Correction for 'A review of the recent progress on heterogeneous catalysts for Knoevenagel condensation' by Jimmy Nelson Appaturi et al., Dalton Trans., 2021, 50, 4445-4469, DOI: 10.1039/d1dt00456e.
Carboxylesterases (CEs) are members of prominent esterase, and as their name imply, they catalyze the cleavage of ester linkages. By far, a considerable number of novel CEs have been identified to investigate their exquisite physiological and biochemical properties. They are abundant enzymes in nature, widely distributed in relatively broad temperature range and in various sources; both macroorganisms and microorganisms. Given the importance of these enzymes in broad industries, interest in the study of their mechanisms and structural-based engineering are greatly increasing. This review presents the current state of knowledge and understanding about the structure and functions of this ester-metabolizing enzyme, primarily from bacterial sources. In addition, the potential biotechnological applications of bacterial CEs are also encompassed. This review will be useful in understanding the molecular basis and structural protein of bacterial CEs that are significant for the advancement of enzymology field in industries.
Recently, the discharge of flue gas has become a global issue due to the rapid development in industrial and anthropogenic activities. Various dry and wet treatment approaches including conventional and hybrid hybrid wet scrubbing have been employing to combat against these toxic exhaust emissions. However, certain issues i.e., large energy consumption, generation of secondary pollutants, low regeneration of scrubbing liquid and high efficieny are hindering their practical applications on industrial level. Despite this, the hybrid wet scrubbing technique (advanced oxidation, ionic-liquids and solid engineered interface hybrid materials based techniques) is gaining great attention because of its low installation costs, simultaneous removal of multi-air pollutants and low energy requirements. However, the lack of understanding about the basic principles and fundamental requirements are great hurdles for its commercial scale application, which is aim of this review article. This review article highlights the recent developments, minimization of GHG, sustainable improvements for the regeneration of used catalyst via green and electron rich donors. It explains, various hybrid wet scrubbing techniques can perform well under mild condition with possible improvements such as development of stable, heterogeneous catalysts, fast and in-situ regeneration for large scale applications. Finally, it discussed recovery of resources i.e., N2O, NH3 and N2, the key challenges about several competitive side products and loss of catalytic activity over time to treat toxic gases via feasible solutions by hybrid wet scrubbing techniques.
In this paper, we report about chemically interaction between Pt Subnano-Clusters on Graphene Nano Sheets (GNS). The aim of this research is to clarify the size effect of Pt clusters on Pt 1-7 wt.%/GNS. This research is an experimental laboratory research. GNS was synthesized by using modified Hummer's method and 1-7 wt.% Pt/GNS were prepared with impregnation method. Then, they were analyzed with TG/DTA, XRD, TEM and XPS, respectively. The results show that Pt clusters are well deposited on GNS (TG/DTA and TEM data). Those data also are consistent with XRD data. The weak and broad peaks appear at 2θ = 39°, indicating Pt metal exists on GNS. The state of Pt is confirmed by using XPS. The appearance of Pt 4f. peaks proves that Pt metal is chemical interaction on GNS. The size of Pt clusters may affect the chemically properties of Pt/GNS catalysts.
To remove harmful volatile organic compounds (VOCs) including 2-butanone (methyl ethyl ketone, MEK) emitted from various industrial plants is very important for the clean air. Also, it is worthwhile to recycle porous spent fluid catalytic cracking (SFCC) catalysts from various petroleum refineries in terms of reducing industrial waste and the reuse of discharged resources. Therefore, Mn and Mn-Cu added SFCC (Mn/SFCC and Mn-Cu/SFCC) catalysts were prepared to compare their catalytic efficiencies together with the SFCC catalyst in the ozonation of 2-butanone. Since the SFCC-based catalysts have a structure similar to that of zeolite Y (Y), the Mn-loaded zeolite Y catalyst (Mn/Y) was also prepared to compare its activity for the removal of 2-butanone and ozone to that of the SFCC-based ones at room temperature. Among the five catalysts of this study (Y, Mn/Y, SFCC, Mn/SFCC, and Mn-Cu/SFCC), the Mn-Cu/SFCC and Mn/SFCC catalysts showed the better catalytic decomposition activity than the others. The increased distributions of the Mn3+ species and the Ovacancy sites in Mn/SFCC and Mn-Cu/SFCC catalysts which could supply more available active sites for the 2-butanone and ozone removal would enhance the catalytic activity of them.
The formation of protein homodimer complexes for molecular catalysis and regulation is fascinating. The homodimer formation through 2S (2 state), 3SMI (3 state with monomer intermediate) and 3SDI (3 state with dimer intermediate) folding mechanism is known for 47 homodimer structures. Our dataset of forty-seven homodimers consists of twenty-eight 2S, twelve 3SMI and seven 3SDI. The dataset is characterized using monomer length, interface area and interface/total (I/T) residue ratio. It is found that 2S are often small in size with large I/T ratio and 3SDI are frequently large in size with small I/T ratio. Nonetheless, 3SMI have a mixture of these features. Hence, we used these parameters to develop a decision tree model. The decision tree model produced positive predictive values (PPV) of 72% for 2S, 58% for 3SMI and 57% for 3SDI in cross validation. Thus, the method finds application in assigning homodimers with folding mechanism.
Herein, two stable lead(II) molecular-bowl-based metal-organic frameworks and their micro- and nanosized forms with open metal sites were presented. These materials could act as Lewis acid catalysts to cyanosilylation reaction. Moreover, the catalytic performances are size-dependent, with the catalyst with nanosized form being 1 order of magnitude more efficient than those with micro- and millisized forms.
Understanding the migration and conversion of nitrogen in wood-based panels (WBPs) during pyrolysis is fundamentally important for potentially transforming the N-containing species into valuable material-based products. This review firstly summarizes the commonly used methods for examining N evolution during the WBPs pyrolysis before probing into the association between the wood and adhesives.The potential effects of wood-adhesive interaction on the pyrolysis process are subsequently analyzed. Furthermore, the controversial statements from literature on the influence of adhesives on wood pyrolysis behavior are discussed, which is followed by the detailed investigation into the distribution and evolution of N-containing species in gas, liquid and char, respectively, during WBPs pyrolysis in recent studies. The differences in N species due to the heating sources (i.e. electrical heating vs microwave heating) are particularly compared. Finally, based on the characteristics of staged pyrolysis, co-pyrolysis and catalytic pyrolysis, the converting pathways for WBPs are proposed with an emphasis on the production of value-added chemicals and carbon materials, simultaneously mitigating NOx emission.
In this study, performances of mesoporous Mo/Al2O3 catalysts prepared by sol-gel and post-hydrolysis methods in hydrocracking of atmospheric residual oil were compared. In addition, different methods: (i) the single step and (ii) conventional impregnation method to incorporate active metal over the mesoporous support were also investigated. For single step method, Mo/Al2O3 catalysts were synthesized directly by sol-gel and post-hydrolysis method. On the other hand, the impregnation method was a two step procedure which involved the production of alumina via sol-gel or post-hydrolysis method and followed by respective Mo impregnation. In general, mesoporous Mo/Al2O3 catalysts prepared by sol-gel method resulted in relatively higher surface area (> 400 m2/g) and large pore volume (- 0.8 cm3/g). Mo/Al2O3 catalysts prepared by sol-gel method exhibited higher hydrocracking activity as well. The Mo crystal size was found to relate directly with the hydrocracking result.
Catalytic hydrolysis of sodium borohydride can potentially be considered as a convenient and safe method to generate hydrogen, an environmentally clean and sustainable fuel for the future. The present effort establishes the development of FeCuCo tri-metallic oxide catalyst by a simple, single-step solution combustion synthesis (SCS) method for hydrogen generation from NaBH4 hydrolysis. Amongst series of FeCuCo tri-metallic oxide catalyst synthesized, FeCuCo with 50:37.5:12.5 wt% respective precursor loading displayed remarkable activity by generating hydrogen at the rate of 1380 mL min-1 g-1 (1242 mL in 18 min) with turnover frequency (TOF) of 62.02 mol g-1 min-1. The catalyst was characterized by using various techniques to understand their physiochemical and morphological properties. The results revealed that the catalyst synthesized by combustion method led to the formation of FeCuCo with appreciable surface area, porous foam-like morphology and high surface acidity. Major factors affecting the hydrolysis of NaBH4 such as catalyst loading, NaOH concentration and temperature variation were studied in detail. Additionally, the FeCuCo catalyst also displayed substantial recyclability performance up to eight cycles without considerable loss in its catalytic activity. Therefore, FeCuCo oxide can be demonstrated as one of the most efficient, cost effective tri-metallic catalyst so far for application in the hydrogen generation.
Metal Organic Frameworks (MOFs) represent a promising class of metallic catalysts for reduction of nitrogen-containing contaminants (NCCs), such as 4-nitrophenol (4-NP). Nevertheless, most researches involving MOFs for 4-NP reduction employ noble metals in the form of fine powders, making these powdered noble metal-based MOFs impractical and inconvenient for realistic applications. Thus, it would be critical to develop non-noble-metal MOFs which can be incorporated into macroscale and porous supports for convenient applications. Herein, the present study proposes to develop a composite material which combines advantageous features of macroscale/porous supports, and nanoscale functionality of MOFs. In particular, copper foam (CF) is selected as a macroscale porous medium, which is covered by nanoflower-structured CoO to increase surfaces for growing a cobaltic MOF, ZIF-67. The resultant composite comprises of CF covered by CoO nanoflowers decorated with ZIF-67 to form a hierarchical 3D-structured catalyst, enabling this ZIF-67@Cu foam (ZIF@CF) a promising catalyst for reducing 4-NP, and other NCCs. Thus, ZIF@CF can readily reduce 4-NP to 4-AP with a significantly lower Ea of 20 kJ/mol than reported values. ZIF@CF could be reused over 10 cycles and remain highly effective for 4-NP reduction. ZIF@CF also efficiently reduces other NCCs, such as 2-nitrophenol, 3-nitrophenol, methylene blue, and methyl orange. ZIF@CF can be adopted as catalytic filters to enable filtration-type reduction of NCCs by passing NCC solutions through ZIF@CF to promptly and conveniently reduce NCCs. The versatile and advantageous catalytic activity of ZIF@CF validates that ZIF@CF is a promising and practical heterogeneous catalyst for reductive treatments of NCCs.
An anodic film with a nanoporous structure was formed by anodizing niobium at 60 V in fluorinated ethylene glycol (fluoride-EG). After 30 min of anodization, the anodic film exhibited a "pore-in-pore" structure; that is, there were smaller pores growing inside larger pores. The as-anodized film was weakly crystalline and became orthorhombic Nb2O5 after heat treatment. The energy band gap of the annealed nanoporous Nb2O5 film was 2.9 eV. A photocatalytic reduction experiment was performed on Cr(VI) under ultraviolet (UV) radiation by immersing the nanoporous Nb2O5 photocatalyst in a Cr(VI) solution at pH 2. The reduction process was observed to be very slow; hence, ethylenediaminetetraacetic acid (EDTA) was added as an organic hole scavenger, which resulted in 100% reduction after 45 min of irradiation. The photocatalytic reduction experiment was also performed under visible light, and findings showed that complete reduction achieved after 120 min of visible light exposure.
Over the past decade, there has been a surge of interest in using char (hydrochar or biochar) derived from biomass as persulfate (PS, either peroxymonosulfate or peroxydisulfate) activator for anthropogenic pollutants removal. While extensive investigation showed that char could be used as a PS activator, its sustainability over prolonged application is equivocal. This review provides an assessment of the knowledge gap related to the sustainability of char as a PS activator. The desirable char properties for PS activation are identified, include the high specific surface area and favorable surface chemistry. Various synthesis strategies to obtain the desirable properties during biomass pre-treatment, hydrochar and biochar synthesis, and char post-treatment are discussed. Thereafter, factors related to the sustainability of employing char as a PS activator for anthropogenic pollutants removal are critically evaluated. Among the critical factors include performance uncertainty, competing adsorption process, char stability during PS activation, biomass precursor variation, scalability, and toxic components in char. Finally, some potential research directions are provided. Fulfilling the sustainability factors will provide opportunity to employ char as an economical and efficient catalyst for sustainable environmental remediation.
Graphitic carbon nitride (g-C3 N4 ) is a kind of ideal metal-free photocatalysts for artificial photosynthesis. At present, pristine g-C3 N4 suffers from small specific surface area, poor light absorption at longer wavelengths, low charge migration rate, and a high recombination rate of photogenerated electron-hole pairs, which significantly limit its performance. Among a myriad of modification strategies, point-defect engineering, namely tunable vacancies and dopant introduction, is capable of harnessing the superb structural, textural, optical, and electronic properties of g-C3 N4 to acquire an ameliorated photocatalytic activity. In view of the burgeoning development in this pacey field, a timely review on the state-of-the-art advancement of point-defect engineering of g-C3 N4 is of vital significance to advance the solar energy conversion. Particularly, insights into the intriguing roles of point defects, the synthesis, characterizations, and the systematic control of point defects, as well as the versatile application of defective g-C3 N4 -based nanomaterials toward photocatalytic water splitting, carbon dioxide reduction and nitrogen fixation will be presented in detail. Lastly, this review will conclude with a balanced perspective on the technical and scientific hindrances and future prospects. Overall, it is envisioned that this review will open a new frontier to uncover novel functionalities of defective g-C3 N4 -based nanostructures in energy catalysis.
The lack of stability is a challenge for most heterogeneous catalysts. During operations, the agglomeration of particles may block the active sites of the catalyst, which is believed to contribute to its instability. Recently, titanium oxide (TiO2) was introduced as an alternative support material for heterogeneous catalyst due to the effect of its high surface area stabilizing the catalysts in its mesoporous structure. TiO2 supported metal catalysts have attracted interest due to TiO2 nanoparticles high activity for various reduction and oxidation reactions at low pressures and temperatures. Furthermore, TiO2 was found to be a good metal oxide catalyst support due to the strong metal support interaction, chemical stability, and acid-base property. The aforementioned properties make heterogeneous TiO2 supported catalysts show a high potential in photocatalyst-related applications, electrodes for wet solar cells, synthesis of fine chemicals, and others. This review focuses on TiO2 as a support material for heterogeneous catalysts and its potential applications.
Boron niride microflakes of 2-5 μm in diameter and greater than 40 μm in length with multilayer structure and highly crystalline nature are synthesized in two states of catalysts and dual role of nitrogen at 1100 °C. Most of the microflakes are flat, smooth and vertically aligned with a wall-like view from the top. Transmission electron microscopy shows overlapped layers of microflakes with an interlayer spacing of 0.34 nm. The h-BN components of the synthesized microflakes are verified from B 1s and N1 s peaks at 190. 7 and 397.9 eV. Raman shift at 1370 (cm(-1)) and sharp peaks in the XRD pattern further confirm the h-BN phase and crystalline nature of the synthesized microflakes. Microflakes of h-BN with the above characteristics are highly desirable for the development of a solid state neutron detector with higher detection efficiency.
The current demands of sustainable green methodologies have increased the use of enzymatic technology in industrial processes. Employment of enzyme as biocatalysts offers the benefits of mild reaction conditions, biodegradability and catalytic efficiency. The harsh conditions of industrial processes, however, increase propensity of enzyme destabilization, shortening their industrial lifespan. Consequently, the technology of enzyme immobilization provides an effective means to circumvent these concerns by enhancing enzyme catalytic properties and also simplify downstream processing and improve operational stability. There are several techniques used to immobilize the enzymes onto supports which range from reversible physical adsorption and ionic linkages, to the irreversible stable covalent bonds. Such techniques produce immobilized enzymes of varying stability due to changes in the surface microenvironment and degree of multipoint attachment. Hence, it is mandatory to obtain information about the structure of the enzyme protein following interaction with the support surface as well as interactions of the enzymes with other proteins. Characterization technologies at the nanoscale level to study enzymes immobilized on surfaces are crucial to obtain valuable qualitative and quantitative information, including morphological visualization of the immobilized enzymes. These technologies are pertinent to assess efficacy of an immobilization technique and development of future enzyme immobilization strategies.
The aim of this study is to identify the optimum thermal conversion of Chlorella vulgaris with neuro-evolutionary approach. A Progressive Depth Swarm-Evolution (PDSE) neuro-evolutionary approach is proposed to model the Thermogravimetric analysis (TGA) data of catalytic thermal degradation of Chlorella vulgaris. Results showed that the proposed method can generate predictions which are more accurate compared to other conventional approaches (>90% lower in Root Mean Square Error (RMSE) and Mean Bias Error (MBE)). In addition, Simulated Annealing is proposed to determine the optimal operating conditions for microalgae conversion from multiple trained ANN. The predicted optimum conditions were reaction temperature of 900.0 °C, heating rate of 5.0 °C/min with the presence of HZSM-5 zeolite catalyst to obtain 88.3% of Chlorella vulgaris conversion.
Palm oil mill effluent (POME) is a serious and expensive environmental problem in Malaysia. In this paper, CaFe2O4 is introduced as a novel photocatalyst for the degradation of POME under visible light irradiation. Two synthesis routes, auto-combustion and co-precipitation, and two calcination temperatures 550 °C and 700 °C were used to produce four CaFe2O4 catalysts AC550, AC700, CP550 and CP700. CP550 exhibited the greatest photocatalytic degradation at 56% chemical-oxygen-demand (COD) removal after 8 h of irradiation which dropped to 49% after three consecutive cycles indicating reasonable conversion and high recyclability. BET analysis indicated CP550 had the highest SBET (27.28 m2/g) and pore volume (0.077 cm3/g) which dropped precipitously for CP700 upon increasing the calcination temperature to an SBET of 9.73 m2/g and pore volume of 0.025 cm3/g due to annealing which created a smoother surface area as evidenced by the SEM images. UV-Vis DRS indicated CP550 had the highest band-gap (1.52 eV) which is likely due to the presence of a highly crystalline pure CaFe2O4 phase compared to the other products which existed as a mixture of Fe oxidation states evidenced by the XRD data. The PL spectra for all catalysts indicated significantly lower recombination rate for both CP550 and CP700. Introduction of IPA into the reaction mixture to eliminate hydroxyl radicals resulted in a diminishing of COD removal from 56% to 7% proving hydroxyl radicals to be the primary reactive species responsible for photodegradation of POME.
Transglycosylation is the in-vivo or in-vitro process of transferring glycosyl groups from a donor to an acceptor, which is usually performed by enzymatic reactions because of their simplicity, low steric hindrance, high region-specificity, low production cost, and mild processing conditions. One of the enzymes commonly used in the transglycosylation reaction is cyclodextrin glucanotransferase (CGTase). The transglycosylated products, catalyzed by CGTase, are widely used in food additives, supplements, and personal care and cosmetic products. This is due to improvements in the solubility, stability, bioactivity and length of the synthesized products. This paper's focus is on the importance of enzymes used in the transglycosylation reaction, their characteristics and mechanism of action, sources and production yield, and donor and acceptor specificities. Moreover, the influence of intrinsic and extrinsic factors on the enzymatic reaction, catalysis of glycosidic linkages, and advantages of CGTase transglycosylation reactions are discussed in detail.