Catalyst For Reaction Research Articles

Armchair ReS2 Nanoribbons: A Promising Catalyst for Hydrogen Evolution Reaction

The two-dimensional material rhenium disulphide (ReS2) is currently receiving immense attention due to its applications in electrocatalysis. This is primarily due to ReS2 possessing excellent qualities like stability in air, easy exfoliation, methanol tolerance etc. However, the two-dimensional monolayer of ReS2 is more or less catalytically inert, due to the sulfur layers covering the Re atoms. Modifications of the two-dimensional monolayer like transition metal decoration, metal cluster deposition, nanoribbon formation etc, is found to lead to enhanced activity. Here, we computationally model a particular nanostructure of two-dimensional ReS2 which is in the form of a nanoribbon, for activity directed towards hydrogen evolution reaction (HER). We study the armchair configuration nanoribbons of ReS2 and find that these have a heightened HER activity compared to the basal plane. Through free energy computations, we predict that armchair ReS2 nanoribbons can have activity comparable to platinum and platinum based catalysts, which are ideal for HER. Using the nudged elastic band method, we investigate the probable mechanism of HER, and find that the Heyrovsky reaction has zero activation barrier for armchair ReS2 nanoribbons. Our results indicate that ReS2 nanoribbon is indeed a promising material as a stable and efficient HER catalyst.

Confining ruthenium nanoparticles in MOF pores for high-performance hydrogen evolution reaction

The exploration of low-cost catalysts for hydrogen evolution reaction holds great significance in application. Ruthenium nanoparticles (Ru NPs)-based composites have emerged as a type of promising candidates. This study focuses on the impact of metal–organic framework (MOF) pore structure on the growth of Ru NPs, as well as the resulting effects on their electrocatalytic properties using two Ru@MOFs electrodes (Ru@Ni-BPM/NF and Ru@Ni-BPDC/NF). 3D Ni-BPM can effectively load Ru NPs with uniform and controlled size, while 2D Ni-BPDC leads to uncontrolled growth of Ru NPs. Consequently, Ru@Ni-BPM/NF shows superior catalytic performance with a smaller overpotential of 12 mV at 10 mA cm−2 and a lower Tafel slope of 40.3 mV dec-1, outperforming Ru@Ni-BPDC/NF and commercial Pt/C in alkaline media. Meanwhile, the pore confinement effect of Ni-BPM significantly reduces the aggregation of Ru NPs during extended stability testing, guaranteeing the structural integrity of the electrode and sustained exposure of the active sites.

Synthesis of Ni decorated MoOx nanorod catalysts for efficient overall urea-water splitting.

Substituting slow oxygen evolution reaction (OER) with thermodynamically favorable urea oxidation reaction (UOR) is considered as one of the feasible strategies for achieving energy-saving hydrogen production. Herein, a uniform layer of NiMoO4 nanorods was grown on nickel foam by a hydrothermal method. Then, a series of Ni-MoOx/NF-X nanorod catalysts comprising Ni/NiO and MoOx (MoO2/MoO3) were prepared through regulating annealing atmosphere and reduction temperature. The optimized Ni-MoOx/NF-3 with a large accessible specific area can act as a bifunctional catalyst for electrocatalytic anodic UOR and cathodic hydrogen evolution reaction (HER). At a current density of 100 mA cm-2, the introduction of urea can significantly reduce the overpotential of Ni-MoOx/NF-3 by 210 mV compared to OER. In addition, Ni-MoOx/NF-3 has a higher intrinsic activity than other catalysts. It only requires -0.21 and 1.38V to reach 100 mA cm-2 in HER and UOR, respectively. Such an excellent performance can be attributed to the synergistic function between Ni and MoOx. The presence of metallic Ni and reduced MoOx in pairs is beneficial for improving the electrical conductivity and modulating the electronic structure, resulting in enhancing the electrocatalytic performance. When assembling Ni-MoOx/NF-3 into an overall urea-water splitting system, it can achieve energy-saving hydrogen production and effective removal of urea-rich wastewater.

Role of Metal-Organic Framework Topology on Thermodynamics of Polyoxometalate Encapsulation.

Polyoxometalates (POMs) are discrete anionic clusters whose rich redox properties, strong Bro̷nsted acidity, and high availability of active sites make them potent catalysts for oxidation reactions. Metal-organic frameworks (MOFs) have emerged as tunable, porous platforms to immobilize POMs, thus increasing their solution stability and catalytic activity. While POM@MOF composite materials have been widely used for a variety of applications, little is known about the thermodynamics of the encapsulation process. Here, we utilize an up-and-coming technique in the field of heterogeneous materials, isothermal titration calorimetry (ITC), to obtain full thermodynamic profiles (ΔH, ΔS, ΔG, and Ka) of POM binding. Six different 8-connected hexanuclear Zr-MOFs were investigated to determine the impact of MOF topology (csq, scu, and the) on POM encapsulation thermodynamics.

Pourbaix Machine Learning Framework Identifies Acidic Water Oxidation Catalysts Exhibiting Suppressed Ruthenium Dissolution.

The demand for green hydrogen has raised concerns over the availability of iridium used in oxygen evolution reaction catalysts. We identify catalysts with the aid of a machine learning-aided computational pipeline trained on more than 36,000 mixed metal oxides. The pipeline accurately predicts Pourbaix decomposition energy (Gpbx) from unrelaxed structures with a mean absolute error of 77 meV per atom, enabling us to screen 2070 new metallic oxides with respect to their prospective stability under acidic conditions. The search identifies Ru0.6Cr0.2Ti0.2O2 as a candidate having the promise of increased durability: experimentally, we find that it provides an overpotential of 267 mV at 100 mA cm-2 and that it operates at this current density for over 200 h and exhibits a rate of overpotential increase of 25 μV h-1. Surface density functional theory calculations reveal that Ti increases metal-oxygen covalency, a potential route to increased stability, while Cr lowers the energy barrier of the HOO* formation rate-determining step, increasing activity compared to RuO2 and reducing overpotential by 40 mV at 100 mA cm-2 while maintaining stability. In situ X-ray absorption spectroscopy and ex situ ptychography-scanning transmission X-ray microscopy show the evolution of a metastable structure during the reaction, slowing Ru mass dissolution by 20× and suppressing lattice oxygen participation by >60% compared to RuO2.

Controlled synthesis of M doped NiMoO4 (M = Co, Cu and Fe) for urea, freshwater and seawater oxidation reaction

Electrocatalytic splitting of urea or seawater for hydrogen production has become one of the most promising methods. In this paper, different foreign ions M (M = Co, Cu and Fe) are introduced into this NiMoO4 material by hydrothermal and impregnation methods. Their electrocatalytic properties were investigated in different electrolytes, such as urea, pure water and seawater. What is noteworthy is that the Co-NiMoO4/NF electrode exhibited superior urea oxidation properties (1.32 V @ 10 mA cm−2). The different reaction mechanisms result in the superior water oxidation performance of this Fe3+-NiMoO4/NF material. What is noteworthy is that the durability of the material needs to be improved. The promoted performance is attributed to rapid electron transfer and improved electrical conductivity. Density functional theory (DFT) also shows that this Fe-NiMoO4/NF electrode presents optimal water adsorption energy and improved electrical conductivity, thus improving the catalytic activity of the material because of introduction of Fe. The work provides novel views for the design of environmentally friendly and inexpensive multifunctional catalysts for urea, freshwater and seawater splitting reaction.

NiP2 as an efficient non-noble metal cathode catalyst for enhanced hydrogen isotope separation in proton exchange membrane water electrolysis

Proton exchange membrane (PEM) water electrolysis is crucial for efficient hydrogen isotope separation (HIS) in liquid water. However, current cathode catalysts like platinum (Pt) suffer from scarcity and limited HIS performance. To overcome this challenge, we propose a simple and effective approach involving the synthesis of highly dispersed NiP2 nanoparticles supported on carbon (NiP2/C) through a solid-phase phosphidation reaction, and for the first time report its enhanced HIS performance as the cathode catalyst in PEM electrolyzer. The NiP2/C catalyst demonstrates excellent catalytic properties as a cathode catalyst for hydrogen evolution reaction (HER) in an acidic electrolyte, achieving low overpotential of only 157 mV at 10 mA/cm2 and Tafel slope of 95.6 mV/dec. Meticulous investigations and density functional theory (DFT) calculations reveal the intrinsic factors behind its performance. Furthermore, DFT calculations predict the HIS performance of both NiP2/C and Ni/C catalysts, revealing the advantages of NiP2/C over Ni/C. Experimental results obtained in practical PEM water electrolysis validate these predictions, as NiP2/C exhibits an impressive separation factor α of 6.36, nearly twice that of the Pt/C catalyst. Moreover, NiP2/C demonstrates reliable and consistent HIS performance during a 100-hour PEM electrolysis process. Importantly, our calculation model for deuterium enrichment in liquid water reveals that catalysts with higher separation factors α show faster deuterium enrichment and higher deuterium recovery rates. The utilization of NiP2/C as a non-noble metal cathode catalyst holds great promise for efficient and sustainable hydrogen isotope separation, addressing the limitations of precious metal catalysts and advancing clean energy technologies.

Synthesis of Methyl N-phenylcarbamate Derivatives by Xphos Pd G2 Catalyzed Intermolecular Amidation Reaction

Abstract: The utilization of palladium catalysts in cross-coupling reactions has emerged as a highly promising method for the facile formation of aryl C-N bonds, operating under mild conditions. In this study, we present an efficient approach for the synthesis of methyl N-phenyl carbamate derivatives through the intermolecular amidation of aryl chlorides, catalyzed by Xphos Pd G2. The developed protocol has demonstrated remarkable efficacy, offering several advantages. Notably, the intermolecular amidation reaction exhibited good chemoselectivity, allowing for the precise targeting of desired C-N bond formations while maintaining the integrity of other functional groups. Additionally, this methodology showcases exceptional functional group compatibility, accommodating a diverse array of moieties, including sensitive groups that are traditionally challenging to handle. The Xphos Pd G2 catalyst has proven to be instrumental in orchestrating this transformation, exhibiting high catalytic activity and selectivity. Furthermore, this protocol stands out for its operational simplicity, making it a practical choice for synthetic chemists seeking a straightforward and reliable route to access methyl N-phenyl carbamate derivatives. Overall, this study not only expands the synthetic toolbox for C-N bond formations, but also underscores the significance of palladium-catalyzed methodologies in modern organic synthesis. The reported findings hold substantial promise for applications in medicinal chemistry and material science, where the facile construction of aryl C-N bonds is of paramount importance.

Transformation of Bi4Cl2S5 into sub-10 nm Bi2O2CO3 nanowires for electrochemical reduction of CO2

The development of highly efficient catalysts for the selective electrochemical reduction reaction of CO2 (eCO2RR) to high-valued formate remains a challenge in achieving carbon neutrality and renewable energy conversion. In this study, ultrathin Bi4Cl2S5 nanowires, synthesized using different branched-chain thiols as sulfur sources, were reported for the first time as precatalysts for eCO2RR to formate. Systematic material characterization demonstrated that Bi4Cl2S5 can undergo in-situ evolution into Bi2O2CO3 nanowires, serving as the genuine electrocatalyst for eCO2RR. Through the fine-tuning of ligands during the synthesis of Bi4Cl2S5 nanowires, the optimized Bi4Cl2S5-derived Bi2O2CO3 nanowires exhibited a maximum formate Faradaic efficiency (FEformate) of 95.3 % in eCO2RR using a traditional H-cell, surpassing other prepared samples. Furthermore, an FEformate of over 92.9 % was achieved in a wide potential window of 500 mV, and high performance was maintained over 20 h. This outstanding performance is attributed to the high intrinsic activity, accelerated charge transfer, and the large electrochemical active surface area associated with the characteristic sub-10 nm diameter nanowire structure. Moreover, density function theory calculations further revealed that Bi2O2CO3 can reduce the energy barriers for the formation of *OCHO intermediate and bolster formate production. Our work provides a novel synthesis strategy for excellent Bi-based catalysts in electrocatalysis.

One-pot synthesis of NiFe foam-supported FeWO4/Ni3Se2 nanocomposites and their enhanced electrocatalytic performance for oxygen evolution reaction

The development of composite nanocatalysts having strong interactions with electrode materials is important to enhance the reactivity and stability of catalysts used in electrochemical reactions. In this study, we report a method for directly growing FeWO4/Ni3Se2 composite nanocatalysts on the nickel–iron foam (NFF) surfaces, utilizing nickel (Ni) and iron (Fe) in NFF as precursors for synthesizing Ni3Se2 and FeWO4, respectively. The composite nanocatalysts, serving as electrode materials, are formed by the reaction of W precursor and Se precursors with NFF and exhibited high catalytic activity and long-term stability in oxygen and hydrogen evolution reactions.

Transition metal oxides in CO2 driven oxidative dehydrogenation: Uncovering their redox properties

Extensive research efforts have been devoted to using greenhouse gas CO2 in upgrading bio-derived feedstock to value-added chemicals using the oxidative dehydrogenation route (CO2-ODH) with low-energy input. To realize the effective deployment of CO2-ODH at an industrial scale, it is imperative to advance the development of robust catalysts that can selectively catalyze C-H over C-C bonds, while simultaneously demonstrating thermodynamic stability to coke formation or sintering. Transition metal-based catalysts exhibit significant potential for being highly selective and reactive in the simultaneous conversion of CO2 and hydrocarbons, owing to their surface reducibility, well-balanced acid/base properties, and dynamic oxygen storage capacity. To stimulate further optimization, it's crucial to discover key design principles, potential trends and descriptors, and effective strategies to fine-tune the catalyst materials. This review comprehensively examines experimental and theoretical research aimed at pinpointing the key catalytic characteristics that affect selectivity in transition metal-based mono, bi, and multimetal oxides. It covers aspects like combinations of active metals and supports, effects of composition and alloying, interfacial structures, adsorption strengths, dynamics of in-situ restructuring, defect creation, surface morphology, and electronic properties, among others. We wrap up by suggesting approaches to overcome present obstacles in catalyst design and reactor technology, potentially bridging the lab-to-industry gap in this domain.

Graphitization transformation of aluminum electrolytic spent carbon cathode

Aluminum electrolysis spent cathode carbon (SCC), as typical solid hazardous waste, poses significant environmental risks. Harmless treatment of SCC and recycling of its carbon component are important research areas. In this study, SCC was subjected to microwave hydrothermal acid leaching to remove harmful components, followed by the production of high-quality graphite via iron-catalyzed graphitization. The effects of reaction temperature, heating time, and catalyst loading on the graphitization conversion of SCC were investigated. The catalytic graphitization process of SCC was optimized using the response surface method. The results show that when the reaction temperature is 1520 °C, the heating time is 85.24 min, and the catalyst loading is 46.15 wt%, the graphitization degree of the sample is 97.61 %. The samples prepared under the optimal conditions were characterized using XRD, Raman, SEM, and TEM. The results reveal that the catalytic graphitization process significantly influences the conversion of microcrystalline structures in SCC into graphite structures. The iron-catalyzed transformation of microcrystalline carbon was analyzed to elucidate the graphitization transformation mechanism. This study offers an effective pathway for the high-value utilization of SCC. It also serves as a technical reference for the catalytic graphitization conversion of carbon materials.

Plasma in liquids induced modification of Cu surfaces

Copper oxide surfaces are commonly used as the catalyst for the CO2 reduction reaction towards hydrocarbons. However, the lifetime of these catalyst surfaces is limited. In this paper, a method of production of copper oxides through in-liquid plasma is explored, which may be a suitable reactivation method in such applications. The influence of the plasma, ignited in distilled water, with copper and its oxides is monitored in − situ using infrared spectroscopy and ex-situ using scanning electron spectroscop and x-ray photoelectron spectroscopy of the samples. It is shown that the interaction of the plasma with the samples causes a reduction of the copper oxide on a fast time scale and an oxidation on a longer time scale. The formation of preferentially oriented copper nanocubes is observed.

Effect of hydrogen sources toward the CO2 photoreduction on boron decorated crystalline carbon nitride

Photocatalytic CO2 conversion to industrial fuels is considered an effective measure to solve energy and environmental problems. Presently, Catalysts for CO2 reduction reaction (CO2RR) are mostly confined to metal-based materials, but non-metal materials are less explored. We decorate the highly crystalline carbon nitride, i.e., poly(triazine) imides (PTI), with non-metallic boron (B) to obtain two B/PTI catalysts: Bi/PTI with B being deposited into the six-fold cavity of the PTI, and Bs/PTI with B substituting for C in PTI. For CO2RR, Bi/PTI follows a quasi Mars-van Krevelen process, but the high exposure of Bi results in an overly strong interaction with intermediates, inhibiting the reactivity. In contrast, Bs/PTI enhances the binding with intermediates by introducing Lewis acid-base pairs (B-N), which reduce the ring conjugation effect and induce the enrichment of electrons at the pyridine N. Hence, CO2 reduction with the adsorbed H* (Ha) hydrogenation mechanism in Bs/PTI has a significant reactivity.

Polyaniline 합성 시 단량체와 산화제 비율이 음이온 교환막 연료전지에 대한 산소 환원 촉매의 활성에 미치는 영향

Polyaniline 합성 시 단량체와 산화제 비율이 음이온 교환막 연료전지에 대한 산소 환원 촉매의 활성에 미치는 영향

Theoretical study of [3 + 3] annulation reaction of bromoenal with β-tetralone catalysed by N-heterocyclic carbene

N-heterocyclic carbenes (NHCs) are effective organocatalysts, which are widely used in various cycloaddition reactions. Among them, the [3 + 3] cycloaddition reaction type can be used for the synthesis of six-membered ring, which is also one of the most important methods for the formation of carbon–carbon bonds in organic chemistry. In this paper, a possible reaction pathway for the stereoselective [3 + 3] cycloaddition of bromoenal and β-tetralone have been investigated at the M06-2X/6–31G(d,p)/IEFPCM(THF) level. Our suggested mechanism includes binding of the NHC to bromoenal, 1,2-proton transfer, debromination, 1,3-proton shift, Michael addition, protonation, deprotonation and cyclisation, and NHC regeneration. The stereochemistry of the reaction is determined by the Michael addition step, and the favourable pathway generates the R-configurational dihydropyranone. Furthermore, through the use of global reactivity indexes (GRIs), we are able to demonstrate that the nucleophilicity of the bromoenal is increased by the NHC. The mechanistic insights gained in this work should be helpful in the rational design of potential catalysts for analogous reactions.

Radicals as Chiral Catalysts for Asymmetric Radical Cyclization Reactions

Radicals as Chiral Catalysts for Asymmetric Radical Cyclization Reactions

Solvent-free synthesis of composite magnetic CoO@ZIF-67 for efficient and practical use

The facile synthesis of composite material, combining magnetic CoO with ZIF-67 (CoO@ZIF-67), has been successfully developed. This innovative approach involves the growth of a crystalline (ZIF-67) derived from stable and abundant CoO, resulting in the formation of the composite magnetic CoO@ZIF-67. The synthesis method, based on a solid-state thermal approach (SST), is straightforward and efficient, conducted in a single step and under solvent-free conditions, leading to the homogeneously composite formation of CoO@ZIF-67. Importantly, the composite magnetic CoO@ZIF-67 material has demonstrated remarkable catalytic performance as a heterogeneous catalyst in various reactions while requiring a lower catalyst loading under comparable conditions to those needed for pure ZIF-67. A significant advantage of this newly developed composite catalyst, CoO@ZIF-67, is its ease of separation and recyclability. The recovery catalyst can be achieved through the use of an external magnet, making it a standout feature of the green and environmentally friendly synthetic procedure used in its production.

N-P covalent bond regulation of mesoporous carbon-based catalyst for lowered oxygen reduction overpotential and enhanced zinc-air battery performance

Developing sustainable metal-free carbon-based electrocatalysts is essential for the deployment of metal-air batteries such as zinc-air batteries (ZABs), among which doping of heteroatoms has attracted tremendous interest over the past decade. However, the effect of the heteroatom covalent bonds in carbon matrix on catalysis was neglected in most studies. Here, an efficient metal-free oxygen reduction reaction (ORR) catalyst is demonstrated by the N-P bonds anchored carbon (termed N,P-C-1000). The N,P-C-1000 catalyst exhibits superior specific surface area of 1362 m2 g−1 and ORR activity with a half-wave potential of 0.83 V, close to that of 20 wt% Pt/C. Theoretical computations reveal that the p-band center for C-2p orbit in N,P-C-1000 has higher interaction strength with the intermediates, thus reducing the overall reaction energy barrier. The N,P-C-1000 assembled primary ZAB can attain a large peak power density of 121.9 mW cm−2 and a steady discharge platform of ∼1.20 V throughout 120 h. Besides, when served as the cathodic catalyst in a solid-state ZAB, the battery shows flexibility, conspicuous open circuit potential (1.423 V), and high peak power density (85.8 mW cm−2). Our findings offer a strategy to tune the intrinsic structure of carbon-based catalysts for improved electrocatalytic performance and shed light on future catalysts design for energy storage technologies beyond batteries.

Planar Core and Macrocyclic Shell Stabilized Atomically Precise Copper Nanocluster Catalyst for Efficient Hydroboration of C-C Multiple Bond.

Atomically precise metal nanoclusters (NCs) have become an important class of catalysts due to their catalytic activity, high surface area, and tailored active sites. However, the design and development of bond-forming reaction catalysts based on copper NCs are still in their early stages. Herein, we report the synthesis of an atomically precise copper nanocluster with a planar core and unique shell, [Cu45(TBBT)29(TPP)4(C4H11N)2H14]2+ (Cu45) (TBBT: 4-tert-butylbenzenethiol; TPP: triphenylphosphine), in high yield via a one-pot reduction method. The resulting structurally well-defined Cu45 is a highly efficient catalyst for the hydroboration reaction of alkynes and alkenes. Mechanistic studies show that a single-electron oxidation of the in situ-formed ate complex enables the hydroboration via the formation of boryl-centered radicals under mild conditions. This work demonstrates the promise of tailored copper nanoclusters as catalysts for C-B heteroatom bond-forming reactions. The catalysts are compatible with a wide range of alkynes and alkenes and functional groups for producing hydroborated products.