Strategies for Enhancing the Photocatalytic and Electrocatalytic Efficiency of Covalent Triazine Frameworks for CO2 Reduction.

Converting carbon dioxide (CO2) into fuel and high-value-added chemicals is considered a green and effective way to solve global energy and environmental problems. Covalent triazine frameworks (CTFs) are extensively utilized as an emerging catalyst for photo/electrocatalytic CO2 reduction reaction (CO2RR) recently recognized for their distinctive qualities, including excellent thermal and chemical stability, π-conjugated structure, rich nitrogen content, and a strong affinity for CO2, etc. Nevertheless, single-component CTFs have the problems of accelerated recombination of photoexcited electron-hole pairs and restricted conductivity, which limit their application for photo/electrocatalytic CO2RR. Therefore, emphasis will then summarize the strategies for enhancing the photocatalytic and electrocatalytic efficiency of CTFs for CO2RR in this paper, including atom doping, constructing a heterojunction structure, etc. This review first illustrates the synthesis strategies of CTFs and the advantages of CTFs in the field of photo/electrocatalytic CO2RR. Subsequently, the mechanism of CTF-based materials in photo/electrocatalytic CO2RR is described. Lastly, the challenges and future prospects of CTFs in photo/electrocatalytic CO2RR are addressed, which offers a fresh perspective for the future development of CTFs in photo/electrocatalytic CO2RR.

Polydopamine-modified MOF-5-derived carbon as persulfate activator for aniline aerofloat degradation.

Residual flotation chemicals in beneficiation wastewater seriously threaten local ecosystems, such as groundwater or soil, and must be treated effectively. Currently, the degradation of organic pollutants using nitrided MOFs-derived carbon to activate persulfate (PDS) has attracted considerable attention. Hence, we developed a new synthetic strategy to load dopamine hydrochloride (PDA) onto MOF-5-derived porous carbon (PC) to form NPC, and the degradation of a typical flotation Aniline aerofloat (AAF) at high salinity by a low dose of the NPC/PDS system was investigated. Several characterization analyses such as TEM, XRD, Raman, FT-IR and XPS demonstrated that the nitrogen-rich indolequinone unit in PDA provided nitrogen to PC during the pyrolysis process. This enabled the core-shell structure of NPC and the synergy among the multiple components to induce the AAF degradation by PDS over a wide pH scale in a short period of time. It was deduced that the degradation of AAF by the NPC-8/PDS system was a non-radical pathway dominated by 1O2, which relied mainly on the conversion of superoxide radicals (O2•-) and surface-bound radicals. Among them, the pyridine N in the sp2 hybrid carbon was considered as a possible active site. This non-radical pathway was resistant to pH changes and background substances in the water, and well overcame the inhibition of the reaction by natural organic substances and inorganic anions in natural water. In this study, A novel approach to the synthesis of homogeneous MOFs nuclear-derived porous carbon was proposed and the application of MOFs-derived porous carbon for AAF remediation of mineral processing wastewater was broadened.

Generation and identification of 1O2 in catalysts/peroxymonosulfate systems for water purification.

Catalysts for peroxymonosulfate (PMS) activation are appealing in the purification of organic wastewater. Singlet oxygen (1O2) is widely recognized as a crucial reactive species for degrading organic contaminants in catalysts/PMS systems due to its adamant resistance to inorganic anions, high selectivity, and broad pH applicability. With the rapid growth of studies on 1O2 in catalysts/PMS systems, it becomes necessary to provide a comprehensive review of its current state. This review highlights recent advancements concerning 1O2 in catalysts/PMS systems, with a primary focus on generation pathways and identification methods. The generation pathways of 1O2 are summarized based on whether (distinguished by the geometric structures of metal species) or not (distinguished by the active sites) the metal element is included in the catalysts. Furthermore, this review thoroughly discusses the influence of metal valence states and metal species with different geometric structures on 1O2 generation. Various potential strategies are explored to regulate the generation of 1O2 from the perspective of catalyst design. Identification methods of 1O2 primarily include electron paramagnetic resonance (EPR), quenching experiments, reaction in D2O solution, and chemical probe tests in catalysts/PMS systems. The principles and applications of these methods are presented comprehensively along with their applicability, possible disagreements, and corresponding solutions. Besides, an identifying procedure on the combination of main identification methods is provided to evaluate the role of 1O2 in catalysts/PMS systems. Lastly, several perspectives for further studies are proposed to facilitate developments of 1O2 in catalysts/PMS systems.

Fe3N nanoparticles embedded in N-doped porous magnetic graphene for peroxymonosulfate activation: Radical and nonradical mechanism.

The persistence of pharmaceutical and personal care products (PPCPs) such as norfloxacin (NFX) poses a serious threat to the water environment, and the development of efficient and cost-effective advanced oxidation catalysts is an important step toward resolving this issue. Herein, Fe and N co-doped graphene (FeNGO) was synthesized from graphene oxide (GO), urea, and iron salt via simple impregnation pyrolysis, and applied for activating peroxymonosulfate (PMS) to degrade NFX. FeNGO possessed a two-dimensional porous sheet structure and was rich in defects, nitrogen species, and active sites. Compared with the control catalyst doped with N or Fe alone, FeNGO/PMS system showed the best degradation performance with 97.7% removal of NFX after 30 min, the rate constant was 7.1 and 1.7 times than that for NGO and FeGO, respectively. Fe3N was the main active site of FeNGO, and it is confirmed that singlet oxygen (1O2) and superoxide radical (O2•-) were the primary oxidation active species (ROS) during NFX degradation. The formation of 1O2 came from the transformation of O2•- and PMS decomposition. FeNGO showed strong pH adaptability, and also exhibited stale degradation performance in saliferous water matrices. It is believed that this work will offer theoretical and practical guidance for PMS activation by non-radical pathways.

Efficient degradation of norfloxacin by carbonized polydopamine-decorated g-C3N4 activated peroxymonosulfate: Performance and mechanism.

The use of metal-free graphite carbon nitride (CN) to activate peroxymonosulfate (PMS) has attracted extensive attention for organic pollutants degradation. In this work, we prepared carbonized polydopamine-decorated g-C3N4 (CP-700) for activation of PMS to degrade norfloxacin (NOR). The CP-700 composite was obtained by using CN as a base material on which dopamine underwent an autopolymerization reaction to form a CN-PDA complex, followed by pyrolysis. The apparent porous structure and graphitization provided a large number of active sites for catalytic degradation, enabling CP-700 to exhibit excellent catalytic performance during PMS activation. The degradation of NOR was not hindered by sulfate radical (SO4•-) and hydroxyl radical (•OH). Singlet oxygen (1O2) and mediated electron transfer were ultimately identified as the primary mechanisms. According to the linear positive correlation (R2 = 0.9922) between the semi-quantitative carbonyl group (CO) and the reaction rate constant, it was determined that the carbonyl group served as the important active site. The excellent electron transfer ability of CP-700 was evidenced by electrochemical techniques and the electron transfer pathway in the system was that PMS was adsorbed on the CP-700 surface to form metastable complex, and then the electron transfer between NOR and metastable complex was achieved. Based on the non-radical pathway, CP-700/PMS system showed a high tolerance to solution pH (3.0-11.0) and inorganic anions. The cyclic degradation experiments indicated that the system maintained a high degradation capability without the addition of additional CP-700, elucidating its potential application in the degradation of organic pollutants in the water.

Synthesis of Porous Biochar Containing Graphitic Carbon Derived From Lignin Content of Forestry Biomass and Its Application for the Removal of Diclofenac Sodium From Aqueous Solution.

Porous biochar containing graphitic carbon materials have received great attention from various disciplines, especially for environmental pollutant treatment, due to their cost-effective and specific textural properties. This study exhibited a two-step strategy to compose lignin-porous biochar containing graphitic carbon (LPGC) from pitch pine sawdust and investigated its adsorptive removal for diclofenac sodium (DCF) from an aqueous solution. Sulfuric acid (H2SO4) was utilized to obtain lignin content from biomass and potassium ferrate (K2FeO4) and was adopted to fulfill the synchronous carbonization and graphitization of LPGC. Through slow pyrolysis in atmospheric N2 (900°C - 2 h), the structure of the as-prepared sample was successfully modified. Using SEM images, a stripped layer structure was observed on the H2SO4-treated sample for both one-step and two-step activated samples, indicating the pronounced effect of H2SO4 in the layering of materials. K2FeO4 acted as an activator and catalyst to convert biomass into the porous graphitic structure. The BET surface area, XRD and Raman spectra analyses demonstrated that LPGC possessed a micro/mesoporous structure with a relatively large surface area (457.4 m2 g-1) as well as the presence of a graphitic structure. Further adsorption experiments revealed that LPGC exhibited a high DCF adsorption capacity (qmax = 159.7 mg g-1 at 298 K, pH = 6.5). The effects of ambient conditions such as contact time, solution pH, temperature, ionic strength, electrolyte background on the uptake of DCF were investigated by a batch adsorption experiment. Results indicated that the experimental data were best fitted with the pseudo second-order model and Langmuir isotherm model. Furthermore, the adsorption of DCF onto the LPGC process was spontaneous and endothermic. Electrostatic interaction, H-bonding interaction, and π-π interaction are the possible adsorption mechanisms. The porous biochar containing graphitic carbon obtained from the lignin content of pitch pine sawdust may be a potential material for eliminating organic pollutants from water bodies.

Synthesis a graphene-like magnetic biochar by potassium ferrate for 17ß-estradiol removal: Effects of Al2O3 nanoparticles and microplastics.

A graphene-like magnetic biochar (GLMB) was synthesized using lotus seedpod and potassium ferrate with simple step and applied for E2 adsorption. GLMB was characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscope (AFM), X-ray photoelectron spectroscopy (XPS), Raman, X-ray diffraction (XRD), vibrating sample magnetometer (VSM) and BET surface area. Several common (solution pH, ionic strength, humic acid and foreign ions) and new (Al2O3 nanoparticles and microplastics (MPs)) water experiment conditions were investigated. Characterization results demonstrated that the sample was fabricated successfully and it possessed some graphene-like properties and a large surface area (828.37 m2/g). Adsorption results revealed that the pseudo-second-order kinetics and Langmuir isotherm models could provide a better description for E2 uptake behavior. The E2 adsorption capacity could be influenced by solution pH, ionic strength and SO42- ions, and the effect of humic acid and background electrolyte (Na+, K+, Ca2+, Mg2+, Cl-, NO3-, PO43-) could be neglected. The presences of Al2O3/MPs significantly decreased the time to reach adsorption equilibrium for E2 adsorption on GLMB, but had no obvious improvement or inhibiting effects on E2 removal when the adsorption reached equilibrium. The adsorption mechanism for E2 adsorption on GLMB was multiple, which involving π-π interactions, micropore filling effects, electrostatic interaction. The regeneration experiments showed that GLMB possessed a good regeneration performance. Based on the experimental results and comparative analysis with other adsorbents, GLMB was an economical, high-efficiency, green and recyclable adsorbent for E2 removal from aqueous solution.

Adsorption studies of 17ß-estradiol from aqueous solution using a novel stabilized Fe-Mn binary oxide nanocomposite.

The removal of 17ß-estradiol (E2) from contaminated water on nanoscale Fe-Mn binary oxide-loaded multiwalled carbon nanotubes (MWCNTs/FMBO) was evaluated in this work. The characterizations of the mesoporous adsorbent were analyzed by using SEM, TEM, VSM, XRD, XPS, and FTIR measurements. The effects of experimental conditions in E2 removal, including stabilizer additional level, adsorption time, initial E2 concentration, solution pH, reaction temperature, and foreign ions, were examined. The maximum monolayer adsorption capacity (qm) of MWCNTs/FMBO for E2 in the experiment was 47.25 mg/g as verified by the Langmuir sorption isotherm study. The adsorption process was pH-sensitive with an optimum pH of 7.0. On the kinetics study, the adsorption data could be satisfactorily fitted by the pseudo-second-order kinetics. Thermodynamic parameters indicated that the adsorption process was spontaneous and exothermal. In addition, the foreign ions did not show any noticeable inhibition for E2 removal from the water solution except for PO43- that was adversely affected for E2 uptake than other anions in a certain concentration. The adsorption capacities of the mesoporous adsorbent remained at 86.16% even after five adsorption-desorption cycles without significant loss of capacity, which demonstrated the stability and reusability for further removal of E2. Moreover, both hydrogen bond and π-π interaction might be the dominating adsorption mechanisms for E2 adsorption onto MWCNTs/FMBO.

Discovery and structure-activity relationship studies of N-substituted indole derivatives as novel Mcl-1 inhibitors.

Myeloid cell leukemia-1 (Mcl-1) is an important antiapoptotic protein functioning through protein-protein interactions. We discovered LSL-A6 (2-((2-carbamoyl-1-(3-(4-methoxyphenoxy)propyl)-1H-indol-6-yl)oxy)acetic acid) with a novel N-substituted indole scaffold to interfere Mcl-1 binding as a novel Mcl-1 inhibitor. Molecular modeling indicated that this compound binds with Mcl-1 by interaction with P2 and R263 hot-spots. Structure modification focused on several moieties including indole core, hydrophobic tail and acidic chain were conducted and structure-activity relationship was analyzed. The most potent compound 24d which exhibited Ki value of 110nM for interfering Mcl-1 binding was obtained after hit-to-lead modification.