Reaction Products Research Articles

Degradation of pharmaceuticals and other emerging pollutants employing bi-metal catalysts/magnesium and/or (green) hydrogen in aqueous solution.

Contaminations by pharmaceuticals, personal care products, and other emerging pollutants in water resources have become a seriously burgeoning issue of global concern in the first third of the twenty-first century. As societal reliance on pharmaceuticals continues to escalate, the inadvertent introduction of these substances into water reservoirs poses a consequential environmental threat. Therefore, the aim of this study was to investigate reductive degradation, particularly, catalytic hydrogenation regarding model pollutants such as diclofenac (DCF), ibuprofen (IBP), 17α-ethinylestradiol (EE2), or bisphenol-A (BPA), respectively, in aqueous solutions at lab scale. Iron bimetals (zero valent iron, ZVI, and copper, Cu, or nickel, Ni) as well as zero valent magnesium (Mg, ZVM) in combination with rhodium, Rh, or palladium, Pd, as hydrogenation catalysts (HK), were investigated. Studies were executed through various short-term batch experiments, with multiple sample collections, over a total range of 120min. The results indicated that DCF was attenuated at over 90 % when exposed to Fe-Cu or a Fe-Ni bimetal (applied as a single model pollutant). However, when DCF was part of a mixture alongside with IBP, EE2, and BPA, the attenuation efficacy decreased to 79 % with Fe-Cu and 23 % with Fe-Ni. Conversely, both IBP and BPA exhibit notably low attenuation levels with both bimetals, less than 50 %, both deployed as single substances or in mixtures. No reaction (degradation) products could be identified employing LC-MS, but sometimes a release of the parent pollutant when applying an acetic acid buffer could be noted to a certain extent, suggesting adsorption processes on corrosion products such as iron hydroxide and/or oxides. Surprisingly, Mg in combination with Rh (Rh-HK) or Pd (Pd-HK) showed a significantly rapid decrease in the concentrations of DCF, EE2, and BPA, in part up to approximately 100 %, that is, within a few minutes only in part due to hydrogenation degradation reactions (related reaction products could actually be identified by LC-MS; adsorption processes were not observed here). Moreover, kinetic modeling of the DCF degradation with Mg-Rh-HK was conducted at different temperatures (15 °C, 20 °C, 25 °C, 35 °C) and varied initial concentrations (2.5mg/L, 5.0mg/L, 7.5mg/L, 10.0mg/L). The outcomes prove that the degradation of DCF at the Rh-HK's surface followed a modified first-order kinetics, most probably by catalytic hydrodehalogenation and subsequent hydrogenation of the aromatic moieties (molecular hydrogen was provided by the corrosion of Mg). From the determined reaction rate constants at four different temperatures, the activation energy was estimated to be 59.6kJ/mol by means of the Arrhenius equation what is in good agreement with similar results reported in the literature. This coupled hydrodehalogenation and hydrogenation approach may be upscaled into a new promising technical process for comprehensively removing such pharmaceuticals and similar pollutants in sewage plants in a single step, furthermore, even in combination with adsorption by activated carbon and/or ozonation which have already been established at some sewage plants in Switzerland and Germany recently.

Anionic Conjugate Addition Oligomerization of Carbon Dioxide/Butadiene Derived Lactones.

Nucleophilic and non-nucleophilic bases have been employed in anionic oligomerization of unsaturated δ-valerolactone (3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one) (1). Compared to the seminal findings with 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), the unsaturated lactone reacts with guanidines, disilazanes, and phosphazenes both in bulk and in solution with higher productivities and activities, reaching full conversion with turnover frequencies up to 382 h-1. Additionally, reactions using phosphazenes and NaHMDS were active at 1 mol % catalyst loadings both in solvent and in bulk monomer at room temperature. Characterization of the reaction products by 1H, 13C, FTIR, MALDI-MS, tandem mass spectrometry (MS/MS), and ion mobility mass spectrometry (IM-MS) revealed microstructural differences dependent on the nucleophilicity of the organocatalytic base and reaction conditions. The products from phosphazene-catalyzed reactions are consistent with selective vinylogous 1,4-conjugate addition, whereas both conjugate addition and ring-opening mechanisms are observed in TBD. DSC reveals that these microstructures can be tuned to have a Tg range between -18 and 80 °C, while SEC and MALDI-MS reveal that only low molar mass oligomers are formed (748-5949 g/mol). From these results, an approach for selectively favoring the vinylogous 1,4-conjugate addition pathway is obtained over ring-opening reactivity.

Instability of Formamidinium Lead Iodide (FAPI) Deposited on a Copper Oxide Hole Transporting Layer (HTL).

Copper oxide appears to be a promising candidate for a hole transport layer (HTL) in emerging perovskite solar cells. Reasons for this are its good optical and electrical properties, cost-effectiveness, and high stability. However, is this really the case? In this study, we demonstrate that copper oxide, synthesized by a spray-coating method, is unstable in contact with formamidinium lead triiodide (FAPI) perovskite, leading to its decomposition. Using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and ultraviolet-visible (UV-vis) spectrophotometry, we find that the entire copper oxide diffuses into and reacts with the FAPI film completely. The reaction products are an inactive yellow δ-FAPI phase, copper iodide (CuI), and an additional new phase of copper formate hydroxide (CH2CuO3) that has not been reported previously in the literature.

Compressive and Tensile Behavior of High-Ductility Alkali-Activated Composites with Polyethylene Terephthalate Powder

Researchers have been engaged in the study of high-ductility concrete (HDC) due to its excellent ductility and cracking control ability. This study combines the concepts of HDC and alkali-activated composites (AAC) to develop high-ductility alkali-activated composites (HDAAC) using polyethylene terephthalate (PET) powder. Experimental investigations were conducted to assess the compressive and tensile properties of HDAAC, focusing on the impact of varying PET powder content (0%, 15%, 30%, and 45%) and fly ash/slag ratios (FA/GGBS, 6:4, 7:3, and 8:2). The results indicated that the compressive strength of HDAAC ranged from approximately 30 MPa to about 100 MPa, with the specimens maintaining good integrity after axial compression failure due to the bridging action of PE fibers. The replacement of quartz powder (QP) with PET powder slightly decreased the compressive strength and elastic modulus of HDAAC, albeit mitigating its brittleness under compression. An increase in GGBS content enhanced the compressive strength and elastic modulus of HDAAC due to the increased formation of the C-A-S-H reaction products, leading to reduced porosity and a denser microstructure. Under axial tension, HDAAC exhibited typical multiple-cracking behavior with significant pseudo-strain hardening. Increases in the PET content and FA/GGBS ratio resulted in finer cracks, indicating excellent crack control and deformation capabilities. The initial cracking strength, tensile strength, and ultimate tensile strain ranged from 3.0 MPa to 4.6 MPa, 4.2 MPa to 8.2 MPa, and 4.1% to 7.2%, respectively. Despite a decrease in the initial cracking strength and tensile strength with higher PET content, the ultimate tensile strain of HDAAC slightly increased. Observations under a scanning electron microscope revealed a distinct interfacial transition zone near the PET powder, leading to poor bonding with the alkali-activated matrix. In contrast, QP dissolved on the surface in highly alkaline environments, forming better interface properties. These variations in interface properties can be used to interpret the variations in the mechanical performance of HDAAC.

Transcriptional control of a metabolic switch regulating cellular methylation reactions is part of a common response to stress in divergent bee species.

Recent global declines in bee health have elevated the need for a more complete understanding of the cellular stress mechanisms employed by diverse bee species. We recently uncovered the biomarker lethal (2) essential for life (l(2)efl) genes as part of a shared transcriptional program in response to a number of cell stressors in the western honey bee (Apis mellifera). Here we describe another shared stress responsive gene, Glycine N-methyl transferase (Gnmt), which is known as a key metabolic switch controlling cellular methylation reactions. We observed Gnmt induction by both abiotic and biotic stressors. We also found increased levels of the GNMT reaction product sarcosine in the midgut after stress linking metabolic changes with the observed changes in gene regulation. Prior to this study, Gnmt upregulation has not previously been associated with cellular stress responses in other organisms. To determine whether this novel stress-responsive gene would behave similarly in other bee species, we first characterized the cellular response to ER stress in lab-reared adults of the solitary alfalfa leafcutting bee (Megachile rotundata) and compared with age-matched honey bees. The novel stress gene Gnmt was induced in addition to a number of canonical gene targets induced in both bee species upon UPR activation, suggesting that stress-induced regulation of cellular methylation reactions is a common feature of bees. Therefore, this study suggests that honey bee can serve as an important model for bee biology more broadly, although studies on diverse bee species will be required to fully understand global declines in bee populations.

Pozzolanic metakaolin reactivity: Time-dependent influence of calcium hydroxide, alkali hydroxides, and sulfates

In the quest for environmentally sustainable binders within the construction industry, metakaolin (MK) has emerged as a highly promising material. Its reactivity and hardening performance encompass a wide range of applications, spanning from lime to cement-based materials. This performance is primarily underpinned by the pozzolanic reaction with calcium hydroxide (CH), leading to the formation of various calcium aluminate silicate hydrates. The intricacies of the hydration kinetics and resultant reaction products hinge on several factors woven into the specifics of the binder type. This study investigates the influence of CH availability, explored through initially mixed MK/CH weight ratios of 0.33 and 1.0. Furthermore, the study examines the impact of introducing alkali hydroxides (KOH and NaOH) and/or sulfates (K2SO4 and Na2SO4) on the pozzolanic reactions. Short-term analysis employed inductively coupled plasma optical emission spectrometry (ICP-OES), and pH measurements for pore solution as well as isothermal calorimetry, and in-situ X-ray diffraction (XRD) on paste samples. Long-term investigations extended to 245 days at 40 °C, incorporating XRD, thermogravimetric (TGA) and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM/EDX). Results provide insights into the kinetics of phase assemblage and compositions of C-A-S-H gels, highlighting the transformation of metastable C2ASH8 and C4AH13 to stable Si-rich hydrogarnet phases, incorporating sulfate, under excess CH conditions. Higher MK/CH enriches Si/Ca, Al/Ca, enhancing C-A-S-H gels, while KOH addition further boosts Al/Ca ratios.

The Influence of Ligands on the Pd-Catalyzed Diarylation of Vinyl Esters

The impact of ligands on the palladium-catalyzed 1,2-diarylation reaction course is presented. The application of Pd-dmpzc as a catalyst provides an efficient, chemoselective and sustainable protocol for the synthesis of valuable 1,2-diphenylethyl acetates. The reaction is conducted in water under mild conditions. Reaction products can be easily separated from the reaction mixture and catalyst by simple extraction. What is more, the rational choice of catalyst significantly reduces the leaching of the metal into the product and its contamination (0.1 ppm). Efficient phase separation and ultralow Pd leaching enable the reuse of the water medium containing the Pd-dmpzc catalyst several times without a significant loss of activity and with even higher selectivity (from 95% to 100% in the third cycle). The recyclability of both the catalyst and the reaction medium together with high chemoselectivity and low palladium leaching reduces the amount of waste and the cost of the process, exhibiting an example of a sustainable and green methodology.

PyQCAMS: Python Quasi-Classical Atom–Molecule Scattering

We present Python Quasi-classical atom–molecule scattering (PyQCAMS v0.1.0), a new Python package for atom–diatom scattering within the quasi-classical trajectory approach. The input consists of the mass, collision energy, impact parameter, and pair-wise/three-body interactions. As the output, the code provides the vibrational quenching, dissociation, and reactive cross sections along with the rovibrational energy distribution of the reaction products. We benchmark the program for a reaction involving a molecular ion in a high-density ultracold gas, RbBa+ + Rb. Furthermore, we treat H2 + Ca → CaH + H reactions as a prototypical example to illustrate the properties and performance of the software. Finally, we study the parallelization performance of the code by looking into the speedup of the program as a function of the number of CPUs used.

Deciphering complexity in Pd–catalyzed cross-couplings

Understanding complex reaction systems is critical in chemistry. While synthetic methods for selective formation of products are sought after, oftentimes it is the full reaction signature, i.e., complete profile of products/side-products, that informs mechanistic rationale and accelerates discovery chemistry. Here, we report a methodology using high-throughput experimentation and multivariate data analysis to examine the full signature of one of the most complicated chemical reactions catalyzed by palladium known in the chemical literature. A model Pd-catalyzed reaction was selected involving functionalization of 2-bromo-N-phenylbenzamide and multiple bond activation pathways. Principal component analysis, correspondence analysis and heatmaps with hierarchical clustering reveal the factors contributing to the variance in product distributions and show associations between solvents and reaction products. Using robust data from experiments performed with eight solvents, for four different reaction times at five different temperatures, we correlate side-products to a major dominant N-phenyl phenanthridinone product, and many other side products.

Separation and characterization of the antioxidant active component from Maillard reaction products in xylose-lysine system

ABSTRACT Maillard reaction products (MRPs) play a crucial role in preserving food quality due to their antioxidant capacity. In this study, we isolated and characterized the antioxidant components from MRPs using a xylose-lysine system under optimal conditions. Methylene chloride and ethyl acetate were employed for sequential extractions, and the ethyl acetate phase underwent thin-layer chromatography and silica column separation. The identified compound, 3-hydroxy-4-methyl-2(5 H)-furanone (3H4MFN), was analyzed using FT-IR, GC-MS, and NMR, revealing its volatile nature with a chemical formula of C5H6O3. Further activity analysis demonstrated that 3H4MFN exhibited higher or comparable antioxidant activity to vitamin C (VC) and vitamin B6 (VB6). This newly discovered compound shows potential as a natural antioxidant in cosmetics, food, and nutraceutical applications.

New Method for Obtaining Carboxylic Derivatives of Oxazolo[5,4-b]pyridine Based on 3-Aminopyridine-2(1H)-ones

Current methods for synthesis of oxazolo[5,4-b]- and oxazolo[4,5-b]pyridines have several limitations, such as severe reaction conditions, lengthy reaction times, low yields and concurrent formation of side reaction products. This article presents the results of study focused on a one-step method for the synthesis of new derivatives of oxazolo[5,4-b]pyridine incorporating an aliphatic carboxylic group as a linker. During the investigation of acylation reactions of 3-aminopyridine-2(1H)-ones with cyclic anhydrides of dicarboxylic acids (succinic, maleic and glutaric), it was found that the monoamides formed at the initial stage undergo intramolecular cyclization yielding derivatives of oxazolo[5,4-b]pyridine. Subsequently, the reaction conditions were studied and optimized to achieve the target compounds with high yield and purity. The potential anti-inflammatory activity of the obtained derivatives of oxazolo[5,4-b]pyridine was evaluated by molecular docking method using AutoDock Vina software. Compounds 11-14b exhibited higher binding affinity with the selected target protein Prostaglandin synthase-2 (1CX2) compared to the reference anti-inflammatory drug diclofenac. Thus, taking into account the results of in silico analyses, the newly synthesized oxazolo[5,4-b]pyridine derivatives based on 3-aminopyridine-2(1H)-ones are promising candidates for further investigation of their potential anti-inflammatory activity through in vivo methods.

Engineered Cementitious Composites with Super-Sulfated Cement: Mechanical, Physical, and Durability Performance

This study aimed to bridge a research gap by exploring the utilization of super-sulphated cement (SSC) in engineered cementitious composites (ECCs) as a sustainable alternative to ordinary Portland cement (OPC)-based mixtures. The SSC was designed with slag, gypsum, and a small amount of OPC. The primary objective was to investigate the effects of incorporating SSC, both with and without fly ash (FA), at various FA/SSC ratios between 0 and 1.5. A comprehensive evaluation was conducted to assess the performance of the ECC-SSC mixtures, including the compressive and flexural strengths, ductility, ultrasonic pulse velocity, rapid chloride permeability, and drying shrinkage. Additionally, advanced microstructural evaluation techniques such as scanning electron microscopy (SEM) with energy dispersive X-ray (EDX) analysis as well as X-ray diffraction (XRD) analysis were employed to analyze the reaction products in selected mixtures. The results showed that the ECC mixture produced with SSC exhibited comparable strength to the ECC-OPC. In general, all the SSC-based ECCs fulfilled the criteria for various engineering applications, especially when the fly ash to SSC ratios were 0 and 0.8. In addition, ECCs with FA/SSC ratios of 1.2 and 1.5 showed ultra-ductile performance higher than the control ECC. Interestingly, all the FA-based ECC-SSC presented lower shrinkage characteristics than the control OPC-based ECC.

Insights in Pt-based electrocatalysts on carbon supports for electro-oxidation of carbohydrates: an EIS-DEMS analysis

In this work, the electrochemical oxidation of carbohydrates (glucose, fructose, and sucrose) was induced at the interface of Pt-nanoparticles supported on different carbon-based materials as carbon vulcan (C) and carbon black (CB). It was found that the support plays an important role during carbohydrates electro-oxidation as demonstrated by electrochemical techniques. In this context, current-concentration profiles of the redox peaks show the behavior of the pathways at carbohydrates-based solutions. Herein, the trend of current measured was glucose > sucrose > fructose, attributed to differences in the organic functional groups and chain-structure. Raman, XRD, SEM-EDS and XPS put in clear important structural, morphological, and electronic differences linked with the intrinsic nature of the obtained material. Differential Electrochemical Mass Spectroscopy (DEMS) indicated that the selectivity and the conversion of the formed reaction products during oxidation is linked with the catalyst nature (distribution, particle size) and the interaction with the carbon-based support.

Simulation of a catalytic deoxygenation reaction of fatty acids to produce biohydrocarbons and evaluation of the influence of reaction parameters on the conversion and selectivity of products

Nowadays, there has been an urgency in the search for sustainable energy sources, such as those derived from biomass. This search is not only limited to minimizing greenhouse gas emissions but is also related to the increasing scarcity of fossil fuels. This work aims to investigate and analyze the production of bio-hydrocarbons from fatty acids through the simulation of the deoxygenation reaction by the DWSim software. In this simulation, a continuous catalytic deoxygenation reactor of the stirred tank with fluidized bed type was selected, aiming to understand the influence of operating parameters on this reaction. The parameters evaluated were temperature, pressure, hydrogen feed, and catalyst mass. For this simulation, hydrogen and stearic acid were chosen as feedstocks, focusing on the heptadecane and octadecane production. The rate law was chosen based on an extensive literature review, as well as reaction conditions. The kinetic model used as a reference was based on reactions of stearic acid and hydrogen in the presence of NiMo/Al2O3 as a catalyst. A stearic acid feed of 2.4 x 104 m3 year-1 was used as a base, representing the average feed of fatty raw material practiced in biodiesel plants located in the state of Minas Gerais, Brazil. From the variation of these parameters for a sensitivity analysis, with conversion as the key response, the following optimal operating conditions were defined: temperature of 650 K, pressure of 50 bar, molecular hydrogen feed of 4.1 x 10-3 m³ s-1, and catalyst mass of 8 kg. Under these new circumstances, the conversion of stearic acid reached a value of 99.23 %. The simulation of this reaction allowed us to understand the effect of the main reaction parameters on the reaction products, proved to be an important and robust tool to be used in projects and feasibility analyses of plants and biorefineries.

Initial Characteristics of Alkali–Silica Reaction Products in Mortar Containing Low-Purity Calcined Clay

An alkali–silica reaction (ASR) is a chemical process that leads to the formation of an expansive gel, potentially causing durability issues in concrete structures. This article investigates the properties and behaviour of ASR products in mortar with the addition of low-purity calcined clay as an additional material. This study includes an evaluation of the expansion and microstructural characteristics of the mortar, as well as an analysis of the formation and behaviour of ASR products with different contents of calcined clay. Expansion tests of the mortar beam specimens were conducted according to ASTM C1567, and a detailed microscopic analysis of the reaction products was performed. Additionally, their mechanical properties were determined using nanoindentation. This study reveals that with an increasing calcined clay content, the amount of the crystalline form of the ASR gel decreases, while the nanohardness increases. The Young’s modulus of the amorphous ASR products ranged from 5 to 12 GPa, while the nanohardness ranged from 0.41 to 0.67 GPa. The obtained results contribute to a better understanding of how the incorporation of low-purity calcined clay influences the ASR in mortar, providing valuable insights into developing sustainable and durable building materials for the construction industry.

Structural insights into catalytic promiscuity of chalcone synthase from Glycine max (L.) Merr.: Coenzyme A-induced alteration of product specificity

Catalytic promiscuity of enzymes plays a pivotal role in driving the evolution of plant specialized metabolism. Chalcone synthase (CHS) catalyzes the production of 2′,4,4′,6′-tetrahydroxychalcone (THC), a common precursor of plant flavonoids, from p-coumaroyl-coenzyme A (-CoA) and three malonyl-CoA molecules. CHS has promiscuous product specificity, producing a significant amount of p-coumaroyltriacetic lactone (CTAL) in vitro. However, mechanistic aspects of this CHS promiscuity remain to be clarified. Here, we show that the product specificity of soybean CHS (GmCHS1) is altered by CoA, a reaction product, which selectively inhibits THC production (IC50, 67 μM) and enhances CTAL production. We determined the structure of a ternary GmCHS1/CoA/naringenin complex, in which CoA is bound to the CoA-binding tunnel via interactions with Lys55, Arg58, and Lys268. Replacement of these residues by alanine resulted in an enhanced THC/CTAL production ratio, suggesting the role of these residues in the CoA-mediated alteration of product specificity. In the ternary complex, a mobile loop (“the K-loop”), which contains Lys268, was in a “closed conformation” placing over the CoA-binding tunnel, whereas in the apo and binary complex structures, the K-loop was in an “open conformation” and remote from the tunnel. We propose that the production of THC involves a transition of the K-loop conformation between the open and closed states, whereas synthesis of CTAL is independent of it. In the presence of CoA, an enzyme conformer with the closed K-loop conformation becomes increasingly dominant, hampering the transition of K-loop conformations to result in decreased THC production and increased CTAL production.

Simultaneous measurements for fast neutron flux and tritium production rate using pulse shape discrimination and single crystal CVD diamond detector

This paper presents the development of a simultaneous measurement method for fast neutron energy spectra and tritium production rates within mixed radiation fields using a single crystal chemical vapour deposition diamond detector combined with a lithium fluoride (LiF) foil. The method involves the separation of pulses with rectangular shapes and the determination of the depth position within the single crystal diamond (SCD) struck by fast neutrons or nuclear reaction products including recoil tritons from the LiF foil based on pulse width, extracting pulse events occurred at the specific bulk region and the surface region of the SCD. Subsequently, unfolding techniques were employed to analyse the energy deposition spectrum of pulses at the specific bulk region which are induced only by fast neutrons, allowing the deduction of the fast neutron energy spectrum. To evaluate the tritium production rate, the energy deposition spectrum of pulses from events occurring at the SCD surface facing the LiF foil was analysed. By estimating the energy deposition spectrum solely induced by fast neutrons striking the SCD surface and subtracting it from the energy deposition spectrum of events at the SCD surface, the contribution of energetic ions, such as recoil tritons generated by the 6Li(n,α)3H reaction in the LiF foil, was determined. The fast neutron flux and tritium production rate obtained through this study were consistent with particle transport calculations, demonstrating the successful development of a method suitable for performance testing of fusion reactor blankets.

Turn-off enzyme activity of histidine-rich peptides for the detection of lysozyme.

Anassay that integrateshistidine-rich peptides (HisRPs) with high-affinity aptamerswas developed enabling the specific and sensitive determination of the target lysozyme. The enzyme-like activity of HisRP is inhibited by its interaction with a target recognized by an aptamer. In the presence of the target, lysozyme molecules progressively assemble on the surface of HisRP in a concentration-dependent manner, resulting in the gradual suppression of enzyme-like activity. This inhibition of HisRP's enzyme-like activity can be visually observed through color changes in the reaction product or quantified using UV-visible absorption spectroscopy. Under optimal conditions, the proposed colorimetric assay for lysozyme had a detection limit as low as 1 nM and exhibited excellent selectivity against other nonspecific interferents. Furthermore, subsequent research validated the practical applicability of the developed colorimetric approach to saliva samples, indicating that the assay holds significant potential for the detection of lysozymes in samples derived from humans.

Development of sustainable alkali-activated slag bricks with high content of carbonated recycled concrete fines: Strength, microstructure and environmental benefit

This research presents a novel method of recycling construction waste while capturing CO2 through the formation of mineral carbon. The technology uses carbonated recycled concrete fines (CRCF) as the primary raw material to produce sustainable, high-performance alkali bricks with high replacement rates. Firstly, a general assessment of the physical and chemical properties of CRCF was carried out, which revealed the formation of silica gel encapsulating the surface of CRCF during carbonation. Subsequently, alkali bricks were prepared utilizing CRCF. The study investigated the impact of various mix proportions, water-to-cement ratios, and manufacturing process parameters on brick strength. Additionally, an in-depth analysis of reaction products and brick microstructures was carried out. The results showed that the bricks produced from CRCF were stronger than those from RCF, indicating enhanced reactivity after carbonation. Finally, an analysis demonstrated that utilizing RCF from construction waste can significantly reduce carbon dioxide emissions, thereby mitigating the environmental impact associated with cement production.

Understanding the Decomposition of Dimethyl Methyl Phosphonate on Metal-Modified TiO2(110) Surfaces Using Ensembles of Product Configurations.

The decomposition of dimethyl methyl phosphonate (DMMP), a simulant for the nerve agent sarin, was investigated on Cu4/TiO2(110) and K/Cu4/TiO2(110) surfaces using a combination of near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) and density functional theory calculations (DFT). Mass-selected Cu4 clusters and potassium (K) atoms were deposited onto TiO2(110) as a metal catalyst and alkali promoter to improve the reactivity and recyclability of the TiO2 surface after exposure to DMMP. Surface reaction products resulting from decomposition of DMMP were probed by NAP-XPS measurements of phosphorus (P) 2p and carbon 1s core-level spectra. The Cu4/TiO2(110) surface is found to be very active for DMMP decomposition with highly reduced P-species observed even at room temperature (RT). The codeposition of K atoms and Cu4 clusters further improves the reactivity with no intact DMMP detectable. Temperature-dependent measurements show that the presence of K atoms promotes the removal of residual P-species at temperatures > 600 K. Detailed DFT calculations were performed to determine the surface structures and energetically accessible pathways for DMMP decomposition on Cu4/TiO2(110) and K/Cu4/TiO2(110) surfaces. The calculations show that DMMP and P-containing reaction products preferentially bind to the TiO2 surface, while the molecular fragments, i.e., methoxy and methyl, bind to both the Cu4 clusters and TiO2. The Cu4 clusters make the P-O, O-C, and P-C bond cleavages of DMMP markedly more exothermic. The Cu4 clusters are highly fluxional with atomic structures that depend on the configuration of fragments bound to them. Finally, the manifold of P 2p chemical shifts calculated for a large number of energetically favorable configurations of decomposition products is in good agreement with the observed XPS spectra and provides an alternative way of interpreting incompletely resolved core-level spectra using an ensemble of observed structures.