschemeng.5c00737 Diamond Proposal Number(s): [32544] Open Access Show Abstract ▼ Abstract: The recent discovery of the PETase enzyme family offers a sustainable solution for depolymerizing poly(ethylene terephthalate) (PET), one of the most widespread plastic compounds, under mild conditions. This enables the environmentally beneficial conversion of plastic waste into value-added products. Among this enzyme family, PETase from Ideonella sakaiensis has been the most extensively studied. Although other similar enzymes have been discovered, our knowledge about the catalytic and structural properties of this class remains limited. In this study, a PETase-like enzyme (PETase SM14) from Streptomyces sp. SM14 was heterologously produced in Escherichia coli, and its activity was tested on post-consumer plastic substrates using high-performance liquid chromatography for product quantification as well as scanning electron microscopy and atomic force microscopy for substrate surface imaging evaluation. PETase SM14 exhibited high salt tolerance (1.5 M), good heat resistance (Tm 56.26 °C), and optimal activity at pH 9.0, highlighting its potential for PET waste bioremediation. Furthermore, its X-ray crystal structure was solved at 1.43 Å resolution, revealing conserved features of the PETase family with potential relevance for future engineering applications.	May 2025
B18-Core EXAFS	Selective oxidation of biomass-derived 5-hydroxymethylfurfural catalyzed by an iron-grafted metal–organic framework with a sustainably sourced ligand Satarupa Das , Giannantonio Cibin , Richard I. Walton Acs Sustainable Chemistry & Engineering DOI: 10.1021/acssuschemeng.3c08564 Diamond Proposal Number(s): [14239] Open Access Show Abstract ▼ Abstract: The efficient conversion of biomass-derived 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) is a major challenge under base-free conditions with inexpensive catalysts. We report a precious-metal-free recyclable MOF-based catalyst (CAU-28), constructed from the FDC ligand, with grafted redox-active Fe sites. This enables the conversion of HMF to FDCA under solvothermal heating or microwave-assisted methods in base-free aqueous conditions. The optimized process achieves 100% HMF conversion producing FDCA at the gram scale with a 70–80% yield in 1 h. The turnover frequency (TOF) and cost-normalized TOF for the best catalyst are >800 h–1 and >1000 h–1 £–1, respectively, surpassing those of conventional catalysts and processes using precious elements or basic additives for HMF conversion. The economic viability and practical applicability of the process are further realized by utilizing the catalytically derived FDCA (without purification) for the successful construction of pristine CAU-28 MOFs and formation of the biodegradable plastic polyethylene furanoate (PEF) after purification.	Mar 2024
E01-JEM ARM 200CF	Role of the deep eutectic solvent reline in the synthesis of gold nanoparticles Sukanya Datta , Julien Mahin , Emanuela Liberti , Iva Manasi , Karen J. Edler , Laura Torrente-Murciano Acs Sustainable Chemistry & Engineering DOI: 10.1021/acssuschemeng.2c07337 Diamond Proposal Number(s): [22073] Open Access Show Abstract ▼ Abstract: This work presents a mechanistic understanding of the synthesis of small (<3 nm) gold nanoparticles in a nontoxic, eco-friendly, and biodegradable eutectic mixture of choline chloride and urea (reline) without the addition of external reducing or stabilization agents. Reline acts as a reducing agent by releasing ammonia (via urea hydrolysis), forming gold nanoparticles even at trace ammonia concentration levels. Reline also affects the speciation of the gold precursor forming gold chloro-complexes, stabilizing Au+ species, leading to an easier reduction and avoiding the otherwise fast disproportionation reaction. Such a capability is however lost in the presence of large amounts of water, where water replaces the chloride ligands in the precursor speciation. In addition, reline acts as a weak stabilizing agent, leading to small particles (<3 nm) and narrow distributions although agglomerates quickly form. Such properties are maintained in the presence of water, indicating that it is linked to the urea stabilization rather than the hydrogen-bonding network. This work has important implications in the field of green synthesis of nanoparticles with small sizes, especially for biomedical and health care applications, due to the nontoxic nature of the components of deep eutectic solvents in contrast to the conventional routes.	Jul 2023
I03-Macromolecular Crystallography	Versatile chemo-biocatalytic cascade driven by a thermophilic and irreversible C–C bond-forming α-oxoamine synthase Ben Ashley , Arnaud Basle , Mariyah Sajjad , Ahmed El Ashram , Panayiota Kelis , Jon Marles-Wright , Dominic J. Campopiano Acs Sustainable Chemistry & Engineering 55 DOI: 10.1021/acssuschemeng.3c00243 Diamond Proposal Number(s): [24948] Open Access Show Abstract ▼ Abstract: We report a chemo-biocatalytic cascade for the synthesis of substituted pyrroles, driven by the action of an irreversible, thermostable, pyridoxal 5′-phosphate (PLP)-dependent, C–C bond-forming biocatalyst (ThAOS). The ThAOS catalyzes the Claisen-like condensation between various amino acids and acyl-CoA substrates to generate a range of α-aminoketones. These products are reacted with β-keto esters in an irreversible Knorr pyrrole reaction. The determination of the 1.6 Å resolution crystal structure of the PLP-bound form of ThAOS lays the foundation for future engineering and directed evolution. This report establishes the AOS family as useful and versatile C–C bond-forming biocatalysts.	May 2023
B18-Core EXAFS	Kinetic modeling of hydrocracking of low-density polyethylene in a batch reactor Abdulrahman Bin Jumah , Maryam Malekshahian , Aleksander A. Tedstone , Arthur A. Garforth Acs Sustainable Chemistry & Engineering DOI: 10.1021/acssuschemeng.1c06231 Show Abstract ▼ Abstract: Hydrocracking offers potential for the selective recovery of useful chemical fractions from polyolefin waste at relatively moderate reaction conditions with the possibility of heteroatom and contaminant tolerance. This study develops a kinetic model for low-density polyethylene (LDPE) hydrocracking over a bifunctional zeolite, namely, 1%Pt-β, using a lumping model that describes the kinetics in a batch process. In developing the kinetic model, mass transfer limitations and vapor–liquid equilibrium were taken into consideration. Kinetic parameters were estimated from experimental results obtained at a hydrogen pressure of 20 bar and different reaction temperatures (250–300 °C) as well as different batch reaction times (0–40 min). Kinetic parameters, mass transfer coefficients, and effectiveness factors were determined using a nonlinear regression model of the experimental results via MATLAB software. The physical properties of the product streams as well as vapor–liquid equilibrium data of the system were estimated using the flash unit in Aspen HYSYS software. The product stream was dominated by the naphtha fraction, decreasing with longer batch times. The results of the model indicate mild gas–liquid mass transfer limitation and unavoidable diffusion limitations of the macromolecules of molten LDPE and heavy liquid through the catalyst pores, especially at high reaction temperatures.	Nov 2021

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