Pyridine Nitrogen Research Articles

A 2D Acridine-Based Covalent Organic Framework for Selective Detection and Efficient Extraction of Gold from Complex Aqueous-Based Matrices.

Developing candidate materials which possess the ability of both selective detection and efficient capture of precious metal gold is highly desirable for environment and economy. However, most of reported materials only focus on single function, which seriously restricts their practical application as probes or adsorbents. Herein, a two dimensional (2D) acridine-based covalent organic framework (TpDa-COF) is prepared via the linkage of imine bonds for gold detection and adsorption. The synthesized COF can achieve both fluorescence and colorimetric dual sensing for Au3+ in a low concentration range (0.1-1.5 ppm) with the limit of detection (LOD) of 0.036 ppm. Impressively, the selectivity of TpDa-COF for the detection of Au3+ is admirable (Fe3+, Fe2+ and Cu2+ for negligible influence on its fluorescence). In addition, TpDa-COF exhibits ultrahigh adsorption capacity of 982.5 mg ⋅ g-1 for gold at pH=4, which is attributed the synergistic effect of both selective coordination and reductive process of Au(III) to Au(0). Meanwhile, both positive entropy change (ΔS=76.07 J ⋅ mol-1 ⋅ K-1) and high distribution coefficient (Kd=12484.8 mL ⋅ g-1) confirm the good affinity between TpDa-COF framework and gold. This work gives us a new insight to prepare COF with pyridine nitrogen sites for gold detection and adsorption.

Heterokaryotic transition-metal dimers embedded monolayer g-C3N3 as promising anchoring and electrocatalytic materials for lithium-sulfur battery: First-principles calculations

g-C3N3 not only has high content of pyridine nitrogen, but also has a special two-dimensional porous structure, which is an ideal diatomic catalytic host materials. In this work, homonuclear and heteronuclear dual-atom catalysts (DACs, TM-TM@g-C3N3, TM = Mn, Fe, Co, Ni) were constructed using single-layer g-C3N3 as the carrier material of DACs, and their potential as sulfur-hosting materials and electrocatalytic materials for lithium-sulfur batteries was explored through first principles comprehensively. The results show that the coupling between the two metal atoms in heteronuclear DACs can regulate the spin state of each other's d-electrons, so that the anchoring and catalytic effects of heteronuclear DACs on polysulfide are more excellent than that of homonuclear DACs. Co-Mn@g-C3N3, when utilized as the cathode material in lithium-sulfur batteries, offers exceptional properties due to the hybridization between Mn2+ high-spin state d electron and Co2+ half-filled dz2 orbital. This unique interaction not only enables the polysulfide to exhibit the lowest Gibbs free energy during conversion, but also results in the lowest reaction energy barrier of 0.26 eV for the conversion of Li2S2 to Li2S. Furthermore, it is found that when 3d transition metal atoms act as heteronuclear DACs, the coupling between metal ions with high-spin states at the active site and metal ions with empty orbitals or half-full d-electrons has the most significant catalytic effect on polysulfides.

Mechanisms of efficient indoor formaldehyde removal via electro-Fenton: Synergy in ·OH generation and utilization through a modified carbon cathode

Indoor formaldehyde poses a significant carcinogenic risk to human health, making its removal imperative. Electro-Fenton degradation has emerged as a promising technology for addressing this concern. In the electro-Fenton system, ·OH is identified as the primary active species responsible for formaldehyde removal. Hence, its generation and utilization are pivotal for the system's effectiveness and economy. Experimental and quantum chemical methods were employed to investigate the effects and mechanisms of nitrogen doping on various aspects influencing ·OH generation and utilization. Results indicate that nitrogen doping synergistically enhances the generation and utilization of ·OH, leading to an improved formaldehyde removal efficiency in nitrogen-doped cathodic systems. The dominant nitrogen type influencing ·OH generation and utilization varies across different stages. Pyridinic nitrogen facilitates H2O2 adsorption through hydrogen bonding, while pyrrolic and graphitic nitrogen contribute to formaldehyde adsorption and catalyze the conversion of H2O2 to ·OH. Both pyridinic nitrogen and pyrrolic nitrogen boost the degradation of formaldehyde by ·OH. In comparison to the unmodified system, the modified system with NAC-GF/700C as cathode exhibits remarkable improvements. The formaldehyde removal efficiency has increased twofold, and energy consumption reduced by 73.45%. Furthermore, the system demonstrates excellent cyclic stability. These advancements can be attributed to the activation temperature, which leads to the appropriate types and high content of nitrogen elements in NAC-GF/700C. The research represents an important step towards more economical and efficient electro-Fenton technology for indoor formaldehyde removal.

High content pyridine nitrogen-doped carbon nanosheets derived from ZIF-L as anode materials of lithium-ion batteries with excellent capacity and rate performance

The precise control of nitrogen doping types in carbon materials is crucial for optimizing energy storage devices. In this study, we synthesize nitrogen-doped carbon nanosheets (NCS) using ZIF-L as a precursor. Comparatively, the two-dimensional crystal structure of ZIF-L provides several advantages over ZIF-8 as a precursor in terms of nitrogen doping efficiency, achieving a higher doping level (14.56 %) and an increased ratio of pyridinic nitrogen (53.60 %). Consequently, NCS display a greater capacity for pseudocapacitive lithium storage. Furthermore, by adjusting the carbonization temperature, we precisely tailor the graphite-nitrogen doping level of NCS within the range of 16.80–31.22 %. Remarkably, when employed as an anode material in lithium-ion batteries, NCS-800 demonstrates exceptional cycling stability, with a capacity retention of 1078 mAh g−1 after 500 cycles at a current density of 0.5 A g−1, as well as excellent rate capability (735 mAh g−1 at 5 A g−1). This study not only compares the impact of precursor crystal structure modifications on nitrogen doping and lithium storage performance but also introduces a novel synthesis methodology for highly nitrogen-doped carbon materials, offering new avenues for future research in this field.

Dual‐Shelled Hollow Leafy Carbon Support with Atomically Dispersed (N,S)‐Bridged Hydroxy‐Coordinated Asymmetric Fe Sites for Oxygen Reduction

AbstractSingle‐atom catalysts (SACs) are widely studied in various chemical transformations due to their high catalytic activity and atom utilization. However, modulating the catalytic performance of catalysts by adjusting the microenvironment remains a great challenge. In this paper, a novel master‐double guest vulcanization‐assisted strategy is reported for synthesizing Fe single‐atom catalysts on N,S codoped porous hollow leaf carbon (FeSA/N,S‐PHLC) with highly exposed FeN3SOH sites. Fe(mIm) (guest I) is loaded on the surface of ZIF‐L (host) and then trithiocyanuric acid (TCA, guest II) is bonded with Fe(mIm), and the resulting ZIF‐L@Fe(mIm)@TCA precursors can be converted to FeSA/N,S‐PHLC with controllable structures. In addition, XPS analysis yield an increase in pyridine N content in FeSA/N,S‐PHLC compared to FeSA/N‐PHLC. It can be demonstrated by theoretical calculations that the N,S‐coordinated axially hydroxy‐coordinated asymmetric Fe centers synergistically with the abundance of pyridinic nitrogen facilitate the adsorption and desorption of oxygen intermediates, and the 3d orbitals of the Fe active centers can be optimized. The prepared FeSA/N,S‐PHLC catalyst has a half‐wave potential (E1/2) of 0.91 V under alkaline conditions, and E1/2 = 0.75 V under acidic conditions. It shows excellent cycle stability (882 h) and power density (217 mW cm−2) in the assembly of zinc–air battery (ZABs) devices.

Study on pyrolysis behavior of municipal sludge based on TG-FTIR-MS

Sludge pyrolysis, as a new sludge disposal technology, can realize the reduction and resource utilization of municipal sludge. Based on TG-FTIR-MS technology, pyrolysis behaviors such as pyrolysis reaction kinetics, pyrolysis product composition and other pyrolysis behaviors of four common municipal sludges (SD, NJ, CS, TJ) at different pyrolysis rates were investigated in this paper, and the migration and transformation of nitrogen elements in municipal sludge were analyzed. The results showed that the pyrolysis of municipal sludge was mainly divided into three stages: dewatering (below 160 °C), volatile decomposition (160–550 °C), and carbonization stage (550–900 °C). The activation energies of the four sludge pyrolysis stages were 189.75 kJ/mol, 138.13 kJ/mol, 300.76 kJ/mol, and 237.83 kJ/mol, respectively. It was found that the sludge pyrolysis stage followed the stochastic nucleation and subsequent growth mechanism through the study of SD and CS sludge. The pyrolysis gaseous product content was affected by the rate of heating and pyrolysis temperature. Moderate temperatures (400–550 °C) favored complete sludge decomposition. Sludge is more likely to decompose in a narrow temperature range at higher heating rates, and increasing the heating rate accelerates sludge decomposition. The nitrogenous compounds in sludge are mainly pyrrole nitrogen, protein nitrogen, and pyridine nitrogen. During sludge pyrolysis, the nitrogenous compounds decompose and precipitate in the form of heterocyclic nitrogen (pyridine, pyrrole), and release small molecules of nitrogenous compounds (NH3, HCN, HCNO). The experimental results can provide a reference for the disposal of municipal sludge by pyrolysis.

Constructing B─N─P Bonds in Ultrathin Holey g-C3N4 for Regulating the Local Chemical Environment in Photocatalytic CO2 Reduction to CO.

The lack of intrinsic active sites for photocatalytic CO2 reduction reaction (CO2RR) and fast recombination rate of charge carriers are the main obstacles to achieving high photocatalytic activity. In this work, a novel phosphorus and boron binary-doped graphitic carbon nitride, highly porous material that exhibits powerful photocatalytic CO2 reduction activity, specifically toward selective CO generation, is disclosed. The coexistence of Lewis-acidic and Lewis-basic sites plays a key role in tuning the electronic structure, promoting charge distribution, extending light-harvesting ability, and promoting dissociation of excitons into active carriers. Porosity and dual dopants create local chemical environments that activate the pyridinic nitrogen atom between the phosphorus and boron atoms on the exposed surface, enabling it to function as an active site for CO2RR. The P-N-B triad is found to lower the activation barrier for reduction of CO2 by stabilizing the COOH reaction intermediate and altering the rate-determining step. As a result, CO yield increased to 22.45µmolg-1h-1 under visible light irradiation, which is ≈12 times larger than that of pristine graphitic carbon nitride. This study provides insights into the mechanism of charge carrier dynamics and active site determination, contributing to the understanding of the photocatalytic CO2RR mechanism.

Cu/N co-doped biochar activating PMS for selective degrading paracetamol via a non-radical pathway dominated by singlet oxygen and electron transfer

The non-free radical oxidation pathway (PMS-NOPs) of peroxymonosulfate (PMS) holds significant promise for practical wastewater treatment applications, owing to its low oxidation potential, high PMS utilization rate, and robust anti-interference capability in the degradation of pollutants. A novel activator copper nitrogen co-doped porous biochar (Cu-N-BC) with rich defect edges and functional groups was obtained by adding Cu and N to the biochar matrix generated by sodium alginate through pyrolysis in this study. Under the condition of 1 mM PMS, 30 mg/L activator was used to activate PMS and achieve efficient degradation of 10 mg/L paracetamol (PCT) within 15 min, with a high reaction rate constants (kobs) of 0.391 min−1. The activation mechanism of the Cu-N-BC/PMS/PCT system was a non-radical activation pathway with the dominance of singlet oxygen (1O2) and the presence of catalyst-mediated electron transfer. The graphite nitrogen, pyridine nitrogen, and Cu–N coordination introduced by Cu/N co-doping, as well as the carbon skeleton and CO functional group of biochar, were considered active sites that promote the 1O2 generation. The Cu-N-BC/PMS system exhibits strong stability, eco-friendliness, effective mineralization, and interference resistance across diverse pH levels (3–11) and interfering ions, including Cl−, H2PO4−, NO3−, SO42−, and humic acid. Remarkably, it efficiently degrades PCT in tap and lake water, achieving a notable 63.73% TOC mineralization rate, with leached copper ions below 0.02 mg/L. This research introduces a novel method for obtaining metal nitrogen carbon activators and enhances understanding of PMS non-radical activation pathways and active sites.

Improving Zinc-Ion Batteries’ Performance: The Role of Nitrogen Doping in V2O3/C Cathodes

This study presents the synthesis and electrochemical evaluation of nitrogen-doped vanadium oxide (N−V2O3/C) as a cathode material for aqueous zinc-ion batteries (AZIBs), using a hydrothermal method. Compared to undoped V2O3/C, N−V2O3/C exhibits enhanced electrical conductivity, capacity, and electrochemical kinetics, attributed to the incorporation of pyridinic and pyrrolic nitrogen. The initial charge–discharge cycles indicate phase transitions to amorphous vanadium oxides, enhancing conductivity. N−V2O3/C shows a high specific capacity of 168.4 mAh g−1 at 10 A g−1 and remarkable reversibility, highlighted by the transient existence of intermediate species during cycling. Optimal electrochemical performance is achieved with a vanadium-to-nitrogen molar ratio of 2:3, indicating the significant impact of the nitrogen doping concentration on the material’s efficiency. This work underscores the potential of N−V2O3/C as a superior cathode material for AZIBs.

A 2D Acridine‐Based Covalent Organic Framework for Selective Detection and Efficient Extraction of Gold from Complex Aqueous‐Based Matrices

Developing candidate materials which possess the ability of both selective detection and efficient capture of precious metal gold is highly desirable for environment and economy. However, most of reported materials only focus on single function, which seriously restricts their practical application as probes or adsorbents. Herein, a two dimensional (2D) acridine‐based covalent organic framework (TpDa‐COF) is prepared via the linkage of imine bonds for gold detection and adsorption. The synthesized COF can achieve both fluorescence and colorimetric dual sensing for Au3+ in a low concentration range (0.1 – 1.5 ppm) with the limit of detection (LOD) of 0.036 ppm. Impressively, the selectivity of TpDa‐COF for the detection of Au3+ is admirable (Fe3+, Fe2+ and Cu2+ for negligible influence on its fluorescence). In addition, TpDa‐COF exhibits ultrahigh adsorption capacity of 982.5 mg·g‐1 for gold at pH = 4, which is attributed the synergistic effect of both selective coordination and reductive process of Au(III) to Au(0). Meanwhile, both positive entropy change (ΔS = 76.07 J·mol‐1·K‐1) and high distribution coefficient (Kd = 12484.8 mL·g‐1) confirm the good affinity between TpDa‐COF framework and gold. This work gives us a new insight to prepare COF with pyridine nitrogen sites for gold detection and adsorption.

Endowing turbostratically porous carbon with rich edge nitrogen active sites for efficient capacitive removal of phosphate

The mitigation of phosphate in water is a pivotal concern for the prevention of eutrophication and enhancement of water quality. Capacitance deionization (CDI) technique possesses the merits of high removal efficacy, facile operation, and environmental friendliness, rendering it a promising strategy for phosphate elimination. Herein, the nitrogen-rich laminar porous carbon composites (NTPCs) prepared by direct pyrolysis of supermolecular precursor were utilized as phosphate capture electrodes. The resulting NTPC800 features a high nitrogen content turbostratically amorphous carbon framework, which facilitates efficient ion diffusion pathways and electron transfer. The abundant presence of edge nitrogen (pyridine and pyrrole nitrogen) optimizes the electronic structure of the carbon system and provides more active sites, thus leading to the boosted electrochemical activity and dephosphorization efficiency. Consequently, NTPC800 demonstrates a rapid phosphate removal capacity, achieving 73.51 mg g−1 within a mere 10 min at 1.2 V condition, which is nearly 6 times more efficient than that of the commercial activated carbon electrode. Moreover, it exhibited consistent phosphate removal efficiency across various pH ranges, coexisting ion interferences, and cyclic stability assessments. This study provides theoretical support for the utilization of edge nitrogen decorated carbonaceous electrodes to enhance charge transfer and provide additional active sites for efficient capacitive dephosphorization.

Norfloxacin adsorption by urban green waste biochar: characterization, kinetics, and mechanisms.

Biochar, as a potential adsorbent, has been widely employed to remove pollutants from sewage. In this study, a lignin-based biochar (CB-800) was prepared by a simple high-temperature pyrolysis using urban green waste (Cinnamomum camphora leaves) as a feedstock to remove norfloxacin (NOR) from water. Batch adsorption test results indicated that CB-800 had a strong removal capacity for NOR at a wide range of pH values. The maximum adsorption achieved in the study was 50.90 ± 0.64mg/g at 298K. The pseudo-first and second-order kinetic models and the Dubinin-Radushkevich isotherm fitted the experimental data well, indicating that NOR adsorption by CB-800 was a complex process involving both physi-sorption and chemi-sorption. The physical properties of CB-800 were characterized by SEM and BET. The mesoporous structures were formed hierarchically on the surface of CB-800 (with an average pore size of 2.760nm), and the spatial structure of NOR molecules was more easily adsorbed by mesoporous structures. Combined with Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) analysis, it was showed that the main NOR adsorption mechanisms by CB-800 included ion exchange, π-electron coordination, hydrogen bonding, and electrostatic adsorption. Meanwhile, the reduction of C = O and pyridine nitrogen, and the presence of C-F2, also indicated the occurrence of substitution, addition, and redox. This study not only determined the reaction mechanism between biochar and NOR, but also provides guidance to waste managers for the removal of NOR from water by biochar. It is envisaged that the results will broaden the utilization of urban green waste.

New Tin (IV) and Organotin (IV) Complexes with a Hybrid Thiosemicarbazone/Hydrazone Ligand: Synthesis, Crystal Structure, and Antiproliferative Activity.

Nowadays, the search for new chemotherapeutic agents with low toxicity and high selectivity is a major concern. In this paper, we report the synthesis and characterization of a hybrid thiosemicarbazone/hydrazone ligand in its neutral form (L1H2) and as the chloride salt ([L1H3]Cl)-, three diorganotin (IV) complexes, and one complex with Sn (IV). The compounds have been fully characterized by IR, mass spectra, 1H, 13C, and 119Sn NMR, 119Sn CP/MAS NMR, and by single crystal X-ray diffraction. The organotin compounds have the empirical formula [SnR2L1] (R = Me, Bu, and Ph), but in the solid state, they are polymeric species with seven coordination number due to weak coordination of the pyridine nitrogen, whereas in solution, the polymeric structure is lost to afford hexacoordinate monomeric species. Reaction with SnI4 yields complex [Sn (L1)2]·EtOH, with the metal in a distorted dodecahedral arrangement. We have evaluated the antiproliferative activity of the two forms of the ligands and the four coordination compounds against MDA-MB-231, HeLa, PC3, and HepG2 cancer cell lines, and WI-38 normal cell line, and all the compounds present higher activity than cisplatin, used as the standard control. To investigate the mode of action, we have selected the most active complex, containing phenyl substituents, and used the triple negative breast cancer cell line MDA-MB-231. The results show that the complex induces apoptotic cell death promoted by generation of reactive oxygen species and by disruption of mitochondrial membrane potential.

Highly enhanced direct catalytic oxidation of cyclohexane to adipic acid by prussian blue analogues-derived C, N doped CuCo composite catalysts

The oxidation of cyclohexane to produce adipic acid suffered from the inefficient and polluting two-step process. We introduce the CuCo Prussian blue analogues derived in situ C, N doped CuCo composite catalysts in the selective oxidation of cyclohexane. Due to the in-situ doping of C and N elements in the form of active graphite carbon and pyridine nitrogen, the oxygen vacancy content and the ability to activate oxygen are improved. The one-step efficient catalytic oxidation of cyclohexane to adipic acid was realized due to the excellent electron transfer performance between C, N elements and metals

Urea-treatment of CoOx carbon nanofibers to improve the electrochemical performance of supercapacitor using aqueous electrolytes

Supercapacitors (SCs) play a crucial role in flexible electronics, necessitating innovative approaches to enhance surface faradaic reactions and minimize faradaic diffusion while using aqueous electrolytes. Thus, the urea treatment of cobalt oxide (CoOx)-decorated carbon nanofibers (CNFs) is proposed in this study to decrease the contribution of faradaic diffusion-limited current. Flexible CoOx/CNF electrodes were obtained by annealing ZIF-67-grafted polyacrylonitrile (PAN) fibers via a wet chemical method. The urea treatment of CoOx/CNFs increased the content of sp2-hybridized carbon and pyridinic nitrogen, as confirmed by X-ray photoelectron spectroscopy, effectively enhancing conductivity and pseudocapacitive charge storage capability via nitrogen doping. Notably, urea-treated CoOx/CNF electrode samples exhibited a capacitance of 750 mF cm-2 at a scan rate of 10 mV s-1, while retaining more than 81% capacitance at a higher scan rate of 100 mV s-1. The cyclic voltammetry curves during variable bending angle testing (0°, 45°, and 90°) exhibited negligible changes, indicating the excellent flexibility of the SCs. The CoOx/CNFs and urea-treated CoOx/CNFs exhibited 80% and 91% capacitance retentions, respectively, after 10,000 galvanostatic charge and discharge cycles. Furthermore, the attained energy densities of 76 and 61 μWh cm-2 at the respective power densities of 2 and 20 mW cm-2 indicated the excellent electrochemical performance of the optimal urea-treated CoOx/CNF electrode.

Mechanism insights into H2O2in situ generation and activation for ciprofloxacin degradation by electro-peroxidation using the ACF@RuO2/Ti cathode

Electrocatalytic H2O2 production via the two-electron oxygen reduction reaction on the cathode surface plays a crucial role in the electro-peroxidation (EO-H2O2). In this work, the H2O2 generation potential of the EO-H2O2 process using an activated carbon fiber attached RuO2/Ti cathode (ACF@RuO2/Ti) was evaluated by simulation experiments with a high-precision syringe pump. Results shown that the actual average H2O2 accumulation rate reached up to 4.92 mg h−1 cm−2, while more than 95 % of the electrogenerated H2O2 was decomposed quickly. Electron paramagnetic resonance and quenching tests confirmed that the primary oxidant •OH was produced from H2O2 activation by ACF, RuO2 catalyst and their synergistic effect, while RuO2 played dominant role. The production of •OH in the EO-H2O2 process was also confirmed by the degradation and mineralization of antibiotic ciprofloxacin. The characterization results indicated that heterogeneous catalysis of cathode was due to both the pyridinic nitrogen and oxygen-containing groups of ACF, along with RuO2 catalyst on the RuO2/Ti surface. This study provides new insights into the mechanisms of the in situ H2O2 generation and activation in the EO-H2O2 process.

Polyacrylonitrile‐based porous polymer spheres and their conversion to N‐doped carbon materials for adsorption and electrocatalysis

AbstractBecause of their tunable porosity and specific surface area, porous materials are of high interest for the purification of wastewater by adsorption as well as in electrocatalysis, where, in particular, developing metal‐free carbon‐based catalysts for the oxygen reduction reaction (ORR) is researched. The carbon spheres presented here can meet these two requirements simultaneously. Porous polyacrylonitrile (PAN) spheres were firstly prepared by droplet shaping cum nonsolvent induced phase separation. Then, they were converted to nitrogen‐doped carbon spheres by two‐step carbonization via preoxidation and pyrolysis. During the pyrolysis step, carbon dioxide was used to reopen the pores of the materials that had been blocked after the preoxidation step. By this way, specific surface area values of carbon spheres of more than 1000 m2/g could be obtained. Best performing carbon materials (C#3) showed high adsorption capacity (e.g., 296 mg/g for methyl orange at solute equilibrium concentration of 24 mg/L in water). The XPS analysis revealed that only quaternary (N‐Q) and pyridinic (N‐6) nitrogen sites were found in these carbon spheres. The best ORR performance was found also for C#3 carbon spheres, with a potential of 0.81 V versus reversible hydrogen electrode (RHE) at −1 mA/cm2 and electron transfer number of 3.5 at 0.6–0.8 V versus RHE, as determined by rotating disk or rotating ring disk electrode tests. In conclusion, all results confirm that these PAN‐derived carbon spheres are potentially valuable materials for both wastewater treatment by adsorption and electrocatalytic oxygen reduction.

Preparation of Cobalt-Nitrogen Co-Doped Carbon Nanotubes for Activated Peroxymonosulfate Degradation of Carbamazepine.

Cobalt-nitrogen co-doped carbon nanotubes (Co3@NCNT-800) were synthesized via a facile and economical approach to investigate the efficient degradation of organic pollutants in aqueous environments. This material demonstrated high catalytic efficiency in the degradation of carbamazepine (CBZ) in the presence of peroxymonosulfate (PMS). The experimental data revealed that at a neutral pH of 7 and an initial CBZ concentration of 20 mg/L, the application of Co3@NCNT-800 at 0.2 g/L facilitated a degradation rate of 64.7% within 60 min. Mechanistic investigations indicated that the presence of pyridinic nitrogen and cobalt species enhanced the generation of reactive oxygen species. Radical scavenging assays and electron spin resonance spectroscopy confirmed that radical and nonradical pathways contributed to CBZ degradation, with the nonradical mechanism being predominant. This research presents the development of a novel PMS catalyst, synthesized through an efficient and stable method, which provides a cost-effective solution for the remediation of organic contaminants in water.

Pyridinic Nitrogen Doping: A Versatile Approach for Precise Structure–Property Manipulations of Nanographenes

Pyridinic Nitrogen Doping: A Versatile Approach for Precise Structure–Property Manipulations of Nanographenes

Robust Covalent Organic Framework Photocatalysts for H2O2 Production: Linkage Position Matters.

Covalent organic frameworks (COFs) are promising photocatalysts for hydrogen peroxide (H2O2) synthesis. However, the nature of organic polymers makes the balance between high activity and stability challenging. We demonstrate that the linkage position matters in the design of robust COF photocatalysts with durable high activity without sacrificial reagents. COFs with ortho- and para-linkages (o-COFs and p-COFs) were constructed by 1,3,5-triformylphloroglucinol with benzene-, pyridine-, pyrazine-orthodiamines and paradiamines. The pyrzaine-containing o-COFs with two pyridinic nitrogen atoms exhibited a H2O2 production rate of 4396μmol g-1 h-1 together with long-time continuous H2O2 photosynthesis performance in pure water (48 h), superior to the corresponding p-COFs. A four-step reaction mechanism is proposed by density function calculations. Moreover, the active sites and origin of stability enhancement for o-COFs are clarified. This workprovides a simple and effective molecular design strategy in the design ofrobust COF photocatalysts for artificial H2O2 photosynthesis.