Catalytic Process Research Articles

Tuning the interfacial reaction environment via pH-dependent and induced ions to understand C–N bonds coupling performance in NO3− integrated CO2 reduction to carbon and nitrogen compounds over dual Cu-based N-doped carbon catalyst

Dual atomic catalysts (DAC), particularly copper (Cu2)-based nitrogen (N) doped graphene, show great potential to effectively convert CO2 and nitrate (NO3−) into important industrial chemicals such as ethylene, glycol, acetamide, and urea through an efficient catalytical process that involves C–C and C–N coupling. However, the origin of the coupling activity remained unclear, which substantially hinders the rational design of Cu-based catalysts for the N-integrated CO2 reduction reaction (CO2RR). To address this challenge, this work performed advanced density functional theory calculations incorporating explicit solvation based on a Cu2-based N-doped carbon (Cu2N6C10) catalyst for CO2RR. These calculations are aimed to gain insight into the reaction mechanisms for the synthesis of ethylene, acetamide, and urea via coupling in the interfacial reaction micro-environment. Due to the sluggishness of CO2, the formation of a solvation electric layer by anions (F−, Cl−, Br−, and I−) and cations (Na+, Mg2+, K+, and Ca2+) leads to electron transfer towards the Cu surface. This process significantly accelerates the reduction of CO2. These results reveal that *CO intermediates play a pivotal role in N-integrated CO2RR. Remarkably, the Cu2-based N-doped carbon catalyst examined in this study has demonstrated the most potential for C–N coupling to date. Our findings reveal that through the process of a condensation reaction between *CO and NH2OH for urea synthesis, *NO3− is reduced to *NH3, and *CO2 to *CCO at dual Cu atom sites. This dual-site reduction facilitates the synthesis of acetamide through a nucleophilic reaction between NH3 and the ketene intermediate. Furthermore, we found that the I− and Mg2+ ions, influenced by pH, were highly effective for acetamide and ammonia synthesis, except when F− and Ca2+ were present. Furthermore, the mechanisms of C–N bond formation were investigated via ab-initio molecular dynamics simulations, and we found that adjusting the micro-environment can change the dominant side reaction, shifting from hydrogen production in acidic conditions to water reduction in alkaline ones. This study introduces a novel approach using ion-H2O cages to significantly enhance the efficiency of C–N coupling reactions.

A Multimetal Approach for the Reticulation of Iridium into Metal-Organic Framework Building Units.

Noble metal elements are ubiquitous in our everyday life, from medical applications to electronic devices and synthetic chemistry. Iridium is one of the least abundant elements, and despite its scarcity, it remains essential for efficient and active catalytic processes. Consequently, the development of heterogeneous catalysts with the presence of active iridium sites is of enormous interest as it leads to the improvement of their recyclability and reusability. Here, we demonstrate a strategy to incorporate iridium atoms into metal-organic frameworks (MOFs), as part of their secondary building units (SBUs), resulting in robust and reusable materials with heterogeneous photocatalytic activity.

Enhancing the Electrocatalytic Hydrogenation of Furfural via Anion-Induced Molecular Activation and Adsorption.

The electrocatalytic hydrogenation (ECH) of furfural (FF) to furfuryl alcohol, which does not require additional hydrogen or high pressure, is a green and promising production route. In this study, we explore the effects of anions on FF ECH in two buffer electrolytes (KHCO3 and phosphate-buffered saline [PBS]). Anions influence the yield of furfuryl alcohol through molecular activation and adsorption. Molecular dynamics simulations show that bicarbonate is present in the first shell layer of the FF molecule and induces strong hydrogen bonding interactions. In contrast, hydrogen phosphate is present only in the second shell layer, resulting in weak hydrogen bonding interactions. Owing to the interfacial anions and hydrogen bonding, FF molecules exhibit strong flat adsorption on the electrode surface in the KHCO3 solution, while weak adsorption is observed in the PBS solution, as confirmed by operando synchrotron-radiation Fourier-transform infrared spectroscopy and in situ Raman spectroscopy. Density-functional theory calculations reveal that the overall anionic hydrogen bonding network promotes the activation of the carbonyl group in the FF molecule in KHCO3, whereas electrophilic activity is inhibited in PBS. Consequently, FF ECH demonstrates much faster kinetics in KHCO3, while it exhibits sluggish ECH kinetics and a severe hydrogen evolution reaction in PBS. This work introduces a new strategy to optimize the catalytic process through the modulation of the microenvironment.

Towards Sustainable Production of Polybutylene Adipate Terephthalate: Non-biological Catalytic Syntheses of Biomass-derived Constituents.

Renewable chemicals, which are made from renewable resources such as biomass, have attracted significant interest as substitutes for natural gas- or petroleum-derived chemicals to enhance the sustainability of the chemical and petrochemical industries. Polybutylene adipate terephthalate (PBAT), which is a copolyester of 1,4-butanediol (1,4-BDO), adipic acid (AA), and dimethyl terephthalate (DMT) or terephthalic acid (TPA), has garnered significant interest as a biodegradable polymer. This study assesses the non-biological production of PBAT monomers from biomass feedstocks via heterogeneous catalytic reactions. The biomass-based catalytic routes to each monomer are analyzed and compared to conventional routes. Although no fully commercialized catalytic processes for direct conversion of biomass into 1,4-BDO, AA, DMT, and TPA are available, emerging and promising catalytic routes have been proposed. The proposed biomass-based catalytic pathways toward 1,4-BDO, AA, DMT, and TPA are not yet fully competitive with conventional fossil fuel-based pathways mainly due to high feedstock prices and the existence of other alternatives. However, given continuous technological advances in the renewable production of PBAT monomers, bio-based PBAT should be economically viable in the near future.

A colorimetric sensor based on multiple elements doped carbon dot nanozyme for rapid detection of 1-naphthol in human urine samples

The residual carbaryl in crops can cause serious damage to the human kidney and nervous system after entering the human body, which may be metabolized to 1-naphthol (1-NAP) and excreted through urine. 1-NAP is often used as the biomarker for carbaryl exposure, so the intake or leakage of carbaryl can be monitored by detecting the concentration of 1-NAP. Herein, Co, N, P ternary co-doped carbon dots (CoNP-CDs) derived from vitamin B12 were synthesized by a facile hydrothermal method. CoNP-CDs exhibited oxidase-like activity and excellent peroxidase-like activity, which was attributed to the Fenton-like reaction of Co2+/Co3+ and the presence of pyrrole N and P elements, which together provided multiple active sites for chromogenic substrates. Due to the dual enzyme-like activity of CoNP-CDs, hydroxyl radicals (OH) and superoxide radicals (O2−) were generated during the catalytic process, which could rapidly oxidize colorless 3,3′,5,5′-tetramethyl benzidine (TMB) to blue oxidation products (oxTMB). The α-carbon in 1-NAP can be attacked by OH, and the catalytic oxidation process of TMB can be inhibited by the consumption of OH, so that the blue color of the solution became lighter. Based on this principle, a smartphone-assisted colorimetric sensing platform was constructed for the detection of 1-NAP, and which resulted in a linear range of 1.07–37.3 μM and a visual detection limit of 0.68 μM. Moreover, the colorimetric sensing system showed satisfactory recoveries in the detection of human urine samples. The colorimetric sensing system owned the advantages of fast response, strong selectivity and simple operation, and provided a potential strategy for the on-site detection of 1-NAP.

Molecular and Dissociative Adsorbed Water Concentration and Surface Protonic Conduction in Nanocrystalline TiO2.

Surface protonic conduction in porous nanocrystalline oxides is commonly involved in catalytic processes. The configuration of surface adsorbed water on oxides plays a crucial role in surface protonic conduction. However, studies on the impact of complex surface adsorbed water configuration on the surface water concentration and diffusivity remain limited, and hinder an in-depth understanding of surface proton transport mechanisms, and the design of better surface proton conductors. Here, in situ Raman spectroscopy is utilized to quantitatively identify the contribution of dissociative and molecular adsorbed water components on porous nanocrystalline TiO2 surfaces between 25 and 200°C. The variations in molecular and dissociative adsorbed water concentration agree with the predominant surface proton conduction mechanisms at three different temperature stages. From 40 to 125°C, the reduced coverage of molecular adsorbed water layer results in the decreasing proton diffusivity. Water dissociation on the nanocrystalline TiO2 surface is easier in wet N2 than in wet O2, resulting in higher proton conductivity in wet N2; while the surface proton diffusivities in these two atmospheres are similar. The in situ spectroscopy technique enables the improvement of surface proton conducting oxides through quantitative evaluation and modulation of the surface proton concentration and diffusivity.

Iron and nitrogen co-doped carbon catalysts derived from ZIF-8 towards enhanced peroxymonosulfate activation and contaminants removal: The synergistic effects of FeNx and α/γ-Fe species

The performance upgrading of iron and nitrogen co-doped carbon (Fe-N-C) for peroxymonosulfate (PMS) activation towards contaminants removal and elucidation of the activation mechanism still remains a challenge. In this study, novel iron and nitrogen co-doped carbon (Fe-N-C) catalysts are fabricated through pyrolysis of Fe-modified zeolitic imidazolate framework-8 (ZIF-8) nanocrystals. Catalytic experiments prove that synergistic effects of FeNx and α/γ-Fe species can boost peroxymonosulfate activation and pollutants degradation. Density functional theory simulations disclose that α/γ-Fe species can optimize the d-band center of FeNx and adsorption energy for PMS activation, and thus achieve the enhanced catalytic activities for degradation process. Mechanism studies testify that Fe-N-C-PMS* complex and 1O2 are main contributors for the catalytic process. This work paves a new way for elaborate design of high-performance Fe-N-C materials and understanding about the non-radical mechanism during environmental applications.

Strengthened ozone adsorption through positive electric field-induced charge migration on various TiO2 crystal surfaces: A mechanistic and theoretical study

This study investigates the enhancement of ozone adsorption on diverse TiO2 crystal interfaces through an innovative electrochemical modulation approach. The research focuses on the effects of applied electric field strength and reaction sites on ozone interfacial adsorption energies for Ti/Anatase TiO2 (0 0 1) and Ti/Rutile TiO2 (1 1 0) interfaces. The findings reveal that positive electric fields significantly enhance ozone adsorption on both interfaces, with adsorption energies increasing by up to 18% for Ti/Anatase TiO2 (0 0 1) and 15% for Ti/Rutile TiO2 (1 1 0). Notably, double water molecule sites (≡(H2O)2) play a crucial role in this enhancement process. The study demonstrates that the applied electric field alters the charge distribution at the TiO2 catalytic interface, thereby increasing interfacial charge density and promoting charge migration to ozone. Furthermore, this process leads to enhanced overlap and hybridization between ≡(H2O)2 sites and the s and p orbitals of ozone molecules, resulting in the formation of chemical bonds with lower Fermi levels. These comprehensive results demonstrate the broad applicability of the electrochemical interfacial ozone adsorption enhancement method across different crystal types and surfaces. Consequently, this study provides essential data to support the advancement of greener and more energy-efficient heterogeneous catalytic ozonation processes, potentially contributing to significant improvements in ozone-based water treatment technologies.

Exploring the dynamic evolution of lattice oxygen on exsolved-Mn2O3@SmMn2O5 interfaces for NO Oxidation

Lattice oxygen in metal oxides plays an important role in the reaction of diesel oxidation catalysts, but the atomic-level understanding of structural evolution during the catalytic process remains elusive. Here, we develop a Mn2O3/SmMn2O5 catalyst using a non-stoichiometric exsolution method to explore the roles of lattice oxygen in NO oxidation. The enhanced covalency of Mn–O bond and increased electron density at Mn3+ sites, induced by the interface between exsolved Mn2O3 and mullite, lead to the formation of highly active lattice oxygen adjacent to Mn3+ sites. Near-ambient pressure X-ray photoelectron and absorption spectroscopies show that the activated lattice oxygen enables reversible changes in Mn valence states and Mn-O bond covalency during redox cycles, reducing energy barriers for NO oxidation and promoting NO2 desorption via the cooperative Mars-van Krevelen mechanism. Therefore, the Mn2O3/SmMn2O5 exhibits higher NO oxidation activity and better resistance to hydrothermal aging compared to a commercial Pt/Al2O3 catalyst.

Boosting hydrogen production via alkaline water splitting: Impact of Ag doping in Gd2O3 nanosheet arrays

Hydrogen is a preferable renewable energy carrier in decarbonization efforts to develop sustainable and carbon-free economies due to its high energy density and absence of pollutant emissions during combustion. Among others, electrochemical water splitting (EWS) is a sustainable and eco-friendly technology for producing green hydrogen, representing an essential initial step towards achieving carbon neutrality. In this study, we synthesized a bifunctional electrocatalyst by vertically anchoring Ag-doped Gd2O3 nanosheet arrays onto a three-dimensional nickel foam (NF) substrate. The developed materials were thoroughly investigated using various analytical techniques. Furthermore, the electrocatalyst effectively performed oxygen evolution reactions (OER) and hydrogen evolution reactions (HER). The Ag4%-Gd2O3/NF exhibited boosted HER activity, achieving higher current densities ranging from 10 to 400 mA cm−2 at an overpotential between 14 and 122 mV. This study also highlights the considerable impact of metal sites in both Ag4%-Gd2O3/NF and Gd2O3/NF on the HER catalytic process. Similarly, the Ag4%-Gd2O3 electrocatalyst exhibited superior OER activity, with an overpotential of 209 mV at 10 mA cm−2. The optimized composition also shows Tafel slope of 25 and 20 mVdec−1. Furthermore, Ag4%-Gd2O3 demonstrated the ability to generate oxygen gas bubbles in approximately 20 h for OER, making it an attractive material for energy conversion and storage devices.

Low temperature coupled oxidative/adsorptive desulfurization catalyzed by FeOOH/rGO nanocomposite

Abstract Desulfurization of fossil fuel products has grabbed increased attention, where many research themes focus on the synthesis of novel materials with enhanced desulfurization potentialities, at a reasonable cost, and within a shorter working time. So, in this work, we synthesized ultrathin FeOOH nanorods and then anchored them over reduced graphene oxide (FeOOH/rGO nanocomposite) to act as catalyst/adsorbent system during in situ oxidative/adsorptive desulfurization of diesel fuel model. The XRD, FTIR and Raman analyses demonstrated the successful combination of the FeOOH with the rGO surface. The BET surface area of the FeOOH/rGO was enhanced by 2.2 folds compared to the parent FeOOH, with pore volume ~0.268 cc/g. TEM investigation proved the FeOOH-rGO conjugation. The catalytic processes were carried out in association with H2O2 as an oxidizing element in different conditions. FeOOH showed a high adsorption capacity of ~960 mg/g, and obeyed pseudo-second order kinetic confirming chemisorption nature, while the process Ea recorded about ~85.4 kJ/mol. On the other hand, FeOOH/rGO system achieved ultra-high adsorption capacity of ~989 mg/g with high removal efficiency (98.9%), which assumed FeOOH/rGO as a highly potential catalyst/adsorbent system for ultra desulfurization process.

Sustainable valorization of waste plastic into nanostructured materials for environmental, energy, catalytic and biomedical applications: A review

The extensive production and utilization of plastic products are inevitable in the current scenario. However, the non-degradable nature of waste plastic generated after use poses a grave concern. Comprehensive efforts are being made to find viable technological solutions to manage the escalating challenge of waste plastic. This review focuses on the progress made in transformation of waste plastic into value-added nanomaterials. An overview is provided of the waste plastic issue on a global level and its ecological impacts. Currently established methodologies for waste plastic management are examined, along with their limitations. Subsequently, state-of-the-art techniques for converting waste plastic into nanostructured materials are presented, with a critical evaluation of their distinct merits and demerits. Several demonstrated technologies and case studies are discussed regarding the utilization of these nanomaterials in diverse applications, including environmental remediation, energy production and storage, catalytic processes, sensors, drug delivery, bioimaging, regenerative medicine and advanced packaging materials. Moreover, challenges and prospects in the commercial level production of waste plastic-derived nanomaterials and their adoption for industrial and practical usage are highlighted. Overall, this work underscores the potential of transforming waste plastic into nanostructured materials for multifaceted applications. The valorization approach presented here offers an integration of waste plastic management and sustainable nanotechnology. The development of such technologies should pave the way toward a circular economy and the attainment of sustainable development goals.

Effect of Fly Ash in Pyrolysis of HDPE, LDPE and PP Plastic Waste

Fly ash is generally obtained as a by-product from the combustion of coal and other waste materials. It is used for making bricks, but it has few limitations. The fly ash consists of Silica, Alumina, and other metal oxide components in minor quantities. Fly ash particles are observed in the range of nanometers to micrometers and can act as a catalyst in various reactions. The use of low-cost catalysts in the pyrolysis of thermoplastic waste would achieve a high percentage of low molecular weight fractions in liquid form which increases its applicability in commercial sectors. Hence, there is a need to enhance these fractions to achieve a sustainable approach in the catalytic pyrolysis process. fly ash, being a side product, is very cheap, so its effect on the plastic waste pyrolysis process has been studied. In the present research paper, Physical & chemical characterization of fly ash has been carried out. As fly ash consists of different metal oxides in proportion, its applicability in the process of pyrolysis of HDPE, LDPE, and PP waste has been studied. The different weight percent of fly ash (i.e., 5, 10, 15, 20) have been tried in all pyrolysis experiments. It has been observed that 5 wt % fly ash is effective for enhancing the yield of liquid fuel as compared to that without a catalyst. Liquid fuel obtained from catalytic pyrolysis of HDPE, LDPE, and PP waste with Fly ash consists of a high percent of low molecular weight fractions as compared to that of liquid fuel without catalyst, which has been concluded by calorific values & GC-MS result.

Highly Efficient Production of Furfural from Corncob by Barley Hull Biochar-Based Solid Acid in Cyclopentyl Methyl Ether–Water System

Furfural, an important biobased compound, can be synthesized through the chemocatalytic conversion of D-xylose and hemicelluloses from lignocellulose. It has widespread applications in the production of valuable furans, additives, resins, rubbers, synthetic fibers, polymers, plastics, biofuels, and pharmaceuticals. By using barley hulls (BHs) as biobased support, a heterogeneous biochar Sn-NUS-BH catalyst was created to transform corncob into furfural in cyclopentyl methyl ether–H2O. Sn-NUS-BH had a fibrous structure with voids, a large comparative area, and a large pore volume, which resulted in more catalytic active sites. Through the characterization of the physical and chemical properties of Sn-NUS-BH, it was observed that the Sn-NUS-BH had tin dioxide (Lewis acid sites) and a sulfonic acid group (Brønsted acid sites). This chemocatalyst had good thermostability. At 170 °C for 20 min, Sn-NUS-BH (3.6 wt%) was applied to transform 75 g/L of corncob with ZnCl2 (50 mM) to generate furfural (80.5% yield) in cyclopentyl methyl ether–H2O (2:1, v/v). This sustainable catalytic process shows great promise in the transformation of lignocellulose to furfural using biochar-based chemical catalysts.

TG-FTIR-Py-GCMS analysis and catalytic pyrolysis mechanism of textile waste by red mud catalyst for liquid fuel production

The substantial generation of textile waste (TW) and red mud (RM) has resulted in significant resource wastage and environmental challenges. Co-utilization technology of solid waste is an effective approach to improve waste utilization efficiency. In this study, RM catalytic pyrolysis experiments of TW were conducted using TG-FTIR and Py-GC–MS for liquid fuel production, and TW and RM were recycled simultaneously. At the optimal experimental conditions (temperature of 600 °C and feed catalyst ratio of 2:1), the tar yield and higher heating value (HHV) of TW pyrolysis catalyzed by RM were 73.43 wt% and 32.34 kJ/g, respectively. Additionally, experiments on the pyrolysis of various TW types revealed that LDPE and PP are suitable for tar production, while cotton, nylon, and PET are more suitable as feedstock for syngas production. The RM catalytic pyrolysis mechanism of textile waste is that Fe2O3 in RM exhibits significant catalytic activity in enhancing tar and syngas yields. However, during the catalytic process, Fe2O3 undergoes reduction to Fe3O4, resulting in diminished catalytic performance of the RM. After five cycles of use, the RM essentially lost its catalytic activity due to the accumulation of char and tar. All experimental findings of this study could offer an effective guideline for TW recycle and promoting RM utilization toward the waste-to-energy circular economy.

Carbon-Based Materials in Combined Adsorption/Ozonation for Indigo Dye Decolorization in Constrain Contact Time.

This study presents a comprehensive evaluation of catalytic ozonation as an effective strategy for indigo dye bleaching, particularly examining the performance of four carbon-based catalysts, activated carbon (AC), multi-walled carbon nanotubes (MWCNT), graphitic carbon nitride (g-C3N4), and thermally etched nanosheets (C3N4-TE). The study investigates the efficiency of catalytic ozonation in degrading Potassium indigotrisulfonate (ITS) dye within the constraints of short contact times, aiming to simulate real-world industrial wastewater treatment conditions. The results reveal that all catalysts demonstrated remarkable decolorization efficiency, with over 99% of indigo dye removed within just 120 s of mixing time. Besides, the study delves into the mechanisms underlying catalytic ozonation reactions, elucidating the intricate interactions between the catalysts, ozone, and indigo dye molecules with the processes being influenced by factors such as PZC, pKa, and pH. Furthermore, experiments were conducted to analyze the adsorption characteristics of indigo dye on the surfaces of the materials and its impact on the catalytic ozonation process. MWCNT demonstrated the highest adsorption efficiency, effectively removing 43.4% of the indigo dye color over 60 s. Although the efficiency achieved with C3N4-TE was 21.4%, which is approximately half of that achieved with MWCNT and less than half of that with AC, it is noteworthy given the significantly lower surface area of C3N4-TE.

Fe-MOFs nanosheets for photo-Fenton degradation of carbamazepine

Iron(II)-based metal organic framework (Fe(II)-MOF) nanosheets have emerged as promising candidates for photo-Fenton catalysis. However, efficiently synthesizing Fe(II)-MOF nanosheets remains a significant challenge. Here, a bottom-up synthesis strategy is proposed to prepare two-dimensional Fe-MOF nanosheets (TFMN) with micrometer lateral dimensions and nanometer thickness, featuring Fe(II) as the metal nodes. The application of TFMN in the photo-Fenton degradation of carbamazepine (CBZ) demonstrates remarkable CBZ degradation performance and excellent efficiency across a wide range of pH values. The electron density and density of states are further calculated by density functional theory. Mechanism analysis identifies h+, •OH and •O2− as the predominant active species contributing to the catalytic oxidation process in the Vis/TFMN/H2O2 system.

Effects of the depth of hydro desulfurization of raw materials on the yields of catalytic cracking products

The article is devoted to the problem of complex processing of oil feedstock and increasing the output of light petroleum products, in particular, catalytic cracking gasoline. Currently, the oil refining industry of Kazakhstan is faced with the task of complex processing of hydrocarbon raw materials, increasing the depth of processing and output of light petroleum products. In this connection it is urgent to solve the problem of lack of raw materials for oil refineries of the Republic of Kazakhstan. The complexity of solving the problem of processing residues of oils, fuel oil and intermediates of secondary processes lies in the fact that they contain a large amount of various sulfur compounds. This problem concerns not only domestic refineries, for example, oil from Uzbekistan fields contains a relatively large amount of SO2 compounds, which in turn contains about 1.28% sulphur. The high content of sulfur compounds in oil not only negatively affects the quality and environmental friendliness of manufactured products, but also reduces the service life of equipment and oil refineries. In this regard, the preparation and hydrodesulfurization of raw materials is one of the main issues of intensifying the process of catalytic cracking of petroleum raw materials of "PKOP" LLP. The issues of possibility of modernisation of catalytic cracking process units by including the process of hydrodesulphurisation of feedstock in order to improve the quality and yield of light products when using fuel oil and secondary intermediates having a large volume of various sulphur compounds in their composition have been considered by the authors. To evaluate the influence of the depth of hydrodesulfurisation of feedstock on the yields and composition of catalytic cracking products, the cracking of crude and hydrotreated hydrogenated vacuum gas oil mixed with fuel oil was carried out on a laboratory unit. The experiments were carried out on a fluidised catalyst bed at mass feed rates of 2h-1 and 4h-1, catalyst to feed ratio of 3:1 and temperature equal to 5100 C. The analysis of the experimental data obtained showed that preliminary hydrotreating of a mixture of vacuum gas oil and sulfur fuel oil followed by catalytic cracking increases the depth of oil refining and helps to increase the yield of catalytic distillate, improves its quality, which ultimately leads to a decrease in environmental pollution with sulfur compounds.

Constructing Pr-doped CoOOH catalytic sites for efficient electrooxidation of 5-hydroxymethylfurfural

Electrocatalytic conversion of renewable biomass is emerging as a promising route for sustainable chemical production; hence it urgently calls for developing efficient electrocatalysts with low potentials and high current densities. Herein, a Pr-doped Co(OH)2 hexagonal sheet (Pr/Co = 1/9, in mole) is synthesized by electrodeposition as highly performant catalyst for 5-hydroxymethylfurfural (HMF) oxidation reaction (HMFOR) to produce 2,5-furandicarboxylic acid (FDCA). This novel and low-cost catalyst possesses a rather low onset potential of 1.05 V (vs. RHE) and requires only 1.10 V (vs. RHE) to reach a current density of 10 mA cm−2 for HMFOR, significantly outperforming Co(OH)2 benchmark (i.e., 210 mV higher to reach 10 mA cm−2). The origin of Pr promotion effect as well as the evolution of CoOOH catalytic sites and HMFOR process has been deeply elucidated by physical characterizations, kinetic experiments, in situ electrochemical techniques, and theoretical calculations. The unique Pr-ameliorated CoOOH active centers enable 100% conversion of HMF, 99.6% selectivity of FDCA, and 99.7% Faraday efficiency, with a superior cycling durability toward HMFOR. This can be one of the most outstanding results for Co-based HMFOR catalysts to date in the literature. Thereby this work can help open up new horizons for constructing novel and efficient Co-based electrocatalysts by the utilization of lanthanide elements.

Net hydrogen bond interaction driven supramolecular deep eutectic solvent formation: The case of cyclodextrins

Supramolecular deep eutectic solvents (SUPRADESs) as green designer solvents can be applied to facilitate key steps of separation, extraction, catalysis, and drug transport processes. However, so far, the details concerning the formation mechanism of SUPRADESs are still not clear, thus hindering full development. The present study is dedicated to the theoretical exploration of the structural properties of co-formers that can form SUPRADESs with cyclodextrins (CDs) to design better-performing task-specific SUPRADESs and further structural modifications. Firstly, a series of aliphatic organic acids (AOAs) with similar structures were screened for forming the SUPRADESs. The structure-property relationship showed that co-formers with a higher hydrogen-bond donating ability were found to favor the propensity to form SUPRADESs. Based on this finding, an empirical rule originating from molecular surface electrostatic potential (ESP) descriptors was proposed that can preliminarily predict the formation possibility of SUPRADESs. Density functional theory (DFT) calculations in conjunction with molecular dynamics (MD) simulations further demonstrated that the formation of SUPRADESs mainly depends on the net hydrogen donating ability of co-formers, which is affected by the electron-withdrawing substituent, the carbon chain length, and the molecular self-association degree. Overall, this study provides important guidance to develop novel and green functional SUPRADESs, which will greatly simplify the SUPRADES manufacturing process and reduce the time cost.