Value-added Chemicals Research Articles

Converting CO2 Into Natural Gas Within the Autoclave: A Kinetic Study on Hydrogenation of Carbonates in Aqueous Solution.

Catalytic conversion of carbon dioxide (CO2) into value-added chemicals is of pivotal importance, well the cost of capturing CO2 from dilute atmosphere is super challenge. One promising strategy is combining the adsorption and transformation at one step, such as applying alkali solution that could selectively reduce carbonate (CO3 2-) as consequences of CO2 adsorption. Due to complexity of this system, the mechanistic details on controlling the hydrogenation have not been investigated in depth. Herein, Ru/TiO2 catalyst was applied as a probe to elucidate the mechanism of CO3 2- activation, in which with thermodynamic and kinetic investigations, a compact Langmuir-Hinshelwood reaction model was established which suggests that the overall rate of CO3 2- hydrogenation was controlled by a specific C-O bond rupture elementary step within HCOO- and the Ru surface was mainly covered by CO3 2- or HCOO- at independent conditions. This assumption was further supported by negligible kinetic isotope effects (kH/kD≈1), similarity on reaction barriers of CO3 2- and HCOO- hydrogenation (ΔH≠ hydr,Na2CO3 and ΔH≠ hydr,HCOONa) and a non-variation of entropy (ΔS≠ hydr≈0). More interestingly, the alkalinity of the solution is certainly like a two sides in a sword and could facilitate the adsorption of CO2 while hold back catalysis during CO3 2- hydrogenation.

S-scheme homojunction of 0D cubic/2D hexagonal ZnIn2S4 for efficient photocatalytic reduction of nitroarenes

The targeted conversion of toxic nitroarenes to corresponding aminoarenes presents significant promise in simultaneously addressing environmental pollution concerns and producing value-added fine chemicals. In this study, we synthesize a 0D/2D ZnIn2S4 homojunction (CH-ZnIn2S4) by in situ growth of cubic ZnIn2S4 (C-ZnIn2S4) quantum dots onto the surface of ultrathin hexagonal ZnIn2S4 (H-ZnIn2S4) nanosheets for photocatalytic reduction of nitroarenes to aminoarenes using water as a hydrogen donor. The optimal performance of photocatalytic nitro reduction over the 0D/2D CH-ZnIn2S4 homojunction reaches 96.1% within 20 min of visible light irradiation, which is 2.45 and 1.52 times than that of C-ZnIn2S4 (39.3%) and H-ZnIn2S4 (63.3%), respectively. The improved photocatalytic performance can be attributed to the formation of a step-type S-scheme homojunction, characterized by identity chemical composition and natural lattice matching. The configuration enables continuous band bending and a low energy barrier of charge transportation, benefiting the charge transfer across the interface while maximizing their redox capabilities. Furthermore, the 2D structure of H-ZnIn2S4 nanosheets offers abundant surface sites to immobilize the 0D C-ZnIn2S4 that provides ample exposed active sites with low overpotential for HER, thereby ensuring high hydrogenation reduction activity of nitroarenes. The study is expected to inspire further interest in the reasonable design of homojunction structures for efficient and sustainable photocatalytic redox reactions.

Anti-defect engineering of Pd/NiCo2O4 hybrid nanocatalysts for enhanced CO2 hydrogenation to formate

Efficiently converting CO2 into value-added chemicals remains a significant challenge due to its inert nature. Here, we present the rational design of Pd/NiCo2O4 hybrid nanocatalysts with diverse morphologies for highly efficient CO2 hydrogenation to formate. The synergistic combination of Pd and NiCo2O4 offers improved catalytic activity towards formate production. Remarkably, the observation of a morphology-dependent Pd-NiCo2O4 interaction, linked to the presence of oxygen vacancies in NiCo2O4, significantly contributes to our understanding of catalytic activity. The rose-like Pd/NiCo2O4 catalyst achieves an impressive formate yield (85.3 molformate moltotalPd−1 h−1) due to its low oxygen vacancy concentration and subsequent generation of less positively-charged Pd species, emphasizing the crucial role of oxygen vacancies in hybrid nanocatalyst performance. These findings were further validated through density functional theory calculations, providing valuable insights into the design and optimization of nanocatalysts for CO2 hydrogenation. This contributes to the development of efficient and sustainable processes for CO2 utilization in the production of formate and other valuable chemicals.

Technology Readiness and Emerging Prospects of Coupled Catalytic Reactions for Sustainable Chemical Value Chains.

Transitioning from both the direct and indirect use of fossil fuels to the renewable and sustainable resources of the near future demands a focal shift in catalysis research - from investigating catalytic reactions in isolation to developing coupled reactions for modern chemical value chains. In this Perspective, we discuss the status and emerging prospects of coupled catalytic reactions across various scales and provide key examples. Besides being a sustainable and essential alternative to current fossil-based processes, the coupling of catalytic reactions offers novel and scalable pathways to value-added chemicals. By emphasizing the specific requirements and challenges arising from coupled reactions, we aim to identify and underscore research needs that are critical to expedite their development and to fully unlock their potential for chemical and fuel production.

Recent Progress in the Conversion of Methylfuran into Value-Added Chemicals and Fuels.

2-methylfuran is a significant organic chemical raw material which can be produced by hydrolysis, dehydration, and selective hydrogenation of biomass hemicellulose. 2-methylfuran can be converted into value-added chemicals and liquid fuels. This article reviews the latest progress in the synthesis of liquid fuel precursors through hydroxyalkylation/alkylation reactions of 2-methylfuran and biomass-derived carbonyl compounds in recent years. 2-methylfuran reacts with olefins through Diels-Alder reactions to produce chemicals, and 2-methylfuran reacts with anhydrides (or carboxylic acids) to produce acylated products. In the future application of 2-methylfuran, developing high value-added chemicals and high-density liquid fuels are two good research directions.

Fabrication of Keggin heteropolyacid modified macroporous covalent triazine frameworks with cyano group-rich defects for high-value utilization of carbohydrates

Designing an efficient, stable and recyclable solid acid for catalytic conversion of biomass and its derived compounds to synthesize high value-added organic chemicals could effectively alleviate the environmental problems caused by the energy crisis and carbon dioxide emissions. We prepared a Keggin heteropolyacid modified macroporous covalent triazine frameworks (PW12-MCTF) catalyst using a simple template method and post-impregnation technology for efficient conversion of carbohydrates to produce 5-hydroxymethylfurfural (HMF). Abundant structural defects of MCTF can be constructed in situ through incomplete polymerization, which can firmly bind H3PW12O40 through physical confinement effect and bonding interactions. Under optimized conditions, PW12-MCTF exhibited high HMF yield (79.4 % or 44.4 %) and the highest turnover frequency (4.39 min−1 or 1.86 min−1) in microwave-assisted catalytic conversion of fructose or inulin, respectively. Its catalytic activity surpassed that of bulk PW12-CTF and commercial acid zeolite and resin catalysts, due to its appropriate acid properties, well-dispersed nature in DMSO, inter-connected pore structure and outstanding nucleophilic effect of N-rich units. Density Functional Theory (DFT) study provides a plausible mechanism in PW12-CTF-catalyzed fructose dehydration. The catalytic performance of PW12-MCTF remained unchanged after three cycles due to strong bonding interaction between the Keggin units and framework of MCTF. This study will provide a new strategy for the fabrication of heteropolyacid modified covalent organic frameworks with structural defects to achieve the high-value utilization of carbohydrates.

Photoreforming of poly(ethylene-terephthalate) plastic into valuable chemicals and hydrogen over BiVO4/MoOx: Synergistic promotion of oxidation and reduction processes

Photoreforming plastic waste into value-added chemicals along with hydrogen evolution is crucial for the circular economy, but its efficiency is limited by mutual constraints between proton reduction and plastic oxidation. Herein, MoOx particles were decorated onto BiVO4 attempting to promote photo-redox reactions, simultaneously. Experiments and theoretical calculations demonstrate that oxygen vacancy in MoOx promotes the adsorption of pretreated poly(ethylene-terephthalate), leading to enhanced oxidation of poly(ethylene-terephthalate). Meanwhile, MoOx boosts the transfer of photoelectrons from BiVO4 to MoOx by Mo5+/6+ ions with variable valence states and lowers the free energy of H+ + e– → H* from 0.39 to –0.12 eV, thereby promoting H2 evolution. Consequently, the photoreforming efficiencies of converting poly(ethylene-terephthalate) into formate, acetate and H2 by BiVO4/MoOx are 0.29, 0.19 and 1.96 mmol g–1 h–1, which are respectively 6.2, 6.0 and 5.9 times higher than that by BiVO4. This work presents avenues for designing high-performance catalysts to efficiently photo-reform plastic.

Preparation of Value-added Chemicals via Chemical Looping Pyrolysis of Corn Straws with Ca-Fe Composite Oxygen Carrier

Biomass chemical looping pyrolysis (BCLPy), which utilizes either reduced or oxidized oxygen carriers for biomass pyrolysis, enables the simultaneous production of high-quality bio-oils and clean syngas. In this study, CLPy of corn straws with a Ca-Fe composite oxygen carrier was investigated to produce value-added chemicals by optimizing both temperature and the mass ratio of oxygen carrier to biomass (OC/B). It has been demonstrated that the reduced Ca-Fe oxygen carrier (Re-OC) promotes hydrocarbon formation and facilitates removal of oxygenated compounds from bio-oils. Under optimal conditions (Re-OC/B = 4:3, T = 650 °C), the relative percentage of benzene, toluene and xylene (BTX) in the bio-oil reaches 27.0 area%, while that of 2-pentenone accounts for 38.0 area% at 550 °C with a Re-OC/B mass ratio of 1:3. The maximum yield based on corn straws approaches 4.7 wt.%. Regarding the oxidized Ca-Fe oxygen carrier (Ox-OC), the relative percentage of 2,3-dihydrobenzofuran (2,3-DHB) reaches a maximum value of 11.6 area% at 600 °C with an Ox-OC/B mass ratio of 2:3. Under catalytic ketonization of Ca2Fe2O5 oxygen carrier, a maximum value of 28.0 area% is achieved with an Ox-OC/B mass ratio of 4:3 at 450 °C. In summary, BCLPy provides a completely new strategy for producing biomass-derived chemicals with added value.

Precursor-Driven Catalytic Performances of Al2O3-Supported Earth-Abundant Ni Catalysts in the Hydrogenation of Levulinic Acid and Hydroxymethylfurfural into Added-Value Chemicals.

It has been shown that the nature of the metal precursor and the thermal effects during calcination determine the physicochemical properties of the catalysts and their catalytic activity in the levulinic acid (LA) and 5-hydroxymethylfurfural (HMF) hydrogenation reactions. The endothermic effect during calcination of the inorganic nickel precursor promoted higher metal dispersion and stronger interaction with the alumina surface. In contrast, the exothermic effects during the calcination of organic nickel precursors resulted in smaller metal dispersion and lower interaction with the support surface. A clear relationship was found between the size of the metal crystallites and the yield of LA hydrogenation reaction. The smaller crystallites were more active in the LA hydrogenation reaction. In turn, the size of the metal particles and their nature of interaction with the surface of the alumina influence the hydrogenation pathways of the HMF.

Cultivation driven transcriptomic changes in the wild-type and mutant strains of Rhodospirillum rubrum

Purple photosynthetic bacteria (PPB) are versatile microorganisms capable of producing various value-added chemicals, e.g., biopolymers and biofuels. They employ diverse metabolic pathways, allowing them to adapt to various growth conditions and even extreme environments. Thus, they are ideal organisms for the Next Generation Industrial Biotechnology concept of reducing the risk of contamination by using naturally robust extremophiles. Unfortunately, the potential of PPB for use in biotechnology is hampered by missing knowledge on regulations of their metabolism. Although Rhodospirillum rubrum represents a model purple bacterium studied for polyhydroxyalkanoate and hydrogen production, light/chemical energy conversion, and nitrogen fixation, little is known regarding the regulation of its metabolism at the transcriptomic level. Using RNA sequencing, we compared gene expression during the cultivation utilizing fructose and acetate as substrates in case of the wild-type strain R. rubrum DSM 467T and its knock-out mutant strain that is missing two polyhydroxyalkanoate synthases PhaC1 and PhaC2. During this first genome-wide expression study of R. rubrum, we were able to characterize cultivation-driven transcriptomic changes and to annotate non-coding elements as small RNAs.

Atomically dispersed Zn-NxCy sites on N-doped carbon for catalytic transfer hydrogenation of ethyl levulinate into γ-valerolactone

Catalytic transfer hydrogenation (CTH) of biomass-derived carbonyl compounds provides a viable strategy to synthesize high value-added chemicals and biofuels, for which the development of efficient catalysts still remains a formidable challenge. Here, we report a Zn-based single-atom catalyst (Zn/NC-950), prepared by pyrolysis of ZIF-8 at 950 °C, for the CTH of ethyl levulinate to γ-valerolactone (GVL). This catalyst exhibited excellent performance, affording a GVL selectivity of 95.3 % at an ethyl levulinate conversion of 100 %, using isopropanol as the hydrogen source at 200 °C and autogenous pressure. The structural characterization and theoretical calculation demonstrate that such extraordinary efficacy of the Zn/NC-950 catalyst is attributed to the dual Zn-N3C1 and Zn-N2C2 sites of low Zn oxidation states, which work synergistically to generate the active hydrogen species and activate the carbonyl bonds, respectively. This work provides a rationale for the precise design of the non-noble metal single-atom catalysts efficient for the biomass valorization.

Separation and conversion of CO2 reduction products into high-concentration formic acid using bipolar membrane electrodialysis

Electrochemical CO2 reduction to value-added chemicals such as formate represents a crucial pathway in advancing carbon-neutral fuel production. However, the separation of formate from KHCO3 electrolyte solutions and its conversion to formic acid remain cost intensive steps in this process. This study demonstrated the use of bipolar membrane electrodialysis (BMED) to efficiently convert and concentrate formic acid directly from a cathodic solution for CO2 electroreduction. The migration of formate ions during BMED was optimized under different cell configurations and current densities. Mathematical modelling was developed to predict the concentration evolution curves of formic acid production. The results showed that formic acid diffusion through an anion-exchange membrane was more pronounced than that a bipolar membrane; the former diffusion was a key factor that limited the formic acid concentration and reduced the current efficiency. A formic acid concentration of 3.49 mol/L was obtained at an optimum current density of 40 mA/cm2 and a salt-to-acid compartment volume ratio of 25:1. Thus, BMED has emerged as a viable and effective technique for isolating high-purity formic acid from a cathodic solution for CO2 electroreduction.

Molybdenum iron carbide-copper hybrid as efficient electrooxidation catalyst for oxygen evolution reaction and synthesis of cinnamaldehyde/benzalacetone

Oxygen evolution reaction (OER) is the efficiency limiting half-reaction in water electrolysis for green hydrogen production due to the 4-electron multistep process with sluggish kinetics. The electrooxidation of thermodynamically more favorable organics accompanied by CC coupling is a promising way to synthesize value-added chemicals instead of OER. Efficient catalyst is of paramount importance to fulfill such a goal. Herein, a molybdenum iron carbide-copper hybrid (Mo2C-FeCu) was designed as anodic catalyst, which demonstrated decent OER catalytic capability with low overpotential of 238 mV at response current density of 10 mA cm−2 and fine stability. More importantly, the Mo2C-FeCu enabled electrooxidation assisted aldol condensation of phenylcarbinol with α-H containing alcohol/ketone in weak alkali electrolyte to selective synthesize cinnamaldehyde/benzalacetone at reduced potential. The hydroxyl and superoxide intermediate radicals generated at high potential are deemed to be responsible for the electrooxidation of phenylcarbinol and aldol condensation reactions to afford cinnamaldehyde/benzalacetone. The current work showcases an electrochemical-chemical combined CC coupling reaction to prepare organic chemicals, we believe more widespread organics can be synthesized by tailored electrochemical reactions.

Toward Durable CO2 Electroreduction with Cu-Based Catalysts via Understanding Their Deactivation Modes.

The technology of CO2 electrochemical reduction (CO2ER) provides a means to convert CO2, a waste greenhouse gas, into value-added chemicals. Copper is the most studied element that is capable of catalyzing CO2ER to obtain multicarbon products, such as ethylene, ethanol, acetate, etc., at an appreciable rate. Under the operating condition of CO2ER, the catalytic performance of Cu decays because of several factors that alters the surface properties of Cu. In this review, these factors that cause the degradation of Cu-based CO2ER catalysts are categorized into generalized deactivation modes, that are applicable to all electrocatalytic systems. The fundamental principles of each deactivation mode and the associated effects of each on Cu-based catalysts are discussed in detail. Structure- and composition-activity relationship developed from recent in situ/operando characterization studies are presented as evidence of related deactivation modes in operation. With the aim to address these deactivation modes, catalyst design and reaction environment engineering rationales are suggested. Finally, perspectives and remarks built upon the recent advances in CO2ER are provided in attempts to improve the durability of CO2ER catalysts.

Crystal phase engineering of CoBOx/NiCoP heterostructures as trifunctional electrocatalysts for overall water splitting and urea electrolysis

Rational design of non-precious metal-based catalysts for value-added chemicals production is crucial but still challenging. Herein, a trifunctional electrocatalyst with heterostructures is developed via phosphating and NaBH4 pretreatment of the pristine ZIF-L for overall water splitting and urea oxidation. The as-prepared CoBOx/NiCoP catalyst exhibits superior electrocatalytic performance with only overpotentials of 100, 283 mV for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) to reach the current density of 10 and 100 mA cm−2, respectively, and the low potential of 1.35 V to achieve a current density of 100 mA cm−2 for urea oxidation reaction (UOR). Theoretical calculations show that the construction of amorphous/crystalline heterostructure can accelerate the charge transfer between the active site and intermediate, thus enhance the intermediates adsorption and reduce the kinetic barrier toward HER/OER process for enhancing electrocatalytic activity. Importantly, the in-situ Raman spectroscopy discloses that the rapid formation of oxidation-state transition metal oxyhydroxide species would provide more active sites for the oxidation reaction. This multiple electrocatalysis demonstrates the great potential of amorphous/crystalline heterogeneous interfaces for high-performing electrocatalytic conversions.

Co-pyrolysis of Baltic wheat straw and low-density polyethylene bags and its kinetic and thermodynamic behaviour

Wheat cultivation represents about 42 % of the total cereal cultivation area in the Baltic Sea region, generating huge amounts of wheat straw (WS) that needs to be optimally managed. In this context, this research aims to investigate the extent of using pyrolysis process in WS valorization. The experiments were performed using a thermogravimetric (TG) analyzer on WS and its mixtures with low-density polyethylene (LDPE) bags at different mixing ratios (1:1, 1:2, 1:3, 1:4). The released TG vapours were monitored using TG-Fourier transform infrared spectroscopy (TG-FTIR) and chromatography-mass spectrometry (GC-MS). The thermochemical activation energy (Ea) were studied by Kissinger-Akahira-Sunose, Flynn-Wall-Ozawa, Friedman, and Vyazovkin models. The pyrolysis results showed that WS and LDPE could be completely decomposed as a single reaction up to 600 °C and 520 °C, respectively. Aromatic-carbonyl and CO2 were the main FTIR functional group for WS vapour versus -CH2- for LEDP vapour. The GC/MS analysis of WS showed various compounds such as sec-Butylamine (11.88 %), acetic acid (10.68 %), etc., while LDPE showed many compounds without specific trend even when the heating rate was changed. While the co-pyrolysis results showed that WS/LDPE could be decomposed individually in two successive reactions at 335 °C (WS) and 495 °C (LDPE). These results were confirmed by FTIR and GC/MS which showed that the functional groups and chemical compounds of vapour generated at these decomposition zones have similar characteristics to those obtained from pyrolysis of WS and LDPE. Finally, kinetic analysis showed that WS-Baltic (227–250 kJ/mol) is more complex compared to WS-Asian (163–217 kJ/mol) due to its higher ash content. While Ea of WS/LDPE was increases upto 274–291 kJ/mol (1:1), 266–297 kJ/mol (2:1), 268–289 kJ/mol (3:1), and 278–299 kJ/mol (1:4). Also, the enthalpy, and Gibbs free energy coefficients of WS were increased by mixing (1:1) up to 272 J/mol K, while its entropy does not change much by mixing (367 J/mol K). Accordingly, the co-pyrolysis process is a key technology in valorization of WS and convert into value-added chemicals and a sustainable energy source.

Funneling lignin hydrolysates into β-ketoadipic acid by engineered Pseudomonas putida KT2440

Bioconversion of lignin into value-added chemicals could promote lignin valorization and the lignin-based bioeconomy. The heterogeneity nature of lignin and the lack of efficient conversion pathways pose limitations on the efficiency of lignin conversion. In this study, Pseudomonas putida KT2440 was successfully engineered for converting lignin to β-ketoadipic acid, a C6 keto-diacid that functions as building block for high performance polymers. Blocking the degradation pathway of β-ketoadipic acid enabled its biosynthesis from both H- and G-type lignin-derived monomers. The aromatic hydroxylation and O-demethylation was identified as the rate-limiting step for producing β-ketoadipic acid from H- and G- type lignin-derived monomers, respectively. Overexpressing pobA and vanAB successfully vanished the accumulation of 4-hydroxybenzoic acid and vanillic acid within 36 h and 30 h, respectively. The beneficial gene operations were integrated into the chromosome to create the strain HE65. Employing this strain, fed-batch strategies were used to achieve a record β-ketoadipic acid production of 14.80 g/L from mixed lignin-derived aromatics in shake-flask experiments. Remarkably, the strain could also thrive in actual lignin hydrolysates from corn stover, yielding a record β-ketoadipic acid output of 2.48 g/L without the need for separation or detoxification processes. Overall, these results underscore the significant potential of engineering P. putida for converting lignin into β-ketoadipic acid, offering a promising pathway for feasible lignin valorization.

Superior electrocatalytic nitrate-to-ammonia conversion activity on CuCo bimetals in neutral media

Electrocatalytic recycling of waste nitrate (NO3-) to valuable ammonia (NH3) has been regarded as a sustainable and promising alternative to the unfriendly Haber-Bosch process. Nevertheless, it is still a challenge to achieve high production rate in a neutral media due to the multi-step electron and proton transfer process. Herein, a nonprecious CuCo tandem catalyst is facilely fabricated and the cooperative active sites enable efficient cascade NO3--to-NH3 conversion with outstanding Faradaic efficiency (FE) and high-rate NH3 generation (95 %, 710 μmol h−1 cm−2 at −0.65 VRHE) in neutral media. In-situ Fourier transform infrared spectroscopy (FTIR) is implemented to identify the reaction intermediates to figure out the tandem pathway. Further combined the density functional theory (DFT) calculations, the structure-activity relationship is unveiled. The introduction of Cu regulates the electronic structure of Co to boost the adsorption capacity of nitrate and shifts the d-band to lower the energy barrier. Moreover, the presence of Cu plays a vital role in inhibiting the binding of H*, which ensures the superior FE. To further maximize the energy utilization efficiency, a two-electrode electrolyzer (Cu45Co55||CuNi) is assembled by replacing the anodic oxygen evolution reaction (OER) with thermodynamically favored 5-hydroxymethylfurfural (HMF) oxidation to produce value-added 2,5-furandicarboxylic (FDCA), an important intermediate in the synthesis of bioplastics. These findings might guide the rational design of efficient and inexpensive electrocatalysts to produce value-added chemicals and hold the promise for contributing to carbon peaking and neutrality goals.

Tailoring Cu-Based Electrocatalysts for Enhanced Electrochemical CO2 Reduction to Alcohols: Structure-Selectivity Relationship.

The use of CO2 as a feedstock for the production of carbon-based fuels and value-added chemicals offers a promising route toward carbon neutrality. In this study, two Cu-based electrocatalysts, namely, Cu24/N-C and Cu2/N-C, are successfully prepared by thermal treatment of Cu24 metal-organic polyhedron-loaded zeolitic imidazolate framework-8 (ZIF-8) nanocrystals (Cu24/ZIF-8) and Cu2 dinuclear compound-loaded ZIF-8 nanocrystals (Cu2/ZIF-8), respectively. Extensive structural and compositional analyses were conducted to confirm the formation of Cu nanocluster-loaded N-doped porous carbon supports in both Cu24/N-C and Cu2/N-C and Cu nanoparticles encapsulated by graphitic carbons in Cu2/N-C as well. These two Cu-based electrocatalysts exhibited different behaviors in the electrochemical CO2 reduction reaction (CO2RR). The Cu24/N-C electrocatalyst showed high selectivity for CO production, while Cu2/N-C showed a preference for alcohol generation. The excellent stability of Cu2/N-C over a 30 h continuous electrochemical reduction further highlights its potential for practical applications. The difference in electrocatalytic performance observed in the two catalysts for CO2RR was attributed to distinct catalytic sites associated with Cu nanoclusters and nanoparticles. This research reveals the significance of their structures and compositions for the development of highly selective electrocatalysts for CO2 reduction.

Computational Assessment of the Mechanistic Journey in Chan-Lam-Based Arylation of Imidazoles.

Cu(II)-catalyzed C-N bond formation reactions remain one of most widely practiced and powerful protocols for the synthesis of value-added chemicals, bioactive molecules, and materials. Despite numerous experimental contributions, the overall mechanistic understanding of the C-N coupling reaction based on the Chan-Lam (CL) reaction methodology is still limited and underdeveloped, particularly with respect to the use of different substrates and catalytic species. Herein, we report an in-depth DFT-based study on the mechanism of N-arylation of imidazoles following Collman's experimental setup. Our findings unfold for the first time the ligand-based CL coupling catalyzed by the [Cu(II)(OH)TMEDA]2Cl2 complex. The transmetalation step with an energy span of 26.2 kcal mol-1 is rate-determining, while the subsequent disproportionation and reductive elimination are relatively facile (δE = 16.4 kcal mol-1) in comparison to the CL amination of secondary amines. The final oxidative catalyst regeneration results in the presence of O2, accompanying an energy span of 12.8 kcal mol-1, where hydrogen transfer from the coordinated water allows the reduction of superoxo linkage. Couplings performed in the presence of a combination of bidentate sp3-N ligands with single and double -(CH2)- spacer units afford a kinetically facile transformation (24.5 kcal mol-1). Furthermore, our results agree with the experimental outcomes of regioselective couplings of substituted imidazoles.