Efficient Metal-free Catalyst Research Articles

Dual-Mechanism Study of Metal-Free g-C3N4 Catalysts for Advanced Oxidation Under Non-Photocatalytic Conditions.

Metal-free materials have been proved to be promising replacements of traditional metal-based catalysts for advanced oxidation reactions. Carbon nitride was found to be able to activate H2O2 and generate hydroxyl radicals (•OH). Nevertheless, the performance of carbon nitride is highly dependent on an external light source. In this work, we report a light-independent, metal-free catalyst based on g-C3N4 prepared using a facile calcination method. It is revealed that two reaction pathways, a radical (•OH) one and a nonradical (H2O2) one, coexist in organics oxidation on g-C3N4. The dominant reaction pathway is dependent on the condensation temperature of UCN. In addition, this g-C3N4 exhibited excellent stability after being recycled and reused for five cycles. The findings in this work can be used for the design of efficient and robust metal-free catalysts with both superior catalytic performance and high stability for various heterogeneous catalytic processes.

Highly Efficient Metal-Free Coal-Based Carbon Aerogel Catalyst for Oxygen Reduction to Produce Hydrogen Peroxide

Highly Efficient Metal-Free Coal-Based Carbon Aerogel Catalyst for Oxygen Reduction to Produce Hydrogen Peroxide

In-situ exfoliating graphene to anchor Mo2C NPs and modulate crystal planes for hydrogen production

An economical and efficient noble metal-free catalyst is necessary for large-scale hydrogen production. Here, Mo2C nanoparticles (NPs) were well-dispersed on the surface of 2D graphene nanosheets by in-situ propping oxide graphene (GO) layers, anchoring molybdate ions between GO layers and pyrolysis. The exposed crystal planes were also adjusted by above strategy. The results indicate that uniform and well-dispersed Mo2C NPs with a narrow size distribution were anchored on 2D rGO nanosheets and exposed dual crystal planes. The results of hydrogen evolution reaction (HER) show that the optimal Mo2C/rGO catalyst only needs low overpotential (η10, 112 mV) to drive 10 mA cm−2 in alkaline solution, and η10 only increased by 12 mV after 1000 cycles test, indicating high activity and stability for HER. Notably, the overpotential is below than that of Pt/C commercial catalyst when current density is more than 100 mA cm−1. The excellent performance is benefit from low hydrogen adsorption Gibbs free energy (ΔGH∗) on the Mo2C catalyst. Therefore, the proposed strategy is efficient to prepare well-dispersed and dual crystal planes-exposed Mo2C NPs for electrocatalytic hydrogen evolution.

N, P Dual-Doped Carbons as Metal-Free Catalysts for Hydrogenation.

The activation of molecule hydrogen (H2) by metal-free catalysts is always a challenge in the field of catalysis. Herein, a series of N, P dual-doped carbon catalysts were constructed by the pyrolysis of chitosan and phytic acid and utilized as metal-free catalysts for the hydrogenation of nitrobenzene. The characterization indicated that the doping of phosphorus atoms not only formed the species with catalytic activity for hydrogenation reaction but also promoted the doping of N. The experimental results indicated that their catalytic performance could be improved by the regulation of pyrolysis temperature and heating rate. CP-900-1 (pyrolysis at 900 °C with a heating rate of 1 °C/min) exhibited a promising catalytic activity with >99% nitrobenzene conversion. N, P codoping was the key factor to its catalytic performance. All results indicated that the excellent catalytic activity of CP-900-1 was attributed to the synergistic interaction among pyridinic N, P-C species, and graphitic N. This work provides an effective route for the rational design and construction of highly efficient metal-free catalysts for hydrogenation.

Electrochemical sensing for simultaneous determination of dopamine and acetaminophen based on ZIF-8@ZIF-67 derived Co/Mo2C embedded in N-doped carbon hollow nanocages

The exploration of an economical and efficient noble metal-free heterogeneous catalyst is of great significance for the construction of an electrochemical method for the simultaneous detection of Dopamine (DA) and acetaminophen (AC). In this paper, we employed a facile strategy to obtain Co/Mo2C nanoparticles embedded in nitrogen-doped carbon hollow nanocages (Co/Mo2C@N-C HNCs) heterogeneous structure by pyrolyzing ZIF-8@ZIF-67 precursor. The unique hollow structure ensures a fast electron transport channel, N doping regulates the local electronic structure of the catalyst, and the synergistic effect with Mo2C and Co nanoparticles provides more electrocatalytic active sites. The Co/Mo2C@N-C HNCs electrode separates the overlapping voltammetry peaks of DA and AC into two distinct voltammetry peaks (△E=200 mV), thereby selectively determining DA in the presence of AC and vice versa. The transfer coefficient (α) and electron transfer number (n) of DA and AC electrocatalytic oxidation were also studied. Using Co/Mo2C@N-C HNCs as electrode, an electrochemical sensor platform for the simultaneous detection of acetaminophen (AC) and dopamine (DA) was first constructed with linear range of 1–185 μM, and 1–100 μM and low detection limit of 0.35 μM and 0.46 μM for AC and DA, respectively. Satisfactory results have been obtained in the determination of human serum and acetaminophen tablets samples. DFT calculation reveals the molecular mechanisms for DA and AC interacting with the Co/Mo2C@N-C HNCs catalysts. This strategy provides a new idea for the selective determination of several analytes in complex substrates.

Oxidative Cleavage of α-O-4, β-O-4, and 4-O-5 Linkages in Lignin Model Compounds Over P, N Co-Doped Carbon Catalyst: A Metal-Free Approach.

Developing efficient metal-free catalysts for lignin valorization is essential but challenging. In this study, a cost-effective strategy is employed to synthesize a P, N co-doped carbon catalyst through hydrothermal and carbonization processes. This catalyst effectively cleaved α-O-4, β-O-4, and 4-O-5 lignin linkages, as demonstrated with model compounds. Various catalysts were prepared at different carbonization temperatures and thoroughly characterized using techniques such as XRD, RAMAN, FTIR, XPS, NH3-TPD, and HRTEM. Attributed to higher acidity, the P5NC-500 catalyst exhibited the best catalytic activity, employing H2O2 as the oxidant in water. Additionally, this metal-free technique efficiently converted simulated lignin bio-oil, containing all three linkages, into valuable monomers. Density Functional Theory calculations provided insight into the reaction mechanism, suggesting substrate and oxidant activation by P-O-H sites in the P5NC-500, and by N-C-O-H in the CN catalyst. Moreover, the catalyst's recyclability and water utilization enhance its environmental compatibility, offering a highly sustainable approach to lignin valorization with potential applications in various industries.

Strain engineering of CoSA[sbnd]N[sbnd]C catalyst toward enhancing the oxygen reduction reaction activity

Developing efficient and cost-effective platinum-group metal-free (PGMF) catalysts for the oxygen reduction reaction (ORR) is crucial for energy conversion and storage devices. Among these catalysts, metal-nitrogen-carbon (MNC) materials, particularly cobalt single-atom catalysts (CoSANC), show promise as ORR electrocatalysts. However, their ORR activity is often hindered by strong hydroxyl (OH) adsorption on the Co sites. While the impact of strain engineering on MNC electrocatalysts has been minimally explored, recent studies suggest its potential to enhance catalytic performance and optimize intrinsic activity in traditional bulk catalysts. In this context, we investigate the effect of surface strain on CoSANC for ORR activity and correlate substrate-strain-induced geometric distortions with catalytic activity using experimental and theoretical methods. The findings suggest that the d-band center gap of spin states (Δεd) may be a preferred descriptor for predicting strain-dependent ORR performance in MNC catalysts. Leveraging CoSANC moiety placed on a substrate with an average size of 1.0 μm, we achieve performance comparable to that of commercial Pt/C catalysts when used as a cathode catalyst in zinc-air batteries. This investigation unveils the structure–function relationship of MNC electrocatalysts regarding strain engineering and provides valuable insights for future ORR activity design and enhancement.

Reaction mechanism of metal-free borophene catalyst electrochemical reduction of CO2

The utilization of electricity generated from renewable energy sources for carbon dioxide reduction reaction (CO2RR) to produce high-value chemical resources is of significant importance for reducing CO2 emissions and for energy storage. However, the search for environmentally friendly and efficient metal-free catalysts to facilitate CO2 conversion continues to present numerous challenges. This study employs density functional theory (DFT) calculation to explore the potential of two-dimensional metal-free borophene catalysts in the activation and conversion of CO2. Through molecular dynamics simulations, energy band and density of states analysis, the stability and electronic properties of metal-free borophene were thoroughly examined. The calculations demonstrated that two specific sites on electron-deficient zigzag borophene possess strong adsorption capabilities for CO2, enabling effective activation of CO2. Further investigation revealed that the reduction of CO2 at site 1 on zigzag borophene efficiently produces CO, HCOOH, CH3OH, and CH4, with the potential determining steps (PDS) requiring overpotentials of 0.11 V, 0.20 V, 0.38 V, and 0.52 V, respectively. In summary, this research provides theoretical foundation for the use of metal-free borophene as an efficient catalyst for CO2RR.

Rational Construction of a 3D Self-Supported Electrode Based on ZIF-67 and Amorphous NiCoP for an Enhanced Oxygen Evolution Reaction.

The development of efficient and Earth-abundant electrocatalysts for the oxygen evolution reaction (OER) is an urgent requirement in the field of electrochemical water splitting. The electrocatalytic performance of the OER can be greatly enhanced by the synergistic combination of zeolite imidazolate frameworks (ZIFs) and transition-metal phosphides, both of which individually exhibit promising capabilities in this regard. In this study, a novel amorphous NiCoP deposited on ZIF-67 sheets supported on Ni foam (labeled as NiCoP/ZIF-67/NF) as an OER electrocatalytic material was successfully synthesized using a simple, secure, and time-efficient two-step strategy. The experimental results demonstrate that NiCoP/ZIF-67/NF possesses a large active surface area with abundant active sites. Also, the synergistic effect and interaction between NiCoP and ZIF-67, as well as between Ni and Co within NiCoP, effectively enhance its electrochemical performance under alkaline conditions. Consequently, NiCoP/ZIF-67/NF exhibits outstanding catalytic activity for OER with an overpotential (η) of 175 mV at a current density of 10 mA cm-2 and a long-term stability over 40 h at 20 mA cm-2 in a 1.0 M KOH electrolyte. The corresponding analyses suggest that the real active sites responsible for the OER are identified as NiOOH and CoOOH species within the structure of NiCoP/ZIF-67/NF. Additionally, the catalytic function and stability of ZIF-67 toward the OER under alkaline conditions were also briefly discussed. This work provides a novel catalytic material for the OER along with a facile strategy to fabricate superior, efficient, and noble metal-free catalysts suitable for energy-related applications.

Effective degradation of tetracycline under visible light by microwave-assisted reflux synthesis of ZnO/MoS2/rGO ternary nanocomposites

ZnO@MoS2 and conducting rGO based ternary nanocomposites were synthesized by a bottom-up microwave-assisted reflux method and effectively investigated for the photocatalytic degradation of tetracycline hydrochloride (TCH) antibiotic. The XRD, EDAX and XPS results corroborates the formation of nanostructure composite with high phase purity. The ZnO nanorods are well grafted on the curled configuration of layered MoS2 and thin surfaced rGO sheets as visualised from HR-TEM analysis. Upon addition of rGO, there is a significant decrease in the bandgap and improved visible light response in the ternary nanocomposites is elucidated by UV–visible Diffuse Reflectance Spectroscopy (UV-DRS) analysis. The suppression in photo-induced electron/hole pair recombination and allowing easy charge transport of ZnMG-50 were evidenced from photoluminescence (PL) and photo-electrochemical impedance (photo-EIS) spectroscopy. From BET and BJH analysis, the enhancement in surface area and pore volume by loading of rGO (SBET = 264.794 m2/g and 0.548 cm3/g). The optimized ZnMG-50 nano-photocatalyst possess a superior photocatalytic performance with higher removal efficiency of 92.18 % was achieved at pH level 10, catalyst dosage 40 mg and TCH concentration 20 ppm within 180 min under illumination. The degradation process compiles a pseudo-first order reaction with a kinetic rate constant of 0.01365 min−1. The nonstop generation of hydroxyl (˙OH) and superoxide (O2˙-) reactive species were beneficial for free electrons in the active participation, which remains as a core factor in the degradation process. The detailed study on ZnMG-50 nanocomposite substantiated to be an efficient noble metal-free synthetic catalyst for enhanced photocatalytic degradation of antibiotics.

3D-interconnected N-doped porous carbon with hierarchical pore structure as a high-efficiency catalyst for H2S oxidation at room temperature

Nitrogen-doped porous carbons (NPCs) have been regarded as an efficient metal-free catalyst for H2S oxidation. However, critical factors affecting their desulfurization ability are still unclear, making it difficult to accurately adjust their desulfurization performance to meet industrial requirements. Herein, a novel 3D-interconnected NPC with hierarchical pore structure was synthesized by one-step “leavening” strategy using rice husk and (NH4)2C2O4 as a carbon source and foaming agent, respectively, for H2S oxidation at room temperature. Pyrolysis temperature is the major factor for physicochemical properties of NPCs, and breakthrough sulfur capacity of the optimal NPC reaches up to 1036.68 mg/g, which can remain stable during three desulfurization-regeneration cycles. Comparative experiment shows that H2S capacity of NPC is 1.8 and 4.0 times those of PC and NC, respectively, revealing the excellent desulfurization performance of NPC. The structure-effect relationships between H2S and NPC reveal that both textural and chemical properties of NPC, especially specific surface area, structural defect, and pyrrolic N, play dominant roles in H2S removal. It is very necessary to balance the relationship between textural performances and pyrrolic N to synthesize optimal NPC catalyst. This work provides a valuable reference for rational design of high-efficiency carbon-based catalysts for persistent desulfurization at room temperature.

Deprotonated 2-thiolimidazole serves as a metal-free electrocatalyst for selective acetylene hydrogenation.

Metal-free catalysts offer a desirable alternative to traditional metal-based electrocatalysts. However, metal-free catalysts, featuring defined active sites, rarely show activities as promising as metal-based materials. Here we report 2-thiolimidazole as an efficient metal-free catalyst for selective electrocatalytic hydrogenation of acetylene into ethylene. Under alkaline conditions, the sulfhydryl and imino groups of 2-thiolimidazole are spontaneously deprotonated into dianions. Deprotonation thus enriches the negative charges of pyridinic N sites in 2-thiolimidazole to enhance the adsorption of electrophilic acetylene through the σ-configuration. Ethylene partial current densities show a volcano relationship with the negative charges of the pyridinic N sites in various imidazole derivatives. Consequently, the deprotonated 2-thiolimidazole exhibits an ethylene partial current density and faradaic efficiency competitive with metal-based catalysts like Cu and Pd. This work highlights the tunability and promising potential of metal-free molecules in electrocatalysis.

OH-Functionalized N-Doped Graphene Quantum Dots as an Efficient Metal-Free Catalysts for Oxygen Reduction Reaction in PEMFCs

OH-Functionalized N-Doped Graphene Quantum Dots as an Efficient Metal-Free Catalysts for Oxygen Reduction Reaction in PEMFCs

Design and Synthesis of N-Doped Carbons as Efficient Metal-Free Catalysts in the Hydrogenation of 1-Chloro-4-Nitrobenzene.

Metal-free catalysts based on nitrogen-doped porous carbons were designed and synthesized from mixtures of melamine as nitrogen and carbon sources and calcium citrate as carbon source and porogen system. Considering the physicochemical and textural properties of the prepared carbons, a melamine/citrate ratio of 2:1 was selected to study the effect of the pyrolysis temperature. It was observed that a minimum pyrolysis temperature of 750 °C is required to obtain a carbonaceous structure. However, although there is a decrease in the nitrogen amount at higher pyrolysis temperatures, a gradual development of the porosity is produced from 750 °C to 850 °C. Above that temperature, a deterioration of the carbon porous structure is produced. All the prepared carbon materials, with no need for a further activation treatment, were active in the hydrogenation reaction of 1-chloro-4-nitrobenzene. A full degree of conversion was reached with the most active catalysts obtained from 2:1 melamine/citrate mixtures pyrolyzed at 850 °C and 900 °C, which exhibited a suitable compromise between the N-doping level and developed mesoporosity that facilitates the access of the reactants to the catalytic sites. What is more, all the materials showed 100% selectivity for the hydrogenation of the nitro group to form the corresponding chloro-aniline.

In-Plane Topological-Defect-Enriched Graphene as an Efficient Metal-Free Catalyst for pH-Universal H2O2 Electrosynthesis.

Developing efficient metal-free catalysts to directly synthesize hydrogen peroxide (H2O2) through a 2-electron (2e) oxygen reduction reaction (ORR) is crucial for substituting the traditional energy-intensive anthraquinone process. Here, in-plane topological defects enriched graphene with pentagon-S and pyrrolic-N coordination (SNC) is synthesized via the process of hydrothermal and nitridation. In SNC, pentagon-S and pyrrolic-N originating from thiourea precursor are covalently grafted onto the basal plane of the graphene framework, building unsymmetrical dumbbell-like S─C─N motifs, which effectively modulates atomic and electronic structures of graphene. The SNC catalyst delivers ultrahigh H2O2 productivity of 8.1, 7.3, and 3.9mol gcatalyst -1h-1 in alkaline, neutral, and acidic electrolytes, respectively, together with long-term operational stability in pH-universal electrolytes, outperforming most reported carbon catalysts. Theoretical calculations further unveil that defective S─C─N motifs efficiently optimize the binding strength to OOH* intermediate and substantially diminish the kinetic barrier for reducing O2 to H2O2, thereby promoting the intrinsic activity of 2e-ORR.

TBAB in One-pot Green Approach for the Synthesis of N-Heterocyclic Compounds: A Comprehensive Review

Abstract: Designing innovative one-pot reactions using eco-friendly methodologies has attracted a lot of attention in drug development, organic synthesis, and material sciences due to the impressive art of mitigating the possibility of side reactions, particularly for the synthesis of Ncontaining heterocycles, which are crucial for the manufacturing and development of new drugs. These moieties have demonstrated a diversity of biological applications, such as anti-tumor, antimicrobial, antibiofilm, antioxidant, and anti-inflammatory. Due to the wide range of medicinal applications, several techniques have been reported in the literature for the synthesis of these physiologically important scaffolds, employing different homogeneous and heterogeneous catalysts. One such highly efficient catalyst is tetrabutylammonium bromide (TBAB), which has gained significant attention as an efficient metal-free homogeneous phase-transfer catalyst to facilitate a reaction when the reactants are in different phases. It is also used as a zwitterionic solvent in many organic transformations and as an effective co-catalyst for a variety of coupling reactions. In the current study, we highlighted recent developments in one-pot reactions involving TBAB as a phase-transfer catalyst or zwitterionic solvent for the efficient synthesis of various biologically promising monocyclic and bicyclic N-heterocycle scaffolds.

Interatomic interaction of 2D crumpled V2O5 nanosheets layered with Ni-MOF as a bifunctional electrocatalyst for overall water splitting and supercapacitor applications

Herein, we have synthesized a highly efficient and economical noble metal-free catalyst via a novel combination of V2O5 nanosheets and Ni MOF. The critical points of this study are (i) achieving a 2D layer structured crumpled V2O5 nanosheets without excessive stacking/aggregation using freeze drying method, (ii) decorating Ni-MOF over the crumpled V2O5 nanosheets to attain an excellent homogeneity and (iii) developing a V2O5 based novel and bifunctional electrocatalyst for overall water splitting and supercapacitor applications. Forming a well-interlinked morphological structure accompanies a homogeneous dispersion of Ni MOF over the V2O5 nanosheet. Among the multiple compositions, the NiV4 exhibited superior electrocatalytic oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) performances with an overpotential (η30) of 336 mV and 108 mV, respectively. NiV4 also displayed remarkable stability as confirmed by chronopotentiometry (24 h) and CV (after 5000 cycles). The excellent OER performance is possible due to the interatomic interaction and the heterojunction formation between V2O5 nanosheets and Ni MOF, resulting in the preferential adsorption of ⁎OOH reaction intermediates to Ni active sites. During HER, the interfacial interaction between V2O5 nanosheets and Ni MOF allowed the OH− to adsorb on the V5+ center. Furthermore, the Ni active sites simultaneously accelerated the Volmer step by promoting the H adsorption. The uniform mass transfer routes aid in fast charge transfer, resulting in excellent OER and HER performances. Interestingly, in the 2-electrode system, the NiV4 exhibited an overpotential of 1.81 V at 10 mA cm−2 and excellent durability over 15 h. For supercapacitor applications, the NiV4 exhibits efficient specific capacitance (546 Fg−1 at 1Ag−1). Furthermore, the NiV4 electrode provides significant long-term stability during the supercapacitor application, with the stability being consistent after 10,000 cycles. The NiV4 offers excellent water splitting and supercapacitor performance due to its multifunctional properties and remarkable structural integrity.

Thermoelectrically polarized amorphous silica promotes sustainable carbon dioxide conversion into valuable chemical products

Electrically polarized amorphous silica (aSiO2) is demonstrated to be an efficient and viable metal-free heterogeneous catalyst for the conversion of CO2 into valuable chemical products.

A recyclable Cu@C2N nano-catalyst applied in the transformation of alkynes: pH switchable access to ketones and 1,3-diynes

We synthesized a reusable heterogeneous Cu@C2N catalyst for pH switchable conversion of alkynes to ketones and 1,3-diynes with 92% and 95% yield. The catalyst has a broad substrate scope, and the reaction conditions are environmentally-friendly.

Carbon doped hexagonal boron nitride as an efficient metal-free catalyst for NO capture and reduction.

The electrochemical NO reduction reaction (NORR) towards NH3 is considered a promising strategy to cope with both NO removal and NH3 production. Currently, the research on NORR electrocatalysts mainly focuses on metal-based catalysts, while metal-free catalysts are quite scarce. In this work, we have systematically investigated the properties of pristine and C/O doped h-BN for efficient NO capture and reduction. Our results reveal that the basal plane of pristine h-BN is inert to the adsorption of NO, while doping C or O can significantly enhance the NO capture abilities of h-BN. Then, we highlight that C-doped h-BN exhibits excellent NORR catalytic performance with a relatively low limiting potential of -0.28 V. Further analysis shows that the suitable adsorption strength of NO on the C-doped h-BN surface is the prime reason for its excellent NO reduction activity, which is shown to be due to appropriate electronic interactions between the active site and NO. Last but not least, the catalytic selectivity of h-BN towards the NORR is confirmed by inhibiting the competing hydrogen evolution reaction. Our findings not only provide deeper insight into the essential effect of element doping on the catalytic activities of h-BN, but also propose general design principles for high-performance metal-free NORR electrocatalysts.