Metal-free Catalysts Research Articles

Coupling Carbon Dioxide and Cyclohexane Oxide Using Metal-Free Catalyst with Tunable Selectivity of Product Under Mild Conditions

Coupling Carbon Dioxide and Cyclohexane Oxide Using Metal-Free Catalyst with Tunable Selectivity of Product Under Mild Conditions

Chiral Polar Bifunctional Polyimide Enantiomers for Asymmetric Photo- and Piezo-Catalysis.

Chiral catalysts for asymmetric catalysis represent a crucial research focus in chemistry and materials science. However, a few cases about chiral-dependent photocatalysts primarily focus on plasmonic noble metals. Particularly, developing chiral nano-catalysts that can be driven by mechanical energy remains in the blank stage. Herein, organic polymer-based enantiomers, chiral polar polyimide (PI) microspheric nano-assembly are synthesized as novel bifunctional catalysts for asymmetric photocatalysis and piezocatalysis. The PI catalyst enantiomers present enantioselectivity towards left- and right-circularly polarized light, demonstrating chiral-dependent H2O2 photoproduction. Interestingly, enantioselectivity of the catalyst reverses under irradiation of different bands, presenting tunability in the interaction between chiral catalysts and circularly polarized light. For the first time, enantioselective piezocatalytic behavior is demonstrated by the chiral polar PI catalysts. They show remarkable chiral preference for asymmetric Diels-Alder reaction and enantioselective conversion of tyrosine substrates under ultrasonic vibration. The findings provide a new perspective into exploring metal-free chiral catalysts and their asymmetric catalysis applications across multiple energy forms.

Efficient paddle-wheel copper cluster-based metal-organic framework for catalytic conversion of CO2 to oxazolidinones under mild conditions

Efficient utilization of CO2 and its conversion into high-value-added products contribute to mitigating environmental issues such as the greenhouse effect. Among these methods, the carboxylation cyclization of CO2 with propargylic amine represents a green and atom-economical approach. Developing cost-effective catalyst that can promote this reaction under mild condition is desirable but challenging. Herein, a unique two-dimensional (2D) metal–organic framework (MOF) {[Cu(QCA)2]∙0.5DMF∙0.5H2O}n (1) (QCA =6-quinolinecarboxylic acid, DMF = N,N-dimethylformamide) have been synthesized and thoroughly characterized. Compound 1 was constructed from paddle-wheel dinuclear copper clusters [Cu2(COO)4] and carboxylate ligands, presenting a two-dimensional framework with new topology. Stability tests indicate that compound 1 undergoes reversible structural changes in different solvents and exhibits good thermal stability. 1 as heterogeneous catalyst enabled the transformation of CO2 and propargylic amine into oxazolidinones under mild conditions with broad substrate generality. In addition, 1 could maintain its catalytic performance with five continuous reactions. This work presents an infrequent example of a 2D noble metal free MOF-based catalyst that shows high catalytic efficiency under mild conditions.

Improvement of Photocatalytic CO2 Reduction with Conjugated Organic Polymers by Rational Modulation of Donor, Acceptor and Bonding Method.

The use of metal-free catalysts to convert CO2 into valuable chemicals is very challenging. Here, we synthesized a conjugated organic polymer (TpTf-1) featuring 2,4,6-Triphenyl-1,3,5-Triazine as the acceptor unit, triphenylamine as the donor unit, and vinylidene bond as the linkage. The local structure of donor-acceptor (D-A) forms an intramolecular electric field that can promote the separation of photogenerated electrons and charges, meanwhile, the vinylidene bond can further change the charge distribution to promote exciton dissociation. Without the use of photosensitizers, the TpTf-1 exhibits outstanding selectivity of CO of up to 91.96 %, with a production rate of 45.2 μmol g-1 h-1 at visible light, which is 3.4-fold than TaTf-1 with the same D-A structure but linking in imine bond and is 2.8-fold than TpTf-2 linking in vinylidene bond but with a different donor unit. Moreover, TpTf-1 has a CO production rate of up to 117.3 μmol g-1 h-1 under full wavelength light irradiation.

Heteroatoms doping for modulation of sp3-hybridized carbon sites for highly efficient bio-electroreduction of oxygen in microbial fuel cells

Due to the fact that single chamber microbial fuel cells (SC-MFCs) generally require efficient, stable, and inexpensive cathode catalysts to promote bioelectricity generation performance, metal-free catalysts have attracted increasing attention in SC-MFCs. However, enhancing the electrocatalytic activity of the oxygen reduction reaction (ORR) using metal-free catalysts remains a challenge. This study introduces a metal-free porous catalyst by synchronously doping phosphorus (P) and nitrogen (N) atoms into the biomass-derived carbon skeleton (AB-N-P). The AB-N-P catalyst, displaying half-wave potentials (E1/2) of 0.89 (alkaline) and 0.832 V (neutral), exhibits superior ORR performances compared to most metal-free catalysts and is comparable to some non-precious metal catalysts. Remarkably, it (E1/2: 0.890 to 0.880 V) matches or even exceeds the stability of commercial Pt/C catalyst (E1/2: 0.864 to 0.849 V) after 3000 cyclic voltammetry cycles. Density functional theory (DFT) calculations demonstrate that P and N co-doping synergistically increases the sp3-hybridized carbon content and redistributes charge density, thereby enhancing the catalytic properties and altering the electronic properties of the active sites. In practical applications in SC-MFCs, the AB-N-P electrocatalyst shows exceptional performance, achieving a higher power density (896.4 mW m−2) than that of commercial Pt/C (538.2 mW m−2). This study offers insightful revelations into the modulation of carbon active-sites by doping heteroatoms to carbon skeleton as metal-free catalyst in bioenergy-generation systems.

Room temperature oxygenated groups addition in carbon materials via ozone oxidation for boosting electrochemical H2O2 production

The crucial yet delicate 2e− oxygen reduction reaction (ORR) for producing the green chemical H2O2 relies on the uniform coordination environment of the active sites, such as oxygenated groups in metal-free carbon material catalysts. However, conventional harsh carbon material synthesis methods inevitably introduce structural defects and alter morphology, hindering the precise control of active site formation. Herein, we developed the ozone oxidation method under controlled reaction conditions to precisely modify carbon materials at room temperature. Through controlling the ozonation of reaction time, concentration, temperature, and relative humidity, we find the mild method allows us to precisely add active carboxyl group (–COOH) without forming structural defects. Electrochemical tests reveal that the optimal catalyst with the highest –COOH content exhibits the most outstanding mass activity of 164 A/g at 0.65 V and the highest H2O2 selectivity of 91 %. The density functional theory calculations demonstrate that the carbon sites directly connected to –COOH possess the optimized binding strength of *OOH intermediate to favor the two-electron oxygen reduction process. This work offers a novel approach to precisely and gently control carbon surface groups while preserving the structural morphology through ozone gas treatment, which can be readily applied to other material designs.

B-containing ionic liquid modified SBA-15 for CO2-epoxide coupling reaction metal-free catalysis

A novel external-skeleton B-containing ionic liquid modified SBA-15 catalyst BBN-Imi-SBA-15-I (BBN denotes borabicyclo[3.3.1]nonane, Imi represents imidazolium ionic liquid) was successfully constructed by a post-modification method for efficiently catalyzing CO2-epoxide coupling reaction under both metal- and solvent-free conditions. 5BBN-Imi-SBA-15-I (5 refers to the molar ratio of Si to B), thanks to its synergistic effects of Lewis acid, weak base sites from tertiary amine and quaternary ammonium, hydrogen bond group and nucleophilic group, displayed good catalytic activity with 97 % product yield and 99 % selectivity at 100 °C, 2 MPa in the absence of cocatalyst. The obtained catalyst demonstrated good recyclability during six consecutive catalytic runs, also presented generality for various mono-substitute epoxides. Through in-situ NH3 diffuse reflectance infrared Fourier transform spectroscopy (NH3-DRIFTS) characterization, the Lewis acidity of organo-boron was verified. Besides, kinetics research also proved the positive effect of multiple active components on efficient catalysis under milder conditions over SiO2-based metal-free catalysts.

High-valence Co deposition based on selfcatalysis of lattice Mn doping for robust acid water oxidation

Non-precious metal cobalt-based oxide inevitably dissolves for acid oxygen evolution reaction (OER). Designing an efficient deposition channel for leaching cobalt species is a promising approach. The dissolution-deposition equilibrium of Co is achieved by doping Mn in the lattice of LaCo1−xMnxO3, prolonging the lifespan in acidic conditions by 14 times. The lattice doping of Mn produces a strain that enhances the adsorption capacity of OH−. The self-catalysis of Mn causes the leaching Co to be deposited in the form of CoO2, which ensures that the long-term stability of LaCo1−xMnxO3 is 70 h instead of 5 h for LaCoO3. Mn doping enhances the deprotonation of *OOH→O2 in acidic environments. Notably, the overpotential of optimized LaCo1−xMnxO3 is 345 mV at 10 mA cm−2 for acidic OER. This work presents a promising method for developing noble metal-free catalysts that enhance the acidic OER activity and stability.

Synthesis of oxygen-rich carbon materials as metal-free catalysts for oxygen reduction reaction in seawater electrolyte

Synthesis of oxygen-rich carbon materials as metal-free catalysts for oxygen reduction reaction in seawater electrolyte

Enhanced Remediation of Textile Dyes via Nonmetal-Modified Layered Graphitic Carbon Nitride: Influence of Various Oxygen Precursors

Layered two-dimensional (2D) graphitic carbon nitride (gCN)) doped with nonmetals has been extensively utilized as a photo-electrocatalyst. Herein, gCN doped with Oxygen was synthesized through a thermal polymerization process. The effect of various oxygen forerunners, namely citric acid (CA), oxalic acid (OX), and lactic acid (LA) on the photocatalytic ability of the gCN was analyzed. The proposed O-doped gCN samples basic characteristics were characterized by different analytical analyses. Indeed, the O-gCN has formed a sheet-like nature with a nanometre range, so often called a nanosheet. Superior photocatalytic performance was measured when the gCN was prepared by the CA as the O-precursor; 95% malachite green (MG) removal was attained within a short treatment time of 40min by adding a 20mg photocatalyst. The influences of different parameters of catalyst concentration, different precursors, and initial pH of MG degradation were also studied. The generation of active radicals played a major part in the degradation of the MG dye solution. These findings offer fundamental insight into utilizing the O-gCN for the remediation of textile effluents in water resources. The preparation of enormous metal-free catalysts via non-metal doping toward the environmental clean-up.

CoFe2O4 nanoparticle embedded carbon nanofibers: A promising non-noble metal catalyst for oxygen evolution reaction

There is a strong demand for noble metal-free durable catalysts to facilitate the advancement of clean, sustainable energy technologies and to replace energy equipment reliant on fossil fuels. In this study, metal-organic framework (MOF)-derived CoFe2O4 (CFO) nanoparticle-embedded electrospun carbon nanofibers (CNFs) were synthesized. Nanofibers were calcined at three different temperatures to obtain optimum electrocatalytic performance in oxygen evolution reaction (OER). Nanofibers annealed at 800 °C (CFO@CNFs 800) displayed a reduced overpotential of 300 mV while maintaining a steady current density of 10 mA cm−2. CFO@CNFs 800 demonstrated Tafel slope 42 mV dec−1 with excellent long-term stability up to 48 h. The synergistic effect of the redox activity of CFO coupled with the high surface area and conductivity of carbon nanofibers is responsible for enhanced OER performance.

Nitrogen Defective Engineering of a Metal-Free Carbon Catalyst for Ammonia Electrosynthesis from Nitrate

Nitrogen Defective Engineering of a Metal-Free Carbon Catalyst for Ammonia Electrosynthesis from Nitrate

C3N4/Se-CNTs as Advanced Metal-Free Catalysts for the Photoassisted Electrocatalytic Oxygen Evolution Reaction.

Photoassisted electrocatalysis is a frontier direction of electrocatalysis for promoting energy conversion. In this work, a metal-free C3N4/Se-CNTs is reported as a novel catalyst for photoassisted electrocatalytic oxygen evolution reaction (OER). C3N4 has an appropriate bandgap, high specific surface area, and long-term stability. CNTs can modulate the electronic environment of C3N4 by strong π-π interaction and greatly enhance the separation efficiency of photogenerated carriers. The distributed Se nanoparticles in CNTs can further increase the charge transfer ability. As a metal-free catalyst, the C3N4/Se-CNTs exhibits an overpotential of 231 mV at a current density of 10 mA cm-2 and a small Tafel slope of 52 mV dec-1 under illumination, which ranks among the best catalysts for photoassisted OER performance, surpassing most noble and transition metal-based catalysts. The result demonstrates the great potential of C3N4-based catalysts in the photoassisted OER process and provides a new perspective to explore the excellent metal-free OER catalysts.

Polymerizable Ionic Liquid-Derived N, S co-Doped sp3/sp2 Carbon as Electrocatalyst for H2O2 Generation.

The H2O2 generation via the green electrochemical process is of high interest. For the H2O2 electrochemical generation, the oxygen reduction reaction (ORR) is important. Unfortunately, the ORR is kinetically sluggish and catalysts are needed. However, noble metal ORR catalysts are pricy and scarcely applicable in applications. Therefore, non-precious metal catalysts are desired. Heteroatom-doped carbons show promise as metal-free ORR catalysts. The ORR catalytic activity will be enhanced by the carbon's sp2 and/or sp3 engineering. For N, S co-Cdoped and sp2/sp3 modulated carbon, a polymerizable ionic liquid of hydrolyzed vinyl imidazolium was studied. The carbon is studied as a metal-free catalyst for the ORR via the 2e- process. It is possible to get an onset potential of 0.88 V vs. RHE with approximately 50 % selectivity for the H2O2. The current study offers a simple technique for synthesizing heteroatom-doped sp2/sp3 designed carbon as catalysts for the electroreduction of O2 to produce H2O2, and a new way of tunning the sp3/sp2 carbon catalytic activity by modulating the ionic liquid.

Recycling Valuable Phenol from Polycarbonate Plastic Waste Via Direct Depolymerization and Csp2-Csp3 Bond Cleavage Under Mild Conditions.

Upcycling plastic waste into commodity chemicals is recognized as an environmentally benign solution and beneficial for the sustained growth of humanity. Nevertheless, transition metal-free catalysts and energy-efficient conditions pose significant challenges due to the robust mechanical properties of plastics. Here, a strategy for selective production of phenol by upcycling polycarbonate waste via direct depolymerization and Csp2-Csp3 bond cleavage in an aqueous medium under mild conditions is reported. The commercial zeolites efficiently catalyze the depolymerization, Csp2-Csp3 bond hydrolysis, and direct Csp2-Csp3 bond scission at Cα of PC. Among all evaluated zeolites, HY (Si/Al=15) showed excellent catalytic performance, attributed to the ~75 % yield of phenol and ~15 % of acetone. The approach also employs different municipal waste PC for upcycling. Studies reveal that HY (15) exhibits high catalytic efficiency and phenol yield due to its optimum acid sites and textual properties. A scale-up experiment demonstrated that 3.1 g of phenol was produced from 5.0 g of PC, and the mass balance was 90 %. A combination of control experiments, NMR analysis, and DFT studies proposed the reaction pathway. Our findings present a sustainable avenue for upcycling PC waste and offer a new way to produce phenol, contributing to the advancement of a circular economy.

CaCO3-activited N-doped diatom biochar for the degradation of tetracycline

In this study, a N-doped diatom biochar (DBC) was prepared by one-step pyrolysis, where CaCO3 formed by marine diatom-mediated calcification was employed as an activator. Due to the activation effect of CaCO3, the specific surface area of the obtained DBC increased by more than 10 times, and the nitrogen presented as pyrrolic nitrogen (58.9%), pyridinic nitrogen (29.7%), and graphitic nitrogen (11.4%) in the DBC. In addition, the effects of important parameters and co-existing ions on the catalytic decomposition of tetracycline (TC) by DBC were investigated by using TC as a typical pollutant and PDS as an oxidant. The DBC/PDS system exhibited high activity over a broad pH range. Through radical scavenging experiments, electron spin resonance, and electrochemical results analysis, it was found that the degradation of TC in the system included both radical and nonradical pathways, and the most dominant reactive species was 1O2. Furthermore, the surficial reactive complexes formed by PDS on the catalysts also played an important role in attacking the adsorbed TC molecules. This study proposes an eco-friendly and economical technique to construct a clean advanced oxidation process capable of treating TC wastewater by utilizing the native biomass of diatom as a metal-free and efficient biochar catalyst while simultaneously reducing the use of chemical reagents.

Promising metal-free green heterogeneous catalyst for quinoline synthesis using Brønsted acid functionalized g-C3N4

Rationally designing distinct acidic and basic sites can greatly enhance performance and deepen our understanding of reaction mechanisms. In our current investigation, we studied the utilization of Brønsted acid sites within layered graphitic carbon nitride (g-C3N4) for the first time to enhance the rate of the Friedländer synthesis. The structural and surface analyses confirm the effective integration of -COOH and -SO3H groups into the g-C3N4 lattice. The surface-functionalized g-C3N4-CO-(CH2)3-SO3H exhibits a remarkable acceleration in quinoline formation, surpassing previously mentioned catalysts, and demonstrating notable recyclability under optimized mild reaction conditions. The heightened reaction rate observed over g-C3N4-CO-(CH2)3-SO3H is attributed to its elevated surface acidity. By probing the Friedländer reaction mechanism through surface characterization, examination of reaction intermediates, and investigation of substrate scope, we elucidate the pivotal role of Brønsted acid sites. This study constitutes a comprehensive exploration of metal-free heterogeneous catalysts for the Friedländer reaction, offering a unique contribution to the field.

Covalent Organic Framework-Derived B/N Co-Doped Carbon FLPs Metal-Free Catalysts for the Selective Hydrogenation of α,β-Unsaturated Aldehydes to Unsaturated Alcohols

Covalent Organic Framework-Derived B/N Co-Doped Carbon FLPs Metal-Free Catalysts for the Selective Hydrogenation of α,β-Unsaturated Aldehydes to Unsaturated Alcohols

Mechanochemical Synthesis ofβ-Sulfenylated Ketones and Esters.

For the first time, ball milling has been employed in the solvent-free synthesis of sulfur-functionalized materials from thiols and α,β-unsaturated ketones and esters, using potassium carbonate as a transition metal-free catalyst. This environmentally friendly protocol makes use of easily accessible reagents to prepare β-sulfenylated carbonyl compounds with yields exceeding 91% under ambient air and solvent-free conditions. Additionally, this innovative synthetic strategy enables the modification of chalcones, compounds with significant medicinal and synthetic potential. The reactions are efficient and easily scalable to gram quantities, offering substantial benefits for practical applications.

Every reaction Detail Matters: An in silico driven Step-by-Step Guide to understand the B2O3-Catalyzed CO2 to cyclic carbonates conversion

The catalytic conversion of carbon dioxide (CO2) to cyclic organic carbonates (COCs) via cycloaddition with epoxides offers a dual benefit of reducing CO2 emissions while producing valuable chemical products. In this detailed in silico study, we employ density functional theory (DFT) to meticulously investigate the mechanisms underlying the B2O3/n-NBu4Br-catalyzed cycloaddition of CO2 and epoxides, following a step-by-step approach according to the reaction details. We provide a comprehensive comparison of the non-catalyzed, n-NBu4Br alone, and B2O3/n-NBu4Br-catalyzed pathways, emphasizing two distinct active sites within the B2O3 framework: Site 1 (six-membered boroxol ring) and Site 2 (open chain configuration). Our computational analysis highlights that the Site 1-catalyzed reaction pathway is more favorable, featuring a lower overall energy barrier of 26.8 kcal/mol, compared to 32.5 kcal/mol for the Site 2-catalyzed pathway. Detailed intrinsic bond orbital (IBO), natural adaptive orbital (NAdO) and distortion-interaction analysis (DIA) reveal significant differences in bonding properties and energy interactions, elucidating why Site 1 exhibits superior catalytic activity over Site 2. These findings are corroborated by experimental observations, which indicate that ball milling B2O3 increases defect sites, thereby enhancing exposure of active sites Site 1 and improving catalytic performance. This study provides an in-depth understanding of how the intrinsic properties of boron active sites influence the catalytic efficiency of B2O3, offering valuable insights for the design and optimization of metal-free catalysts for CO2 conversion.