Catalytic Reaction Research Articles

Cooperative Diarylborinic Acid/Chloride-Catalyzed Formal SNi Reaction of cis-4-Hydroxymethyl-1,2-Cyclopentene Oxides.

A catalytic formal SNi reaction was designed to achieve stereoretentive products for cis-4-hydroxymethyl-1,2-cyclopentene oxides by using diarylborinic acid as a dual role catalyst and chloride as a catalytic transient nucleophile through a double-displacement mechanism. This reaction offers the advantages of a low catalyst loading of 0.1 mol % and wide substrate scope, even including N-substituents. The use of chiral boron acid as a catalyst for this reaction was also attempted.

A red cell membrane-camouflaged nanoreactor for enhanced starvation/chemodynamic/ion interference therapy for breast cancer

In this study, a multifunctional Cu-doped CaO2 nanoreactor loaded with GOx and camouflaged with a folic acid-modified cell membranewas developed for breast cancer treatment. The as-developed composite nanoreactor showed a synergistic effect on calcium overload to damage mitochondria, thus killing tumor cells to achieve ion interference therapy (IIT). The loaded GOx could deplete glucose to “starve” tumor cells. The H2O2 released by CaO2 decomposition and enzyme catalytic reactions from GOx could not only be highly toxic in the tumor microenvironment but also enhance the efficiency of chemodynamic therapy (CDT) with Cu2+. The red blood cell membranes modified by folic acid achieved a combination of active targeting and passive targeting, thereby enhancing the targeting ability of the as-prepared multifunctional composite nanoreactor and prolonging its retention time at the tumor sites for more than 48 h.

Microbial lipases: propitious biocatalysts for various biotechnological applications

The use of microbial lipases is very important because they have a broad spectrum of catalytic reactions. Lipases catalyze reactions in aqueous and non-aqueous media and have advantages when compared to chemical catalysts, due to their specificity, enantioselectivity and stability at pH and temperature. The interest in research for microbial lipases occurs because of their applicability in various sectors and industries, such as food and beverage production, cosmetics, pharmaceuticals, surfactants, dairy products, treatment of effluents containing oils and fats, biofuels, among others. Biocatalysts can be obtained by submerged fermentation (SF) or solid-state fermentation (SSF), which has advantages over SF, because it is possible to use agroindustrial waste as substrate or growth support for microorganisms, becoming an alternative to reduce production costs. SSF is a promising technology for enzyme production, because besides using low-cost substrates, the biocatalyst can be produced in a more concentrated form, facilitating its recovery from the culture medium when necessary. Thus, this paper intends to discuss and review studies on microbial lipases, with direct application of the fermented solid (SSF), focusing on the main microorganisms, substrates and supports used in SSF, applicability of lipases in several industrial sectors, besides presenting conversion results using different microorganisms or/and substrates.

Catalytic Asymmetric Barbier Reaction of Ketones with Unactivated Alkyl Electrophiles.

The Barbier reaction is a reductive-type addition of an aldehyde or ketone with an organic electrophile in the presence of a terminal metal reductant, providing a straightforward and efficient method for carbon-carbon bond formation. This reaction possesses the advantage of circumventing the preparation of moisture- and air-sensitive organometallic reagents. However, the catalytic Barbier reaction of ketones to construct tetrasubstituted stereogenic centers is largely underdeveloped, despite its great potential for accessing synthetically challenging chiral tertiary alcohol. Particularly, the leveraging of unactivated alkyl electrophiles as coupling components is still rarely exploited. Herein, we disclose a photoredox-assisted cobalt-catalyzed asymmetric alkylative Barbier-type addition reaction of ketones to address the aforementioned challenges, thereby allowing for the construction of highly congested tetrasubstituted carbon centers. The alkyl addition fragments could be either readily accessible unactivated alkyl halides or redox-active esters generated through a decarboxylative pathway. Both types of alkyl electrophiles include primary, secondary, and tertiary ones, thus affording diverse enantioenriched tertiary alcohols with a broad substrate scope. This enantioselective protocol is applied for the expedient synthesis of core structure of Sofdra, a very recent FDA-approved drug in 2024. The newly developed bisoxazolinephosphine (NPN) ligand enables high enantioselectivity in this asymmetric reductive addition process.

Highly Acidic Electron-Rich Brønsted Acids Accelerate Asymmetric Pictet-Spengler Reactions by Virtue of Stabilizing Cation-π Interactions.

Electron-rich heteroaromatic imidodiphosphorimidates (IDPis) catalyze the asymmetric Pictet-Spengler reaction of N-carbamoyl-β-arylethylamines with high stereochemical precision. This particular class of catalysts furthermore provides a vital rate enhancement compared to related Brønsted acids. Here we present experimental studies on the underlying reaction kinetics that shed light on the specific origins of rate acceleration. Analysis of Hammett plots, kinetic isotope effects, reaction orders, Eyring plots, and isotopic scrambling experiments, allowed us to gather insights into the molecular interactions between the chiral Brønsted acid and catalytically formed intermediates. Based on rigorously determined pKa values as well as the experimental evidence, we propose that attractive intermolecular forces offered by electron-rich π-surfaces of the chiral counteranion enthalpically stabilize cationic intermediates and transition states by way of cation-π interactions. This view is furthermore supported by in-depth density functional theory calculations. Our deepened understanding of the reaction mechanism allowed us to develop a method for accessing 1-aryltetrahydroisoquinolines from aromatic dimethyl acetals, a substrate class that was thus far inaccessible via catalytic asymmetric Pictet-Spengler reactions.

Aclarubicin Reduces the Nuclear Mobility of Human DNA Topoisomerase IIβ.

DNA topoisomerase II (TOP2) is an enzyme that resolves DNA topological problems arising in various nuclear processes, such as transcription. Aclarubicin, a member of the anthracyclines, is known to prevent the association of TOP2 with DNA, inhibiting the early step of TOP2 catalytic reactions. During our research on the subnuclear distribution of human TOP2B, we found that aclarubicin affects the mobility of TOP2B in the nucleus. FRAP analysis demonstrated that aclarubicin decreased the nuclear mobility of EGFP-tagged TOP2B in a concentration-dependent manner. Aclarubicin exerted its inhibitory effects independently of TOP2B enzymatic activities: TOP2B mutants defective for either ATPase or topoisomerase activity also exhibited reduced nuclear mobility in the presence of aclarubicin. Immunofluorescence analysis showed that aclarubicin antagonized the induction of DNA damage by etoposide. Although the prevention of the TOP2-DNA association is generally considered a primary action of aclarubicin in TOP2 inhibition, our findings highlight a previously unanticipated effect of aclarubicin on TOP2B in the cellular environment.

Flipping Water Orientation at the Surface of Water-in-Salt and Salt-in-Water Solutions.

Salt-in-water and water-in-salt mixtures are promising for battery applications and fine-tuning of room-temperature ionic liquid (RTIL) properties. Although critical processes take place at interfaces of these systems, including charge transfer and heterogeneous catalytic reactions, the microscopic interfacial structures remain unclear. Here, we apply heterodyne-detected sum-frequency generation spectroscopy to aqueous solutions of imidazolium-based RTILs to unveil the microscopic structure of the interfaces of these solutions with air. Our results show that, under salt-in-water conditions, the orientation of the OH group hydrogen-bonded to the other water molecules flips from the OH group pointing down into the liquid for pure water to up due to the accumulation of anions in the cation-rich interfacial region. However, under the water-in-salt condition, the interfacial water molecules are confined by RTIL, and their orientation is down. Details of the water organization depend critically on the alkyl chain length of the imidazolium cation. Our results demonstrate that the surface structure can be tuned by altering the molecular structure and concentration of the RTIL.

Less is more: Optimisation of variable catalyst loading in CO[formula omitted] electroreduction

The electrochemical conversion of CO2 is a promising method of carbon-neutral chemical production. However, commercial realisation in aqueous electrolytes is challenging, due to competition with the hydrogen evolution reaction (HER), and the propensity for CO2 to participate in the carbonate equilibrium reactions. These two phenomena are linked through OH− ions, as both the by-product of the catalytic reactions and the culprit behind the parasitic carbonate reactions. By reducing the local catalyst loading where the CO2 concentration is low, the HER is decreased more than the reactions that are dependent on CO2 as a reactant. Therefore, it is possible to improve reaction selectivity and reactant utilisation while reducing the capital cost of catalyst. We demonstrate this theory through an analytical solution of a 1D flow electrolyser model. We extend this to a comprehensive model of a contemporary gas-diffusion electrode (GDE) setup. We find that the operation costs are dominated by the electrolyser power consumption and, to a lesser degree, the cost of CO2 and its recovery at the anode. We numerically obtain the catalyst loading profiles that maximise operating profit. The optimisation process reveals that profits are maximised for high gas flow rates, and consequently, low single pass conversions, where the CO2 concentration is as high as possible. However, when lower gas flow rates are used for practical reasons, variable catalyst loadings are shown to lead to significant operational improvements, especially in the production of higher C products that require a greater number of electrons transferred. The model is made freely available in MATLAB and its use is encouraged in determining the applicability of variable catalyst loading to future experimental setups.

Chiral Nanostructured Ag Films for Multicarbon Products from CO2 Electroreduction.

The formation of multicarbon products from CO2 electroreduction is challenging on materials other than Cu-based catalysts. Ag has been known to be a typical metal catalyst, producing CO in CO2 electroreduction. The formation of C2+ products by Ag has never been reported because the carbon-carbon (C-C) coupling is an unfavorable process due to the high reaction barrier energy of *OCCO. Here, we propose that the chirality-induced spin polarization of chiral nanostructured Ag films (CNAFs) can promote the formation of triplet OCCO by regulating its parallel electron spin alignment, and the helical lattice distortion of nanostructures can decrease the reaction energy of *OCCO, which triggers C-C coupling and promotes subsequent *OCCO hydrogenation to facilitate the generation of C2+ products. The CNAFs with helically lattice-distorted nanoflakes were fabricated via electrodeposition using phenylalanine as the symmetry-breaking agent. C2+ products (C2H4, C2H6, C3H8, C2H5OH, and CH3COOH) with a Faradaic efficiency of ∼4.7% and a current density of ∼22 mA/cm2 were generated in KHCO3 electrolytes under 12.5 atm of CO2 (g). Our findings propose that the chiral nanostructured materials can regulate the multifunctionality of catalytic performance in the catalytic reactions with triplet intermediates and products.

Supramolecular Anchoring of Fe(III) Molecular Redox Catalysts into Graphitic Surfaces Via CH‐π and π–π Interactions for CO2 Electroreduction

AbstractPhotoelectrochemical devices require solid anodes and cathodes for the easy assembling of the whole cell and thus redox catalysts need to be deposited on the electrodes. Typical catalyst deposition involves drop casting, spin coating, doctor blading or related techniques to generate modified electrodes where the active catalyst in contact with the electrolyte is only a very small fraction of the deposited mass. We have developed a methodology where the redox catalyst is deposited at the electrode based on supramolecular interactions, namely CH‐π and π–π between the catalyst and the surface. This generates a very well‐defined catalysts‐surface structure and electroactivity, together with a very large catalytic response. This approach represents a new anchoring strategy that can be applied to catalytic redox reactions in heterogeneous phase and compared to traditional methods involves about 4–5 orders of magnitude less mass deposition to achieve comparable activity and with very well‐behaved electroactivity and stability.

Removal of arsenic from aqueous solution using magnetic biochar derived from Spirulina platensis

Arsenic contamination in surface waters and groundwater affects millions of people on a daily basis. Oxidation of As(III) to less toxic As(V) is a widely used strategy to enhance the removal of As from solution. This study developed and evaluated a Fe-modified biochar (FeSP600). Spirulina platensis (SP) is one of the most promising microalgae because of its physicochemical properties and potential applications. The high N content of SP may affect the physicochemical properties of the biochar, which could be used as an inherent N source for N doping biochar by carbonization. After Fe modification, the formed Fe species and N-containing components of SP were used to introduce pyridinic N, which can be coordinated with Fe to form Fe-N. We demonstrated that the formed Fe species (Fe0, Fe2+ and Fe3+) and the defective structures in FeSP600 could act as active sites for surface catalytic reactions. FeSP600 not only had magnetic properties but also could effectively remove As from an aqueous solution. These properties were attributed to the release of Fe2+ and the reactive oxygen species (ROSs) generated by the γ-Fe2O3 particles on the crystalline defect structure. As(III) and As(V) removal were affected by the initial pH values. The removal efficiencies for As(III) increased from 57.2 % to 94.9 % as the pH increased from 3 to 9, whereas that for As(V) decreased from 80.1 % to 46.8 %. The presence of coexisting ions either completely (PO43−) or partially (Cl−, CO32− and SO42−) inhibited As removal. The removal of As(V) depended on electrostatic interactions, but As(III) removal was a complex process, including both oxidation and surface adsorption, as the ROSs were able to oxidize As(III) to As(V). Our study demonstrates that FeSP600 has properties that are beneficial for the removal of As(III) and As(V) from aqueous environments. The findings of this study have potential for real-world application in treating As-contaminated water sources, particularly in improving drinking water purification systems in developing countries. More importantly, an assessment of the impact of FeSP600 usage on aquatic ecosystems is required to ensure the safe application of this technology. Therefore, developing methods for mass production of FeSP600 is essential for the commercialization of this technology, necessitating process engineering studies in this area.

Enhanced Hydrolysis of Carbonyl Sulfide in Coking Oven Gas Utilizing an Efficient Ca-Ba-γ-Al2O3 Catalyst

China possesses a substantial capacity for coke production, resulting in the annual generation of over 100 billion standard cubic meters of the by-product coke oven gas. The comprehensive utilization of this gas has emerged as a matter of significant concern within the coking industry. The removal of carbonyl sulfide (COS) from coke oven gas is crucial for enhancing gas quality, mitigating equipment corrosion, minimizing environmental pollution, elevating the quality of recovered products, and fostering the production of high-quality steel. A novel Ca-Ba-γ-Al2O3 catalyst has been devised, employing γ-Al2O3 as the catalyst matrix and integrating calcium hydroxide (Ca(OH)2) alongside barium hydroxide octahydrate (Ba(OH)2·8H2O) as the alkaline activating components. The impact of various factors, including reaction temperature, humidity, and the number of activating components loaded, on the hydrolysis efficiency of COS has been meticulously investigated. Furthermore, the catalytic reaction mechanism has been elucidated utilizing advanced characterization techniques such as X-ray diffraction (XRD) and Brunauer–Emmett–Teller (BET) analysis. The outcomes of this research reveal that, under optimal conditions of a reaction temperature of 55 °C and a humidity of 56%, the Ca-Ba-γ-Al2O3 catalyst achieves a remarkable COS hydrolysis efficiency of 95.22%.

Dual optimization strategy assisted m-phenylenediamine-based hypercrosslinked polymer loaded ultrafine bimetallic nanoparticles for efficient formic acid dehydrogenation

Heterogeneous catalysts based on Pd play a vital role in enabling efficient formic acid decomposition (FAD). Nevertheless, the performance of Pd-based catalysts is constrained by inherent challenges, such as Pd particles’ tendency to aggregate and possess localized electronic structures. Therefore, there is an urgent need to develop an effective strategy to simultaneously overcome these challenges. In response to this, we synthesized knitting hypercrosslinked polymers (HCPs) using m-phenylenediamine (MPD) as the aromatic monomer. A dual-optimization approach was proposed, aiming to mitigate the adverse effects of excessive coordination and maximize the involvement of residual Fe3+ in the bimetallic synergistic effect. Experimental findings, DFT calculations, and ab initio molecular dynamics simulations (AIMDs) collectively suggest that reducing the coordination effect leads to enhanced nitrogen exposure in the HCPs, consequently reducing the size of Pd species. Furthermore, the incorporation of residual Fe3+ into Pd forms Pd-Fe bimetallic species, which then adjusts the catalytic reaction barrier and enhances catalytic activity. Notably, the optimized Pd@MHCP-2 catalyst exhibited exceptional performance in the FAD reaction at 323 K, achieving a remarkable turnover frequency (TOF) value of 1486 h−1. This research introduces a novel perspective for the design and development of next-generation Pd-based catalysts.

Boosting Fenton-like catalytic performance and environmental stability of nano zero-valent copper (nCu(0)) catalyst by inhibiting the formation of oxide layer: Catalytic performance and mechanistic study

Nano zero-valent copper (nCu(0)) as Fenton-like catalyst has shown great potential in the treatment of organic wastewater. However, nCu(0) is prone to be agglomerated and oxidated, causing to the reduction in catalytic ability. Herein, biochar supported highly dispersed nCu(0) (Cu/C) was synthesized by the carbonization method. And acid-modified strategy was proposed to inhibit the oxidation of nCu(0). Physicochemical properties of Cu/C catalysts modified by different acid (HCl, H2SO4 and HNO3) were analyzed by various characterizations. The results showed that only the introduction of HCl could obviously inhibit the formation of oxide layer on Cu(0), while HNO3 and H2SO4 couldn’t. Furthermore, the content of oxide layers decreased with the increase in HCl addition. Correspondingly, the catalytic performance enhanced gradually. Cu(0) was proved to be the active centers. And the presence of oxide layers was adverse to the catalytic reaction. When the adding amount of HCl reached to 1 mL, the Cu/C-HCl-1.0 catalyst showed the optimal catalytic performance. 97.1 % of p-nitrophenol (PNP) was degraded within 60 min. The reaction rate was 7.6 times that of unmodified Cu/C catalyst. Furthermore, Cu/C-HCl-1.0 catalyst possessed excellent environmental stability. After being directly exposed to air for 4 months, catalytic performance had no obvious decrease. In addition, the catalyst showed efficient degradation ability to phenols, dyes and antibiotics. And it was not sensitive to the initial pH of the organic solution (3.7 ∼ 11.2). OH was confirmed to be the main reactive species for the degradation of organic pollutants, which was formed by the decomposition of PMS by obtaining electrons from Cu(0). This work proposed a novel and efficient method to enhance the catalytic ability and environmental stability of Cu(0) by inhibiting the formation of oxide layer.

CO oxidation on single Pt atom supported by two-dimensional ZnO monolayer: Reaction mechanism and precursor activation

CO oxidation is an effective solution for controlling CO emissions, and supported single-atom catalysts have shown excellent catalytic reactivity for chemical reactions. CO oxidation on a single Pt atom supported by a two-dimensional ZnO monolayer is investigated by combing ab initio molecular dynamics and density functional theory calculations. Seven reaction mechanisms are identified, including two new trimolecular Elie-Riedel mechanisms; six of them, except for the Mars-van Krevelen mechanism, have rate-limiting step energy barriers between 0.31 and 0.47 eV, which is lower than the experimental activation barrier of 0.81 eV on single Pt atoms supported by bulk ZnO, and is much lower than that of about 1.0 eV on Pt(111) surface. Furthermore, two preferred reaction mechanisms are discovered, an Eley-Rideal mechanism and a trimolecular Eley-Rideal mechanism, both of which have rate-limiting step energy barriers as low as 0.31 eV. Our results show that the more antibonding orbitals are filled in the reaction precursor, the higher its activation level. Activation of precursors plays an important role in CO oxidation and leads to different mechanisms. These results provide insights into the design of efficient single-atom catalysts supported by two-dimensional materials for the removal of CO pollutants.

Study of the Sodium Borohydride Hydrolysis Reaction's Performance via a Kaolin-Supported Co-Cr Bimetallic Catalyst

Hydrogen is an attractive source of energy because of its properties, which include superior quality, effectiveness, pureness, dependability, and sustainability. Technologies for producing and storing hydrogen are being developed in parallel with fuel cell development. Chemical storage of hydrogen in a metal hydride containing boron eliminates the problem of hydrogen transportation and storage. Through catalytic reactions, hydrogen stored in solid form in boron hydrides can be recovered. In this study, a nowel developed Co-Cr bimetallic catalyst supported by kaolin, a natural mineral, was synthesized to be used for hydrogen production by hydrolysis of sodium boron hydride. The structural characteristics of the produced Co-Cr@Kaolin catalyst were ascertained by EDX, FTIR, and SEM analyses. Next, the ideal conditions for the hydrolysis reaction of sodium borohydride (NaBH4) catalyzed by Co-Cr@Kaolin were examined. These included the concentration of the catalyst, the amount of support material (kaolin), the amount of catalyst, and the concentration of NaBH4. The optimal hydrolysis conditions were found to be 2.5% NaOH concentration, 40 mg of catalyst, and 2% NaBH4 concentration at 303 K. The maximum rate of hydrogen production was determined as 5007 ml g-1 min-1 under optimal conditions. After conducting hydrolysis operations at different temperatures to elucidate the reaction kinetics, it was found that the catalytic hydrolysis reaction was of the 0th order and that the reaction activation energy was 19.36 kJ mol-1. The hydrogen production rate obtained as a result of the hydrolysis reaction accompanied by a Co-Cr catalyst was determined as 3166 ml g-1 min-1. It is therefore established that supporting kaolin to Co-Cr catalyst enhances its efficacy.

Viscosity Reduction of Heavy Oil Based on Rice Husk Char-Based Nanocatalysts of NiO/Fe2O3

In recent years, catalytic hydrothermal cracking has gained significant attention as an effective technology for reducing the viscosity of heavy oil in the field of heavy oil recovery. However, the current catalyst temperature window is relatively high, leading to high energy consumption in heavy oil extraction. The development of catalysts that can effectively reduce the viscosity of heavy oil at low temperatures is important to reduce energy consumption in the thermal recovery process of heavy oil. Biochar-based catalysts exhibit good low-temperature activity. Therefore, this study used modified rice husk char as a carrier to develop NiO-RHC, Fe2O3-RHC, and NiO/Fe2O3-RHC catalysts, and investigated their performance in low-temperature catalytic viscosity reduction. Various methods were used to characterize the physical and chemical properties of the catalysts, and the effects of catalyst type and addition amounts on the catalytic viscosity reduction reaction were examined. The results showed that the catalytic performance of the dual-active component catalyst was better than that of NiO-RHC and Fe2O3-RHC. Under the catalysis of NiO/Fe2O3-RHC, the viscosity of heavy oil decreased by 81.81%. As the catalyst addition amounts increased, the viscosity reduction rate of heavy oil also increased. The optimal catalyst addition amount was 1.00wt.%, and the heavy component content in the oil sample was reduced by 4.14% after the catalytic reaction. Finally, the mechanism of heavy oil viscosity reduction was analyzed. It was found that the breaking of C-S bonds was a significant factor in reducing heavy oil viscosity, and the S in H2S mainly came from thioether and sulfoxide sulfur. This study provides valuable references for further research on low-temperature viscosity reduction in heavy oil.

MCM‐41 Supported Anthracene Based Cu(II)‐Schiff Base Complex: A Heterogeneous Catalyst for the Synthesis of 4H‐Pyrans/Chromene

AbstractThe anthracene‐appended Schiff base N1‐(anthracene‐9‐methylene)benzene‐1,2‐diamine and its Cu(II) complex has been synthesized and anchored on MCM‐41 support (MCM@CP@AnL@Cu 1). The synthesized catalyst was characterized by various analytical techniques including single crystal X‐ray. Malononitrile, 1,3‐dione, and aromatic aldehydes with various substituents were used in one‐pot, three‐component synthesis of 2‐amino‐3‐cyano‐4H‐pyran/chromene derivatives using above catalyst 1. All the products of the catalytic reaction were characterized by 1H and 13C NMR spectra. We have also proposed a probable reaction mechanism involved in the catalytic reaction. The present catalyst has several advantages like works in mild reaction conditions, that is, at 80 °C, gives higher yields up to 97%, has thermal stability up to 295 °C, and can be reused up to 5 cycles. The immobilized material did not show any considerable leaching or deterioration throughout the catalytic reactions, confirming that it possesses a practical benefit over homogeneous catalysis. The MCM@CP@AnL@Cu (1) is believed to be a good solid heterogeneous catalyst and meets the need of green chemistry for sustainable environment. To the best of our knowledge, this is first example of anthracene‐based Cu (II)‐Schiff base complexes immobilized on modified MCM‐41 surfaces for the multicomponent synthesis of 4H‐pyrans.

Na+ and Cl- adsorption derived enhancement in 4-nitrophenol reduction using Au/Ag nanoparticle: An experimental and theoretical study

4-Nitrophenol (4-NP) is an organic contaminant attached to textiles, pharmaceuticals, and pesticides. Its presence has been increasingly detected in various water bodies such as lakes, rivers, and occasionally in drinking water. The present work shows the reduction of 4-NP using a hybrid catalytic system composed of gold and silver nanoparticles supported onto the biogenic porous silica (AgAu-SiO2). The AgAu nanoparticles were fabricated in situ onto the salinized biogenic silica substrates through a green synthesis. The catalytic reaction was analyzed with NaBH4 and the proposed AgAu-SiO2 catalyst. Mimicking 4-NP reduction reaction in different spiked river/marine water samples revealed superior catalytic activity in marine water. Subsequently, interference studies performed in the presence of different metal salts and pHs (found in the marine water) showed the vital role played by NaCl in the 4-NP reduction as the increase in the NaCl concentration enhances the catalytic activity of the proposed catalyst. Additional reusability of the proposed catalyst demonstrated its efficacy up to 10 cycles. The density functional theory (DFT) results supported the experimental findings, confirming the crucial role of Na+ and Cl- in the catalytic process. Our experimental results, which have significant implications for the field, have been explained by comparing them with DFT calculations. The main reason behind the enhanced catalysis performance in our systems was deduced at the atomic scale. The study included the adsorption energies and electronic density of molecular structures (4-NP and 4-AP) on different surface coverages. In exceptional cases, at the intermediate of 4-NP on Au(111)-NaCl, a displacement of the electronic density is observed, leading to a quinoline-type ring weakening the N-O bond and favoring the catalytic performance.

Reducing the overpotential of overall water spitting by micro-pump-like electrode engineering

Electrolyzing water for hydrogen generation consumes a significant amount of electricity. Minimizing bubble accumulation on the electrodes can reduce the overpotential, thereby enhancing the efficiency of water electrolysis. In this work, Co1.8Mn1.2S4 as the catalyst for oxygen evolution reaction (OER) was optimized from 54 compounds of oxides and sulfides of Ni, Co, and Mn, then designed a three-dimensional electrode with a pump-like function to expel bubbles from the electrodes. Using laser-assisted curing 3D printing technology, a capillary array with side holes was fabricated and utilized as a support structure for the Co1.8Mn1.2S catalyst. During water electrolysis, the electrolyte enters the interior of the capillary through the side holes, and the bubbles inside the capillary are released from both ends of the capillary. The optimized electrode achieved 10 mA cm−2 at an overpotential of 345 mV during the OER, and reached 100 mA cm−2 at an overpotential of 435 mV. In-situ optical microscopy observations and fluid dynamics simulations demonstrated that bubbles were effectively released through the main outlet of the capillary. In overall water splitting, the current density reached 10 mA cm−2 at 1.646 V, without significant current decay after 60 h continuous operation. The electrode design presented holds promise for broader applications in catalytic reactions, such as CO2 reduction, electrochemical ammonia synthesis, and electrochemical treatment of water pollutants.