Traditional Metal Catalysts Research Articles

Encapsulating Transition Metal Nanoparticles inside Carbon (TM@C) Chainmail Catalysts for Hydrogen Evolution Reactions: A Review

Green hydrogen energy from electrocatalytic hydrogen evolution reactions (HERs) has gained much attention for its advantages of low carbon, high efficiency, interconnected energy medium, safety, and controllability. Non-precious metals have emerged as a research hotspot for replacing precious metal catalysts due to low cost and abundant reserves. However, maintaining the stability of non-precious metals under harsh conditions (e.g., strongly acidic, alkaline environments) remains a significant challenge. By leveraging the curling properties of two-dimensional materials, a new class of catalysts, encapsulating transition metal nanoparticles inside carbon (TM@C) chainmail, has been successfully developed. This catalyst can effectively isolate the active metal from direct contact with harsh reaction media, thereby delaying catalyst deactivation. Furthermore, the electronic structure of the carbon layer can be regulated through the transfer of electrons, which stimulates its catalytic activity. This addresses the issue of the insufficient stability of traditional non-precious metal catalysts. This review commences with a synopsis of the synthetic advancement of the engineering of TM@C chainmail catalysts. Thereafter, a critical discussion ensues regarding the electrocatalytic performance of TM@C chainmail catalysts during hydrogen production. Ultimately, a comprehensive review of the conformational relationship between the structure of TM@C chainmail catalysts and HER activity is provided, offering substantial support for the large-scale application of hydrogen energy.

The strong metal-support interaction at Ni–O–Pt interface facilitates rapid electrocatalytic hydrogen production

Electrocatalytic water splitting technology, as an essential method for storing and converting renewable energy, has garnered significant attention. However, traditional electrolytic water splitting is hampered by issues such as noble metal catalysts are expensive and unstable, limiting its widespread application. To address this challenge, this study proposes an innovative method that utilizes nickel metal-organic framework (Ni-MOF) as a support to firmly anchor platinum (Pt) nanoparticles on its surface. This approach not only overcomes the high cost and instability associated with traditional noble metal catalysts but also leverages the strong chelation effect of ethylenediaminetetraacetic acid disodium salt (EDTA·2Na) and the strong metal-support interaction (SMSI) at the Ni–O–Pt interface, prompting catalysts to possess excellent stability and catalytic activity. The catalyst exhibits excellent performance in promoting the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and overall electrolysis of water, maintaining stability throughout the entire electrochemical process. At a current density of 10 mA cm−2, the overpotentials for HER and OER with Pt1·5/Ni-MOF are only 29 mV and 234 mV, respectively. When Pt1·5/Ni-MOF serves as both the cathode and anode for overall water splitting, only a low voltage of 1.557 V is needed. This study offers fresh insights into the development of stable, efficient, and low-budget dual-functional catalysts for water electrolysis, with the potential to drive the commercialization of water electrolysis technology and make significant contributions to the advancement of clean energy.

Effective oxygen evolution of NCF@CoNiO2 with one-dimensional core-shell structure synthesized by induced effect of polymer nanofibers

The non-noble bimetallic oxides have recently received more and more attention in electrocatalytic oxygen evolution reaction (OER) because of their potential to replace traditional precious metal catalysts, but the low activity and stability limit their wide application. Herein, the bimetallic oxide CoNiO2 layers are decorated on the nitrogen-doped carbon nanofibers (NCF) through in situ grown of Ni(Co) bimetal organic frameworks (Ni(Co)-MOFs) on polyacrylonitrile nanofibers and subsequent pyrolysis process, so that a new NCF@CoNiO2 electrocatalyst with one-dimensional (1D) core-shell structure is synthesized by structural induced effect of polyacrylonitrile nanofibers. Importantly, the unique interconnected network formed in the 1D NCF@CoNiO2 electrocatalyst effectively improves electron mobility and mass transport capacity, thus exhibiting the glorious OER activity and long-term stability in alkaline solutions. As a result, the optimal NCF@CoNiO2-7 electrocatalyst requires an overpotential of 518 mV for OER at the current density of 100 mA cm−2, which is obvious lower than that of RuO2 (633 mV) and CoNiO2/C-7 as a contrast sample (569 mV), respectively. This work opens up a new path for structural control of 1D bimetallic oxides to improve OER activity and stability.

Catalysts for Biomass Upgrading: Transforming 5‐Hydroxymethyl Furfural into 2,5‐Furan Dicarboxylic Acid for Fine Chemicals, Featuring Mil‐100(Fe) Mof as a Novel Catalyst

AbstractThis review underscores the potential of metal‐organic frameworks (MOFs), exemplified by MIL‐100(Fe), as catalysts in the conversion of 5‐Hydroxymethyl Furfural to 2,5‐Furan Dicarboxylic Acid, which is crucial in bioplastics and value‐added chemical production. MOFs exhibit advantages, including recyclability, stability, and catalytic potential under mild conditions. Despite promising results, MOFs in this application are underexplored compared to traditional metal catalysts. Noble metal catalysts (Au, Pt, and Pd) face challenges such as cost and limited recyclability. Mechanistic studies favor the DFF route, highlighting the oxidation of HMF's hydroxyl group as predominant. Molecular oxygen proves effective for HMF to FDCA transformation, with gold‐based catalysts noted for selectivity. Ongoing industrial efforts by companies like Avantium indicate a shift towards sustainable alternatives. This review highlights research gaps concerning the necessity for custom Metal‐Organic Framework (MOF) catalysts in the transformation of hydroxymethylfurfural (HMF) into 2,5‐furandicarboxylic acid (FDCA). The study recommends, among other things, 1) the adoption of base‐free conversion systems, 2) a focus on large‐scale FDCA manufacturing, prioritizing environmental sustainability despite prevailing cost challenges, and 3) fostering multidisciplinary collaboration. Utilizing advanced engineering software, such as ASPEN HYSYS, is proposed for optimizing these processes and paving the way for the successful industrialization of FDCA in the future.

Tailoring Hydrogen Evolution Reaction with single-atom catalysts on Ti[formula omitted]B MBenes: Insights from computational screening

The utilization of single-atom catalysts (SACs) in the context of the Hydrogen Evolution Reaction (HER) holds significant promise for advancing electrocatalysis. Upon implantation or anchoring on two-dimensional (2D) materials, these catalysts exhibit improved stability, selectivity, and reactivity. This study uses density functional theory-based computational techniques to demonstrate the potential of SACs embedded on novel 2D materials, such as MBenes. To assess their HER activity, the transition metals (TMs) are screened as SACs embedded in Ti2B monolayer. Our results indicate that the inclusion of a single TM can finely adjust hydrogen adsorption, resulting in a characteristic volcano-like pattern, and particularly Pd-Ti2B emerges as a standout candidate, with an optimal Gibbs free energy of −0.057 eV. Moreover, Pd-Ti2B exhibits a notable exchange current density of 1.25 × 10−4 Acm−2 surpassing that of numerous traditional metal catalysts, including Pt(111), by approximately 105%. Furthermore, we underscore the electronic characteristics contributing to the extraordinary electrocatalytic activity of a single TM atom encased in Ti2B, viz., Pd-Ti2B, for HER. This study contributes greatly to our understanding of electrocatalytic processes and facilitates the development of potent MBenes-based catalysts for hydrogen evolution.

Fe/Thiol Cooperative Hydrogen Atom Transfer Olefin Hydrogenation: Mechanistic Insights That Inform Enantioselective Catalysis.

Asymmetric hydrogenation of activated olefins using transition metal catalysis is a powerful tool for the synthesis of complex molecules, but traditional metal catalysts have difficulty with enantioselective reduction of electron-neutral, electron-rich, and minimally functionalized olefins. Hydrogenation based on radical, metal-catalyzed hydrogen atom transfer (mHAT) mechanisms offers an outstanding opportunity to overcome these difficulties, enabling the mild reduction of these challenging olefins with selectivity that is complementary to traditional hydrogenations with H2. Further, mHAT presents an opportunity for asymmetric induction through cooperative hydrogen atom transfer (cHAT) using chiral thiols. Here, we report insights from a mechanistic study of an iron-catalyzed achiral cHAT reaction and leverage these insights to deliver stereocontrol from chiral thiols. Kinetic analysis and variation of silane structure point to the transfer of hydride from silane to iron as the likely rate-limiting step. The data indicate that the selectivity-determining step is quenching of the alkyl radical by thiol, which becomes a more potent H atom donor when coordinated to iron(II). The resulting iron(III)-thiolate complex is in equilibrium with other iron species, including FeII(acac)2, which is shown to be the predominant off-cycle species. The enantiodetermining nature of the thiol trapping step enables enantioselective net hydrogenation of olefins through cHAT using a commercially available glucose-derived thiol catalyst with up to 80:20 enantiomeric ratio. To the best of our knowledge, this is the first demonstration of asymmetric hydrogenation via iron-catalyzed mHAT. These findings advance our understanding of cooperative radical catalysis and act as a proof of principle for the development of enantioselective iron-catalyzed mHAT reactions.

Recent advances in polyethylene glycol as a dual‐functional agent in heterocycle synthesis: Solvent and catalyst

AbstractReactant solubility, which dictates achievable concentrations, and the stability of reaction intermediates (excited states), solvents modulate the potential energy landscape and influence reaction rates. Consequently, solvent selection is pivotal in optimizing process productivity, economic feasibility, and environmental footprint. At present, organic synthesis pivots around the idea of sustainability. In particular, PEG‐400, a popular solvent and phase transfer catalyst, is considered greener as it can be reused several times without significant loss in its catalytic activity, which checks the box regarding sustainability. This review highlights the emerging potential of Polyethylene Glycol 400 (PEG‐400) as a dual‐threat agent in sustainable organic synthesis. We explore its efficacy as a catalyst, promoting various reactions under mild conditions and often eliminating the need for traditional metal catalysts. Additionally, PEG‐400's role as a green solvent is addressed, emphasizing its biodegradability, low toxicity, and ability to facilitate reactions without hazardous Volatile Organic Compounds (VOCs). The review examines recent research on PEG‐400 mediated reactions, showcasing its effectiveness in diverse transformations, thus exploring the potential of PEG 400 as a facilitator for heterocycle synthesis in both multicomponent reactions and stepwise approaches. It identifies exciting research directions that promise to expand the boundaries of polymer‐based solvents in heterocyclic chemistry.

Non-precious metal high-entropy electrocatalysts (Al0.5NiCoCr-X0.5) for OER application

The high entropy alloy electrocatalysts demonstrate exceptional efficiency in the production of hydrogen through water electrolysis. Consequently, the development of durable and economically efficient electrocatalysts has become an urgent objective to accomplish. In order to achieve this goal, a bulk non-precious metal high-entropy alloy, Al0.5NiCoCr-X0.5 (Mo, Mn, Cu, V, Fe), was synthesized and characterized in this study through physical phase analysis and electrochemical property test. To explore the reasons for the influence of the five added elements on the catalytic performance of high entropy alloys in this system and to find the OER electrocatalyst with the best catalytic performance. Electrochemical performance tests were performed in 1 M KOH electrolyte. At a current density of 10 mA·cm−2, the overpotential of the high-entropy alloy catalyst Al0.5NiCoCrMo0.5 was lower than that of the high-entropy alloy with the addition of the other four elements respectively, which was only 327 mV, and lower than that of the conventional noble metal catalyst RuO2, which had an overpotential of 342 mV. This is attributed to the addition of Mo element, which makes Al0.5NiCoCr produce a large number of HCP phases on top of the original FCC phase and a very small number of BCC phases, which is more conducive to the generation of active sites on the surface of the catalysts, and thus improves the OER activity, and the stability can be maintained for at least 20 hours. Therefore, Al0.5NiCoCrMo0.5 high-entropy alloy catalysts can be used in industrial hydrogen production instead of the traditional precious metal catalysts, and it has a rather broad application prospect, and at the same time, it lays a solid foundation for the application of transition metals in catalysts.

Phosphorus Modification of Iron: Mechanistic Insights into Ammonia Synthesis on Fe2P Catalyst.

Ammonia (NH3) is a critical chemical for fertilizer production and a potential future energy carrier within a sustainable hydrogen economy. The industrial Haber-Bosch process, though effective, operates under harsh conditions due to the high thermodynamic stability of the nitrogen molecule (N2). This motivates the search for alternative catalysts that facilitate ammonia synthesis at milder temperatures and pressures. Theoretical and experimental studies suggest that circumventing the trade-off between N-N activation and subsequent NHx hydrogenation, governed by the Brønsted-Evans-Polanyi (BEP) relationship, is key to achieving this goal. Recent studies indicate metal phosphides as promising catalyst materials. In this work, a comprehensive density functional theory (DFT) study comparing the mechanisms and potential reaction pathways for ammonia synthesis on Fe(110) and Fe2P(001) is presented. The results reveal substantial differences in the adsorption strengths of NHx intermediates, with Fe2P(001) exhibiting weaker binding compared to Fe(110). For N-N bond cleavage, multiple competing pathways become viable on Fe2P(001), including routes involving the pre-hydrogenation of adsorbed N2 (e.g., through *NNH*). Analysis of DFT-derived turnover rates as a function of hydrogen pressure (H2) highlights the increased importance of these hydrogenated intermediates on Fe2P(001) compared to Fe(110) where direct N2 dissociation dominates. These findings suggest that phosphorus incorporation modifies the ammonia synthesis mechanism, offering alternative pathways that may circumvent the limitations of traditional transition metal catalysts. This work provides theoretical insights for the rational design of Fe-based catalysts and motivates further exploration of phosphide-based materials for sustainable ammonia production.

Heteronuclear Dual Metal Atom Electrocatalysts for Water-Splitting Reactions.

Hydrogen is considered a promising substitute for traditional fossil fuels because of its widespread sources, high calorific value of combustion, and zero carbon emissions. Electrocatalytic water-splitting to produce hydrogen is also deemed to be an ideal approach; however, it is a challenge to make highly efficient and low-cost electrocatalysts. Single-atom catalysts (SACs) are considered the most promising candidate to replace traditional noble metal catalysts. Compared with SACs, dual-atom catalysts (DACs) are capable of greater attraction, including higher metal loading, more versatile active sites, and excellent catalytic activity. In this review, several general synthetic strategies and structural characterization methods of DACs are introduced, and recent experimental advances in water-splitting reactions are discussed. The authors hope that this review provides insights and inspiration to researchers regarding DACs in electrocatalytic water-splitting.

Amine Synthesis Using the Amine Donor N-Phenyl Putrescine and the Johnson Matthey Transaminase Biocatalyst Library

Chiral amines are important building blocks in the pharmaceutical, agrochemical and chemical industries. There is a drive to augment traditional transition metal catalysts with ‘green’ alternatives such as biocatalysts. Transaminase (TA) biocatalysts can be used in combination with ‘smart’ sacrificial amine donors to synthesise a variety of aliphatic and aromatic amines from the corresponding aldehydes and ketones. Despite their enormous potential, the unfavourable reaction equilibrium often limits the widespread application of TAs for industrial synthesis. Recently we disclosed a new biomimetic amine donor N-phenyl putrescine (NPP), which was inspired by the biosynthesis of the dipyrroloquinoline alkaloids. NPP was demonstrated to have good activity with a library of commercial and wild-type TAs (total 25 TAs). This work focused on exploring the use of NPP with the Johnson Matthey TA kit (17 biocatalysts; eight S-selective and nine R-selective) and three different amine acceptors (vanillin, benzaldehyde and acetophenone). NPP worked well with all 17 TAs and gave the corresponding amine products vanillylamine, benzylamine and methylbenzylamine (MBA) in up to 85% high-performance liquid chromatography (HPLC) yield. From the screen, STA-14 was identified as a good biocatalyst for further analysis and used in a comparative screen of NPP versus the commonly used donor iPrNH2. It was found that NPP was the best amine donor and used to prepare S-methylbenzylamine in >99.5% enantiomeric excess (e.e.). This work, combined with our previous study, highlights the potential of NPP in the biocatalytic synthesis of amines.

Loading IrOx Clusters on MnO2 Boosts Acidic Water Oxidation via Metal-Support Interaction.

Noble metal-based electrocatalysts are crucial for efficient acidic water oxidation to develop green hydrogen energy. However, traditional noble metal catalysts loaded on inactive substrates show limited intrinsic catalytic activity, and their large sizes have compromised the atom efficiency of these noble metals. Herein, IrOx nanoclusters with sizes below 2 nm, displaying high atom-utilization efficiency of Ir species, were supported on a redox-active MnO2 nanosubstrate (IrOx/MnO2) with different phases (α-MnO2, δ-MnO2, and ε-MnO2) to explore the optimal combination. Electrochemical measurements showed that IrOx/ε-MnO2 had excellent OER performance with a low overpotential of 225 mV at 10 mA cm-2 in 0.5 M H2SO4, superior to its counterpart, IrOx/α-MnO2 (242 mV) and IrOx/δ-MnO2 (286 mV). Moreover, it also delivered robust stability with no obvious change in operating potential at 10 mA cm-2 during 50 h of continuous operation. Combining the XPS results and Bader charge analysis, we demonstrated that the strong metal-support interactions of IrOx/ε-MnO2 could effectively regulate the electronic structures of the active Ir atoms and stabilize IrOx nanoclusters on supports to suppress their detachment, resulting in significantly enhanced catalytic activity and stability for acidic OER. DFT calculations further supported that the enhanced catalytic OER performance of IrOx/ε-MnO2 could be ascribed to the appropriate strength of interactions between the active Ir sites and the reaction intermediates of the potential-determining step (*O and *OOH) regulated by the redox-active substrates.

2D-COFs-derived heteroatom-doped carbon nanosheets as high-efficiency all-solid frustrated lewis pair metal-free hydrogenation catalyst

Metal-free catalysts without metal active sites participating in the reactions have obtained growing attraction under the drive of the economic and environmental problems. Here, 2D-COFs-drived B/N co-doped carbon nanosheets as metal-free catalyst was synthesized by Schiff-based coupling reaction and self-templated carbonization. It shows excellent catalytic performance in nitro compound hydrogenation reaction as all-solid FLP catalyst in H2 system (100 % conversion of nitrobenzene and 99.89 % selectivity to aniline) without any metal active species in the catalyst. This result is the most promising compared to the previous literatures. In the study, the high crystallinity of precursor 2D-COFs is imperative for catalytic stability, and the function of B atoms modification and the B-N synergism were investigated carefully. The formation of B-N bond as a fixed all-solid FLP active center was verified, and it also indicates that B atoms introduction can make the carbon nanosheets orderly and enhance the strength and amount of the acid and base sites. The catalytic mechanism of hydrogen activation was also studied by combining the characterization results and density functional theory (DFT) calculations. The results show that the B atoms doping and defects formation efficiently accelerate the charges aggregation between B-N bonds to form Lewis pairs, and the TS searching calculations shows the significant decrease of H2 dissociation barrier energy and the reaction energy, demonstrating the effectiveness of N and B co-doping strategy. This work is very promising and the metal-free catalyst is the potential alternative to traditional metal catalysts.

Fe and Cr doped porous Co3O4@C nanosheets with abundant oxygen vacancies for highly efficient oxygen evolution reaction

Transition metal oxides have received much attention in the field of oxygen evolution reaction due to their abundance and stability, and are expected to replace traditional noble metal catalysts. In this paper, porous Co3O4@C nanosheets with spinel structure were synthesized by the method of high-temperature combustion, and the elements of Fe and Cr were doped into the spinel structure of Co3O4 to improve the performance of the oxygen evolution reaction. Electrochemical results display that the catalytic performance of Fe and Cr-doped porous Co3O4@C nanosheets is better than that of the noble metal oxide catalyst RuO2 and achieves the overpotential of 230mV at 100mA cm−2. Meanwhile, the overpotential only increases by 13mV after 30 h of a long cycle, which indicates that this catalyst has good cycle stability. The doping with Fe and Cr elements induces the lattice distortion of Co3O4, leading to the increase of oxygen vacancies and the ratio of Co2+/Co3+, which is conducive to improving the performance of the oxygen evolution reaction. Our study shows a simple strategy for the development of highly efficient catalysts with earth-abundant elements for water electrolysis.

Hexagonal Boron Nitride/Reduced Graphene Oxide Heterostructures as Promising Metal‐Free Electrocatalysts for Oxygen Evolution Reaction Driven by Boron Radicals

Developing highly efficient earth‐abundant alternatives to traditional noble metal catalysts is essential for clean and sustainable energy‐conversion and energy‐storage technologies, yet still challenging in limited active sites and weak resistance to electrochemical corrosion. Herein, density‐functional theory calculations demonstrate that hexagonal boron nitride (h‐BN), albeit often being considered inert, can generate boron‐active radicals at defective sites by forming heterogeneous structures with graphene‐containing point vacancies, leading to a substantial electron delocalization and charge transfer, indicating a superior catalytic activity. Experimentally, the van der Waals heterostructure is rationally designed with h‐BN nanosheets (BNNs) anchored on reduced graphene oxide (rGO) as strongly coupled composite catalysts. Despite the poor conductivity in BN and lower catalytic activity in rGO, the created heterostructures demonstrate unexpected, improved oxygen evolution reaction (OER) activity with excellent stability in alkaline electrolyte. Qualitative analysis of the valence band offset and theoretical calculation reveal that the formation of heterostructures can significantly drive the electron transfer between C and B atoms near the vacancies across the interface and cause a half‐metallic property of BN, decreasing the free energy barrier of four‐electron OER kinetics. Herein, the synthetic schemes of h‐BNNs are guided as highly active metal‐free OER electrocatalysts.

Cu/CeO2 and Cu/Gd-Substituted CeO2 Aerogels as Active, Selective, and Stable COPROX Catalysts

Purifying hydrogen feedstocks necessitates preferential oxidation of carbon monoxide (COPROX), but traditional precious metal catalysts are poorly selective, while transition metal catalysts suffer from insufficient activity and stability. We report that Cu nanoparticles supported on CeO2 or Gd(III)-substituted CeO2 (GCO) aerogels deliver a rare combination of high activity, selectivity, and stability for COPROX. The reducing oxide disperses Cu and stabilizes its more active low-valent state. Aerogel-supported Cu oxidizes CO at low temperature but requires higher temperatures to oxidize H2 and, therefore, shows wide temperature ranges with >95% CO conversion and >95% selectivity vs H2. This performance is maintained for >16 h of continuous operation in dry or humidified reaction streams. The Cu/GCO aerogel is less active than Cu/CeO2 under dry feedstreams but experiences less loss of activity under humid conditions because the higher surface area of the former distributes surface-adsorbed water along the network and reacts it at oxygen vacancies. Aerogel-based architected catalysts offer an effective design route to achieve high and stable catalytic activity under industrially relevant conditions.

Theoretical study the catalytic performance and mechanism of novel designed single atom catalysts M1/2DMs for 1,3-butadiene hydrogenation

Selective hydrogenating 1,3-butadiene to butene is an important tool for the removal of 1,3-butadiene which is a by-product of olefin production. Traditional noble metal catalysts are expensive and relatively low selective for 1-butene. In order to decrease the catalyst cost and improve the 1-butene selective, single-atom catalysts were designed by doping non-noble metals single atom (Pd, Ru, Fe, Co, Ni) on two-dimensional material carriers, hexagonal BN and graphene. It is found that 1,3-butadiene tends to be dominated by mono-π-adsorption on single-atom catalysts, resulting in dissociated H atom preferentially attack the one end CC bond of 1,3-butadiene. Unlike the metallic nanomaterials, low energy barriers for the hydrogenation of 1,3-butadiene to 1-butene were obtained (Ru1/BN: 0.20 eV, Fe1/GR: 0.23 eV, Co1/BN: 0.36 eV, Ru1/GR: 0.44 eV, Co1/GR: 0.59 eV, Ni1/GR: 0.61 eV, Ni1/BN: 0.62 eV). The 1-butene desorption energies are smaller than the further hydrogenation energy barriers on the Pd1/GR, Ni1/GR, Pd1/BN Co1/BN and Ni1/BN surfaces, which indicated better selectivity on these catalysts’ surfaces. By contrast, Ni1/GR and Ni1/BN single-atom catalysts would be the best catalysts among all the studied catalyst in terms of adsorption energies of feed gas, dissociation ability of H2, hydrogenation energy barrier and 1-butene desorption energy.

Trends in CO2 Reduction on Transition Metal Dichalcogenide Edges

Electrocatalytic CO2 reduction is a promising solution to close the anthropogenic carbon cycle. However, linear scaling relations among reaction intermediates of the CO2 reduction reaction (CO2RR) and the competing hydrogen evolution reaction (HER) limits the Faradaic efficiencies and selectivities of traditional transition metal catalysts. The two-dimensional transition metal dichalcogenides (TMDCs) is a promising class of catalysts for the reaction. Selected transition metal dichalcogenides have been shown experimentally to effectively reduce CO2 and in some cases produce “beyond CO” products. The majority of theoretical investigations have focused on MoS2 and WS2, materials that have been widely studied for various applications, e.g desulfurization, HER, Li metal batteries and optical devices. In this computational study, we go beyond Mo and W and study the edge configurations, adsorption properties and aqueous stability of a range of TMDC materials in the 2H phase. We show that the most stable edge configuration is highly dependent on the specific composition of the material, while adsorption properties of H, CO, and COOH vary significantly with edge configuration. We furthermore find that, while a linear scaling among H and CO adsorbates is observed within each group of the sulfides, selenides, and tellurides, respectively, the scaling is shifted toward weaker H bonding and stronger CO bonding going from sulfides to selenides to tellurides. A similar trend is observed for CO/COOH for some edge configurations. The results indicate that the transition metal ditellurides are a promising class of materials with the potential of reducing CO2 further than CO while limiting HER.

Graphene Encapsulated Low-Load Nitrogen-Doped Bimetallic Magnetic Pd/Fe@N/C Catalyst for the Reductive Amination of Nitroarene Under Mild Conditions.

The online version contains supplementary material available at 10.1007/s10562-023-04273-7.

Sustainable design of co-doped ordered mesoporous carbons as efficient and long-lived catalysts for H2S reutilization

Selective catalytic oxidation of H2S into elemental sulfur has been recognized as the optimal route for H2S reutilization, but traditional metal catalysts show poor sulfur resistance. Herein, we report a solvent-free route for designing nitrogen and defects co-doped, ordered mesoporous carbons (ND-OMCs) from co-assembly of block copolymer template with nitrogen-containing oligomers and silica defects directing agent. Through thermal curing, carbonization and etching of silica, the microporosity tandem ordered mesopores, abundant nitrogen sites (6.13 wt%) and structural defects were introduced into ND-OMCs. The ND-OMCs were successfully applied as efficient and long-lived metal-free catalysts for H2S selective oxidation to sulfur, giving nearly 100 % H2S conversion and sulfur selectivity at only 150 °C. Their remarkable activities of ND-OMCs can be well-maintained over 157 h of continuous reaction, exhibiting the sulfur capacity as high as 3295 mg/g, which were much better than mostly desulfurizes such as commercial Fe2O3, g-C3N4, and nitrogen-containing, ordered mesoporous carbons.