Fine Chemicals Research Articles

Wulff Constructions for an Equilibrium MFI-Type Zeolite Shape Modelling under Different Conditions

As an MFI-type zeolite, ZSM-5 zeolite has wide applications in industry, such as in the fine chemical, petrochemical, and coal chemical industries. However, shape control of ZSM-5 nanocrystals constitutes one of the major challenges of current nanotechnology. Here, the MFI framework structure was used as the theoretical model of pure silicon ZSM-5 to investigate the surface energy and Wulff shape. The models with different crystal surfaces were simulated by molecular dynamics (MD) with the assistance of machine learning potentials (MLPs). The factors influencing the crystal surface energy, such as temperature, pH, and ionic concentration, have been studied in detail. Depending on the calculated surface energies, the crystal surface morphology and its ratio were obtained by means of the Wulff theorem. The results show that the area in the equilibrium shape of the (110) surface is usually the largest, and its proportion varies with external conditions. A high temperature and high concentration of the aluminum source promoted the growth of the (110) crystal surface, and the theoretical value of the crystal surface ratio was as high as 90%. This study provides theoretical insight into the synthesis of zeolites with different morphologies of all-silicon or low-aluminum.

Ammonium Phosphotungstate Bonded on Imidazolized Activated Carbon for Selective Catalytic Rearrangement of α-Epoxypinane to Carveol

Carveol is a rare fine chemical with specific biological activities and functions in nature. The artificial synthesis of carveol from plentiful and cheap turpentine is expected to further improve development of pharmaceutical and industrial applications. A new green catalytic system for the preparation of high-value carveol from α-epoxypinane is presented. A novel ammonium salt solid acid (AC-COIMI-NH4PW) was obtained from phosphotungstic acid bonded with imidazole basic site on nitrogen-doped activated carbon which, after ammonia fumigation, presented an excellent catalytic performance for the selective rearrangement of α-epoxypinane to carveol in DMF as solvent under mild reaction conditions. At 90 °C for 2 h, the conversion of α-epoxypinane could reach 98.9% and the selectivity of carveol was 50.6%. The acidic catalytic sites exhibited superior durability and the catalytic performance can be restored by supplementing the lost catalyst. Based on the investigation of catalytic processes, a parallel catalytic mechanism for the main product was proposed from the rearrangement of α-epoxypinane on AC-COIMI-NH4PW.

Mineral and bioresource exploitation for transformation and sustainability of the chemical industry in Zambia

Zambia depends mainly on copper mining and imports the bulk of chemicals needed for academic, domestic, and industrial consumption. The country has never had an economically viable chemical industry despite having vast minerals and bioresources key to the stimulation of a sustainable chemical industry. This paper proposes a theory of change model for the establishment of the chemical industry in Zambia to enhance economic growth. Availability of minerals and bioresources have been assumed as a strong driver to establish an economically viable chemical industry in Zambia. The paper discusses the economic status of Zambia, explains current economic drivers and proposes establishment of a chemical industry as a critical missing link to transform the economy. Briefly a thorough literature desk review was done with cue search words such as “Chemistry professionals Zambia”, “Policy Chemicals industry Zambia”, “Chemical industry Zambia”, “National Development Plan Zambia”, “Petrochemicals Zambia”, “Specialty chemicals Zambia”, “Gross Domestic product Zambia” in the Google scholar search engine. Results revealed that exclusion of chemical industry in policy formulation and implementation, lack of political will in promoting chemistry, underutilization of available mineral and bioresources remains part of the main reason for lack of growth of the chemical industry and serial failure of the seven national development plans to adequately plan for this since independence in 1964. The period from 1961 to 2021 was considered and the 2006 to 2021 comprising the fifth, sixth and seventh national development plans was isolated, and analysis of variance done for the three plans with respect to gross domestic product (GDP) and GDP per capita. There was a statistical significance for both parameters. A p = 0.0004 for GDP and 0.0003 for GDP per capita values showed that there was negative or almost no growth within each period of the national development plan. None of the seven development plans addressed a deliberate setting up of the chemical industry to reduce capital flight in terms of huge imports. Hence, we opine that the chemical industry in Zambia is desperately needed to provide agrochemicals and other specialty chemical feedstocks.

Integrating MOF‐Based Catalysis with Nanocavity‐Confined Pd Catalysis over Multifunctional Pd‐MOF‐Fe for Acceptorless Dehydrogenation of Alcohols under Visible Light

AbstractSolar‐driven hydrogen (H2) evolution combined with synchronously selective oxidation for fine chemicals production is of great significance in energy and synthetic chemistry. Herein, ultrafine Pd nanoparticles‐encapsulated MIL‐100(Fe) (Pd‐MOF‐Fe) nanocomposites are synthesized through double‐solvent impregnation integrated with photo‐reduction method. Integrating MOF‐based catalysis and Pd‐based catalysis, the Pd‐MOF‐Fe can serve as multifunctional catalyst for photoinduced alcohol dehydrogenation reaction. Optimal generation rates of H2 (3.61 mmol g−1 h−1) and benzaldehyde (3.40 mmol g−1 h−1) are gained over Pd‐MOF‐Fe, ca. 4.1 times that of the Pd/MOF‐Fe, in which Pd crystals with size ranging from 3 to 6 nm are immobilized on the intersurface of MOFs. Besides, controlled experiments reveal the pivotal role of the opened FeO6 nodes of MIL‐100(Fe) as Lewis acid sites toward alcohol activation. This work provides a controllable approach for metal nanoparticle immobilization. Furthermore, considering the diversified MOF structures, this study also highlights the infinite possibility of metal nanoparticle/MOFs as multifunctional platform for solar energy conversion and chemicals production.

Effect of Pink Water Biosolve on Expression of some Cytokines in Hepatocyte of Wistar Rat

The use of Pink Water Biosolve for clean-up of the environment as a bioremediating chemical has a wide application in the clean-up of crude oil spill in Nigeria. BioSolve is a water-based formulation of nonionic surfactants and other specialty chemicals. The level of toxicity resulting from environmental exposure of plants and animals, including humans, to this chemical has not been well understood. Thus, the level of expression of pro-inflammatory and anti-inflammatory cytokines in liver cells of Wistar rats exposed to drinking water obtained from cleaned-up environment was investigated in this study. Reverse transcriptase PCR technique was used to assess the expression of selected hepatic cytokines. The results showed that 10% Soluble Crude Oil Portion (SCP) caused an increased expression of the Interleukin 1-beta (IL1β), Nuclear Factor kappa-B (NF-κB), Interleukin 6 (IL-6), Interleukin 10 (IL-10), Mitogen-activated protein kinase 8 (MAPK8) and Toll-like receptor 4 (TLR4) respectively when compared to the control. The combination of 10% SCP with 0.36mg/L BS and 0.50mg/L BS respectively caused significant (p<0.05) increases in the expression of IL-6, IL-10, MAPK8 and TLR4 respectively. IL-1B was nonsignificantly (p<0.05) increased when compared to the control. This suggests that the presence of the substance in underground/surface water, if found in concentration as low as 0.36mg/L, would be toxic to Wistar rats when consumed over a prolonged period (above 2 weeks).

The Evolution of the Chemical Industry: From Basic Chemicals to Specialty Products

The chemical industry has undergone a significant transformation since its inception in the 19th century, evolving from the production of basic chemicals to a diversified array of specialty products. This paper explores the historical development, key milestones, and current trends within the industry. It delves into the transition from basic chemicals and commodity chemicals to polymers and specialty chemicals, emphasizing the impact on consumer products and the growth of major chemical companies. Through a detailed examination of these phases, the paper highlights the pivotal role of innovation and market demand in shaping the chemical landscape.

Seawater electrolysis for fuels and chemicals production: fundamentals, achievements, and perspectives.

Seawater electrolysis for the production of fuels and chemicals involved in onshore and offshore plants powered by renewable energies offers a promising avenue and unique advantages for energy and environmental sustainability. Nevertheless, seawater electrolysis presents long-term challenges and issues, such as complex composition, potential side reactions, deposition of and poisoning by microorganisms and metal ions, as well as corrosion, thus hindering the rapid development of seawater electrolysis technology. This review focuses on the production of value-added fuels (hydrogen and beyond) and fine chemicals through seawater electrolysis, as a promising step towards sustainable energy development and carbon neutrality. The principle of seawater electrolysis and related challenges are first introduced, and the redox reaction mechanisms of fuels and chemicals are summarized. Strategies for operating anodes and cathodes including the development and application of chloride- and impurity-resistant electrocatalysts/membranes are reviewed. We comprehensively summarize the production of fuels and chemicals (hydrogen, carbon monoxide, sulfur, ammonia, etc.) at the cathode and anode via seawater electrolysis, and propose other potential strategies for co-producing fine chemicals, even sophisticated and electronic chemicals. Seawater electrolysis can drive the oxidation and upgrading of industrial pollutants or natural organics into value-added chemicals or degrade them into harmless substances, which would be meaningful for environmental protection. Finally, the perspective and prospects are outlined to address the challenges and expand the application of seawater electrolysis.

Carbon-vacancy engineering approach to g-C3N4 for selective 5-hydroxymethylfurfural oxidation coupled with H2O2 production

CN modified with carbon and nitrogen vacancies was obtained through calcination under different atmospheres, resulting in efficient visible-light-driven photocatalysts for the conversion of biomass-relevant alcohols into fine chemicals.

Recent advances in Pd-catalyzed asymmetric cyclization reactions.

Over the past few decades, there have been major developments in transition metal-catalyzed asymmetric cyclization reactions, enabling the convenient access to a wide spectrum of structurally diverse chiral carbo- and hetero-cycles, common skeletons found in fine chemicals, natural products, pharmaceuticals, agrochemicals, and materials. In particular, a plethora of enantioselective cyclization reactions have been promoted by chiral palladium catalysts owing to their outstanding features. This review aims to collect the latest advancements in enantioselective palladium-catalyzed cyclization reactions over the past eleven years, and it is organized into thirteen sections depending on the different types of transformations involved.

Advances in morphology-controlled alumina and its supported Pd catalysts: synthesis and applications.

Alumina materials, as one of the cornerstones of the modern chemical industry, possess physical and chemical properties that include excellent mechanical strength and structure stability, which also make them highly suitable as catalyst supports. Alumina-supported Pd-based catalysts with the advantages of exceptional catalytic performance, flexible regulated surface metal/acid sites, and good regeneration ability have been widely used in many traditional chemical industry fields and have also shown great application prospects in emerging fields. This review aims to provide an overview of the recent advances in alumina and its supported Pd-based catalysts. Specifically, the synthesis strategies, morphology transformation mechanisms, and structural properties of alumina with various morphologies are comprehensively summarized and discussed in-depth. Then, the preparation approaches of Pd/Al2O3 catalysts (impregnation, precipitation, and other emerging methods), as well as the metal-support interactions (MSIs), are revisited. Moreover, Some promising applications have been chosen as representative reactions in fine chemicals, environmental purification, and sustainable development fields to highlight the universal functionality of the alumina-supported Pd-based catalysts. The role of the Pd species, alumina support, promoters, and metal-support interactions in the enhancement of catalytic performance are also discussed. Finally, some challenges and upcoming opportunities in the academic and industrial application of the alumina and its supported Pd-based are presented and put forward.

A sequential flow process of CO2 capture and conversion using cost-effective porous organic polymers

A sequential flow process utilizing cost-effective porous organic materials to capture CO2 and directly convert it into fine chemicals has been achieved, which could improve the practical applicability of CO2 capture and utilization technologies.

A superhydrophobic MOF facilitating efficient solvent-free catalytic chemical fixation of CO2 and oxidation of hydrocarbons and MOF@cotton@starch composite-based selective sensing of a herbicide

Superhydrophobic Zr-MOF unveils solvent-free chemical fixation of CO2 at 1 bar, along with efficient aerobic oxidation of hydrocarbons into fine chemicals and fast, nanomolar detection of aclonifen in wastewater, vegetables, and fruits.

Application of Carbonylation in the Synthesis of Bulk and Fine Chemicals

Application of Carbonylation in the Synthesis of Bulk and Fine Chemicals

Harnessing Trace Water for Enhanced Photocatalytic Oxidation of Biomass-Derived Alcohol to Aldehyde

The photocatalytic conversion of biomass into valuable chemicals offers a more energy-efficient and low-carbon alternative to traditional thermal catalysis, representing a promising strategy for fine chemicals production without relying on...

Expedient alkyne semi-hydrogenation by using a bimetallic AgCu-C3N4 single atom catalyst.

Metal-catalyzed semi-hydrogenation of alkynes is an important step in organic synthesis to produce diverse chemical compounds. However, conventional noble metal catalysts often suffer from poor selectivity owing to over-hydrogenation. Here, we demonstrate a high-loading bimetallic AgCu-C3N4 single-atom catalyst (SAC) for alkyne semi-hydrogenation. The AgCu-C3N4 SACs exhibit higher activity and selectivity (99%) than their low-loading variants due to the synergistic interaction of heteronuclear Ag-Cu sites at small inter-site distances. Using a combination of techniques such as phenylacetylene-DRIFTS, H2-temperature programmed desorption and DFT calculations, we showed that the cooperative bimetallic interaction during alkyne semi-hydrogenation was achieved by isolated Ag centers as hydrogen activation sites and isolated Cu centers as alkyne activation sites. Our work highlights the importance of achieving high catalyst loading to reduce the inter-site distance in bimetallic SACs for cooperative interactions, which can potentially open new catalytic pathways for synthesizing fine chemicals and pharmaceuticals.

Navigating the landscape of enzyme design: from molecular simulations to machine learning.

Global environmental issues and sustainable development call for new technologies for fine chemical synthesis and waste valorization. Biocatalysis has attracted great attention as the alternative to the traditional organic synthesis. However, it is challenging to navigate the vast sequence space to identify those proteins with admirable biocatalytic functions. The recent development of deep-learning based structure prediction methods such as AlphaFold2 reinforced by different computational simulations or multiscale calculations has largely expanded the 3D structure databases and enabled structure-based design. While structure-based approaches shed light on site-specific enzyme engineering, they are not suitable for large-scale screening of potential biocatalysts. Effective utilization of big data using machine learning techniques opens up a new era for accelerated predictions. Here, we review the approaches and applications of structure-based and machine-learning guided enzyme design. We also provide our view on the challenges and perspectives on effectively employing enzyme design approaches integrating traditional molecular simulations and machine learning, and the importance of database construction and algorithm development in attaining predictive ML models to explore the sequence fitness landscape for the design of admirable biocatalysts.

Hydrogenolysis of furfuryl alcohol over CuCeMgAl mixed metal oxide catalysts derived from layered double hydroxides

LDH-derived CuCeMgAl mixed metal oxide catalysts were synthesized. Ce addition promoted Cu dispersion and improved catalyst basicity, resulting in high activity in furfuryl alcohol hydrogenolysis and high selectivity toward 1,2-pentanediol.

Continuous-Inline Extraction of Polar Co-solvent During Sequential Flow Reactions

The development of multistep flow synthesis methods for fine chemicals and pharmaceuticals is desirable in terms of cost and energy efficiency. Methods for connecting the first and second flow reactions...

Selective electrooxidation of 5-hydroxymethylfurfural to 5-formyl-furan-2-formic acid on non-metallic polyaniline catalysts: structure-function relationships.

The biomass-derived HMF oxidation reaction (HMFOR) holds great promise for sustainable production of fine chemicals. However, selective electrooxidation of HMF to high value-added intermediate product 5-formyl-furan-2-formic acid (FFCA) is still challenging. Herein, we report the electrocatalytic HMFOR to selectively produce FFCA using carbon paper (CP) supported polyaniline (PANI) as a catalyst. The PANI/CP non-metallic hybrid catalyst with moderate oxidation capacity exhibitsoptimized FFCA selectivity up to 76% in alkaline media, which has reached the best performance in reported literature studies. Identification and quantification of active sites for the HMFOR are further realized via linking the activity to structural compositions of PANI; both polaronic-type nitrogen (N3) and positively charged nitrogen (N4) species are proved responsible for adsorption and activation of HMF, and the intrinsic activity of N4 is higher than that of N3. The present work provides new physical-chemical insights into the mechanism of the HMFOR on non-metallic catalysts, paving the way for the establishment of structure-function relations and further development of novel electrochemical synthesis systems.

One-pot fabrication of vanadium-doped ordered mesoporous zirconium oxophosphate catalyst for the synthesis of carbonyl compounds

V/M-ZrPO composites as promising heterogeneous catalysts for sustainable carbonyl production.