Polyolefin-derived substrate-grown carbon nanotubes as binder-free electrode for hydrogen evolution in alkaline media.

Switching from a linear mode of waste management to a circular loop by transforming plastic waste into carbon nanotubes (CNTs) is a promising approach to current plastic waste treatment. One of the many applications of CNTs is its use for electrocatalytic water splitting for hydrogen evolution. Existing methods of CNTs-based hydrogen evolution reaction (HER) electrode fabrication involve additives like polymeric binders and additional steps to improve CNT dispersion, which are detrimental to the CNT structure and properties. The in-situ fabrication approach can potentially be a one-pot solution to HER electrode synthesis. In this study, polyolefins pyrolysis gas and a Co:Ni:Mg catalyst were used to fabricate binder-free CNTs-based electrodes on different substrates for HER. The study assessed CNT quality on conductive carbon paper, semiconductive silicon, and dielectric glass substrates, evaluating their HER performance in 1 M KOH. A mixture of hollow-core, bamboo-like, and cup-stacked arrangement nanotubes were synthesized on the substrates, with CNTs on glass and carbon paper substrates possessing better graphitization than CNTs grown on silicon. This is in agreement with HER performance, whereby the as-prepared electrodes required overpotentials of 267 mV, 241 mV, and 216 mV for silicon, glass, and carbon paper, respectively, to achieve 10 mA/cm2. Despite being poorly conductive, the glass substrate electrode achieved a lower overpotential than the silicon electrode. Additionally, the as-prepared silicon electrode faced a delamination issue likely attributed to the lower surface energy of the silicon substrate surface, demonstrating the weaker adhesion between the CNTs and silicon surface. The proposed approach thus showed that the in-situ fabricated electrodes performed better than separately synthesized CNTs prepared into electrodes by 27.4% and 14.2% for carbon paper and glass substrates, respectively. The improved performance of the as-prepared, binder-free electrodes can be linked to the lower charge-transfer resistance and reduced contact resistance between the CNTs and substrate.

Carbon Dioxide Capture from Biomass Pyrolysis Gas as an Enabling Step of Biogenic Carbon Nanotube Synthesis and Hydrogen Recovery.

Utilization of renewable raw materials as feedstock defossilizes industrial manufacturing while subsequent carbon capture reduces carbon footprint. We applied this concept to design a new pyrolysis-based process for synthesis of biogenic multi-walled carbon nanotubes (MWCNTs) and H2 from biomass. It was demonstrated that the conversion of hydrocarbon compounds in pyrolysis gas into MWCNTs and H2 is detrimentally influenced by accompanied CO2 released from biomass decomposition. Capturing CO2 with a calcium sorbent upgraded the pyrolysis gas into a suitable gaseous precursor for downstream production of MWCNTs and H2 -rich gas. Furthermore, the results suggest that CO2 capture with the sorbent has a potential to outperform a liquid alkaline scrubber owing to avoided liquid organic waste generation, sorbent regenerability and higher H2 recovery from biomass pyrolysis gas.

Defossilization and decarbonization of hydrogen production using plastic waste: Temperature and feedstock effects during thermolysis stage.

The replacement of natural gas with plastic-derived pyrolysis gas can defossilize H2 production, while subsequent capture, utilization and storage of carbon in a solid form can decarbonize the process. The objective of this study was to investigate H2 production from three types of plastics using a process comprising pyrolysis (600 °C) and thermolysis stages (1200-1500 °C). Depending on the plastic feedstock and thermolysis temperature, the laboratory-scale setup generated 1000-1350 mL/min product gas with H2 purity of 74.3-94.2 vol%. The recovery of 5-9 wt% molecular H2 per mass of plastics was achieved. Other products included solid residue (0.1-12 wt%) and oil (8-52 wt%) from the pyrolysis reactor, solid carbon (36-53 wt%) and gas impurities (2-16 wt%) from the thermolysis reactor. The purity of H2 gas was detrimentally influenced by polyethylene terephthalate in the feedstock due to the dilution of gas by CO. The decomposition of methane containing in the pyrolysis gas was the limiting reaction step during H2 production and improved at higher thermolysis temperature. Three solid carbon structures were formed during the thermolysis stage regardless of the plastic type: carbon black aggregates, carbon black aggregates coated with a layer of pyrolytic carbon and a carbon film on the inner reactor wall. Among the three types of carbon, the highest valorization potential was identified for carbon black aggregates. Plastic feedstock composition had little if any effect on carbon black properties, while high thermolysis temperature (1500 °C) reduced the particle sizes and increased the surface area of aggregates.

Nanocomposite Foams with Balanced Mechanical Properties and Energy Return from EVA and CNT for the Midsole of Sports Footwear Application.

Polymer foam that provides good support with high energy return (low energy loss) is desirable for sport footwear to improve running performance. Ethylene-vinyl acetate copolymer (EVA) foam is commonly used in the midsole of running shoes. However, EVA foam exhibits low mechanical properties. Conventional mineral fillers are usually employed to improve EVA's mechanical performance, but the energy return is sacrificed. Here, we produced nanocomposite foams from EVA and multi-walled carbon nanotubes (CNT) using a chemical foaming process. Two kinds of CNT derived from the upcycling of commodity plastics were prepared through a catalytic chemical vapor deposition process and used as reinforcing and nucleating agents. Our results show that EVA foam incorporated with oxygenated CNT (O-CNT) demonstrated a more pronounced improvement of physical, mechanical, and dynamic impact response properties than acid-purified CNT (A-CNT). When CNT with weight percentage as low as 0.5 wt% was added to the nanocomposites, the physical properties, abrasion resistance, compressive strength, dynamic stiffness, and rebound performance of the EVA foams were improved significantly. Unlike the conventional EVA formulation filled with talc mineral fillers, the incorporation of CNT does not compromise the energy return of the EVA foam. From the long-cycle dynamic fatigue test, the CNT/EVA foam displays greater properties retention as compared to the talc/EVA foam. This work demonstrates a good balanced of mechanical-energy return properties of EVA nanocomposite foam with very low CNT content, which presents promising opportunities for lightweight-high rebound midsoles for running shoes.

Importance of carbon structure for nitrogen and sulfur co-doping to promote superior ciprofloxacin removal via peroxymonosulfate activation.

Herein, five N, S-co-doped carbocatalysts were prepared from different carbonaceous precursors, namely sawdust (SD), biochar (BC), carbon-nanotubes (CNTs), graphite (GP), and graphene oxide (GO) and compared. Generally, as the graphitization degree increased, the extent of N and S doping decreased, graphitic N configuration is preferred, and S configuration is unaltered. As peroxymonosulfate (PMS) activator for ciprofloxacin (CIP) removal, the catalytic performance was in order: NS-CNTs (0.037 min-1) > NS-BC (0.032 min-1) > NS-rGO (0.024 min-1) > NS-SD (0.010 min-1) > NS-GP (0.006 min-1), with the carbonaceous properties, rather than the heteroatoms content and textural properties, being the major factor affecting the catalytic performance. NS-CNTs was found to have the supreme catalytic activity due to its remarkable conductivity (3.38 S m-1) and defective sites (ID/IG = 1.28) with high anti-interference effect against organic and inorganic matter and varying water matrixes. The PMS activation pathway was dominated by singlet oxygen (1O2) generation and electron transfer regime between CIP and PMS activated complexes. The CIP degradation intermediates were identified, and a degradation pathway is proposed. Overall, this study provides a better understanding of the importance of selecting a suitable carbonaceous platform for heteroatoms doping to produce superior PMS activator for antibiotics decontamination.

Converting polyolefin plastics into few-walled carbon nanotubes via a tandem catalytic process: Importance of gas composition and system configuration.

Polyolefins such as polyethylene (PE) and polypropylene (PP) are abundant components of plastic waste. Chemical recycling of PE and PP via pyrolysis followed by chemical vapor deposition typically results in the growth of multi-walled carbon nanotubes (CNTs). Here, a tandem catalytic system for the growth of few-walled CNTs is reported. The successful synthesis of few-walled CNTs in the system relies on the catalytic processing of pyrolysis gas from plastics into intermediate gas mixtures containing mainly paraffins and hydrogen (700 °C, catalyst: 40 wt% Co, 10 wt% Mo and 50 wt% MgO). Under appropriate conditions (1000 °C, catalyst: Co 3 wt%, Mo 2 wt% and MgO 95 wt%, synthesis time: 20 min), the obtained intermediate gas mixture was selectively converted into few-walled CNTs with > 95% CNTs having small outer diameters of 1-7 nm, containing CNTs with as little as three walls and having distinct radial breathing mode in Raman spectra at wave lengths 100-400 cm-1. The proposed synthesis process opens new opportunities for production of high value few-walled CNTs from plastic waste.

Tailoring Fe2O3-Al2O3 catalyst structure and activity via hydrothermal synthesis for carbon nanotubes and hydrogen production from polyolefin plastics.

Fe2O3-Al2O3 catalysts applied for conversion of polyolefin plastic waste into multi-walled carbon nanotubes (MWCNTs) and H2 are typically produced by impregnation, co-precipitation or sol-gel synthesis at atmospheric pressure and temperatures below 100 °C. This study utilized hydrothermal conditions and established the role of precipitating agents (urea, N-methylurea and N,N'-dimethylurea) on properties and catalytic activity of Fe2O3-Al2O3 catalysts (Fe-u, Fe-mu and Fe-dmu, respectively). The precipitating agent played a key role in tailoring the properties, such as crystallization degree, surface area and reducibility. The precipitating agents influenced the yield and outer diameters of MWCNTs but did not affect graphitization degree. Among the synthesized catalysts, Fe-u had the largest surface area and preferential formation of the highly reducible α-Fe2O3 crystalline phase. As a result, Fe-u had the highest activity during conversion of pyrolysis gas from low-density polyethylene (LDPE) into MWCNTs, yielding 0.91 g·g-1-catalyst MWCNTs at 800 °C as compared to 0.42 and 0.14 g·g-1-catalyst using Fe-dmu and Fe-mu, respectively. Fe-dmu favored the growth of MWCNTs with smaller outer diameters. Fe-u demonstrated high efficiency during operation using a continuous flow of pyrolysis gas from a mixture of polyolefins (70 wt% polypropylene, 6 wt% LDPE and 24 wt% high density polyethylene) producing 4.28 g·g-1-catalyst MWCNTs at 3.2% plastic conversion efficiency and a stable H2 flow for 155 min (25-32 vol%). The obtained data demonstrate that the selection of an appropriate precipitating agent for hydrothermal synthesis allows for the production of highly active Fe2O3-Al2O3 catalysts for the upcycling of polyolefin plastic waste into MWCNTs and H2.

High temperature slagging gasification of municipal solid waste with biomass charcoal as a greener auxiliary fuel.

During high temperature slagging gasification of municipal solid waste (MSW), coal coke is typically used as an auxiliary fuel to maintain the high temperature in the gasifier and convert ashes into slag. Herein, biomass charcoal was utilized as a greener and more sustainable auxiliary fuel to replace the coal coke during stable and continuous gasification of MSW. Several monitoring characteristics were assessed, like operating conditions of the gasifier, influence of local MSW properties generated in Singapore, environmental impacts, and main by-products (slag, fly ash and metals). The performance data revealed that the replacement of coal coke with biomass charcoal provided significant environmental benefits. The use of biomass charcoal resulted in 78% less SO2 emissions, and 22% less generated fly ash because the lower sulfur content in biomass charcoal resulted in a 32% reduced use of sorbent for flue gas treatment. Furthermore, there was clear evidence of a 22% carbon footprint reduction due to replacing fossil fuel as auxiliary fuel. In addition, the slag characteristics demonstrated lower heavy metals leaching as compared to the incineration bottom ash generated from the conventional MSW incineration plant suggesting its great potential in the application as clean and green waste-derived material in the construction industry.

Activated multi-walled carbon nanotubes decorated with zero valent nickel nanoparticles for arsenic, cadmium and lead adsorption from wastewater in a batch and continuous flow modes.

Nickel nanoparticles (NiNPs) supported on activated multi-walled carbon nanotubes (MWCNTs) were used as an adsorbent applied towards Pb(II), As(V) and Cd(II) remediation from industrial wastewater. The result revealed the hydrophilic surface of MWCNTs-KOH was enhanced with the incorporation of NiNPs enabling higher surface area, functional groups and pore distribution. Comparatively, the removal of Pb(II), As(V) and Cd(II) on the various adsorbents was reported as NiNPs (58.6 ± 4.1, 46.8 ± 3.7 and 40.5 ± 2.5%), MWCNTs-KOH (68.4 ± 5.0, 65.5 ± 4.2 and 50.7 ± 3.4%) and MWCNTs-KOH@NiNPs (91.2 ± 8.7, 88.5 ± 6.5 and 80.6 ± 5.8%). Using MWCNTs-KOH@NiNPs, the maximum adsorption capacities of 481.0, 440.9 and 415.8 mg/g were obtained for Pb(II), As(V) and Cd(II), respectively. The experimental data were best suited to the Langmuir isotherm and pseudo-second order kinetic model. The fitness of experimental data to the kinetic models in a fixed-bed showed better fitness to Thomas model. The mechanism of metal ion adsorption onto MWCNTs-KOH@NiNPs show a proposed electrostatic attraction, surface adsorption, ion exchange, and pore diffusion due to the incorporated NiNPs. The nanocomposite was highly efficient for 8 adsorption cycles. The results of this study indicate that the synthesized nanocomposite is highly active with capacity for extended use in wastewater treatment.

Technical and environmental assessment of laboratory scale approach for sustainable management of marine plastic litter.

Laboratory scale recycling of marine plastic litter consisting of polyethylene terephthalate (PET) bottle sorting, pyrolysis and chemical vapor deposition (CVD) was conducted to identify the technical and environmental implications of the technology when dealing with real waste streams. Collected seashore and underwater plastics (SP and UP, respectively) contained large quantities of PET bottles (33.2 wt% and 61.4 wt%, respectively), suggesting PET separation was necessary prior to pyrolysis. After PET sorting, marine litter was converted into pyrolysis oil and multi-walled carbon nanotubes (MWCNTs). Water-based washing of litter prior to pyrolysis did not significantly change the composition of pyrolysis products and could be avoided, eliminating freshwater consumption. However, distinct differences in oil and MWCNT properties were ascribed to the variations in feedstock composition. Maintaining consistent product quality would be one of challenges for thermochemical treatment of marine litter. As for the environmental implications, life cycle assessment (LCA) demonstrated positive benefits, including improved climate change and fossil depletion potentials. The highest positive environmental impacts were associated with MWCNT production followed by pyrolysis oil and PET recovery. The benefits of proposed approach combining PET sorting, pyrolysis and CVD allowed to close the waste loop by converting most of the marine litter into valuable products.

Temperature-dependent synthesis of multi-walled carbon nanotubes and hydrogen from plastic waste over A-site-deficient perovskite La0.8Ni1-xCoxO3-δ.

Thermochemical conversion of plastic wastes into carbon nanotubes (CNTs) and hydrogen is a promising management option to eliminate their hazardous effect. The yields and morphologies of CNTs strongly depend on the catalyst design and reaction conditions. To boost the efficiency, tuning of bimetallic nanoparticles as catalyst is an effective approach. For that reason, A-site-deficient perovskite La0·8Ni1-xCoxO3-δ (LN1-xCx, x = 0.15, 0.5, 0.85) was developed and used as a catalyst precursor to achieve in situ formation of bimetallic Ni-Co nanoparticles. At an optimized Ni-to-Co ratio, the LN0.5C0.5 exhibited the highest yields of multi-walled CNTs, namely 840 and 853 mg/gcatalyst from high density polyethylene and polypropylene, respectively. This could be attributed to the higher catalytic capability of LN0.5C0.5 catalyst for the decomposition of hydrocarbons into hydrogen and carbon. In both cases, multi-walled CNTs had regular shapes when the reaction temperature was 700 °C. At higher reaction temperatures, the morphological changes of carbon products were observed from multi-walled CNTs to carbon nano-onions. The Raman spectra showed that compared with the commercial multi-walled CNTs, the as-prepared multi-walled CNTs had a lower degree of defects.

Upcycling of exhausted reverse osmosis membranes into value-added pyrolysis products and carbon dots.

Polymeric reverse osmosis (RO) membranes are widely used worldwide for production of fresh water from various sources, primarily ocean desalination. However, with limited service life, exhausted RO membrane modules often end up as plastic wastes disposed of predominantly by landfilling. It is imperative to find a feasible way to upcycle end-of-life RO membrane modules into valuable products. In this paper, the feasibility of RO membrane recycling via pyrolysis and subsequent conversion of resulting char into carbon dots (CDs) through H2O2-assisted hydrothermal method was investigated. RO membrane module pyrolysis at 600 °C produced oil (28 wt%), non-condensable gas (17 wt%), and char (22 wt%). While oil and gas can serve as fuel and chemical feedstock due to rich hydrocarbon content, char was found a suitable precursor for the synthesis of functional CDs. The resulting CDs doped with N (4.8%) and S (1.8%) exhibited excellent water dispersibility, narrow size distribution of 1.3-6.8 nm, high stability, and strong blue fluorescence with a quantum yield of 6.24%. CDs demonstrated high selectivity and sensitivity towards Fe3+ in the range of 0-100 µM with the limit of detection of 2.97 µM and were capable of determining Fe3+ in real water samples (tap water and pond water).

Environmental footprint of voltammetric sensors based on screen-printed electrodes: An assessment towards "green" sensor manufacturing.

Voltammetric sensors based on screen-printed electrodes (SPEs) await diverse applications in environmental monitoring, food, agricultural and biomedical analysis. However, due to the single-use and disposable characteristics of SPEs and the scale of measurements performed, their environmental impacts should be considered. A life cycle assessment was conducted to evaluate the environmental footprint of SPEs manufactured using various substrate materials (SMs: cotton textile, HDPE plastic, Kraft paper, graphic paper, glass, and ceramic) and electrode materials (EMs: platinum, gold, silver, copper, carbon black, and carbon nanotubes (CNTs)). The greatest environmental impact was observed when cotton textile was used as SM. HDPE plastic demonstrated the least impact (13 out of 19 categories), followed by ceramic, glass and paper. However, considering the end-of-life scenarios and release of microplastics into the environment, ceramic, glass or paper could be the most suitable options for SMs. Amongst the EMs, the replacement of metals, especially noble metals, by carbon-based EMs greatly reduces the environmental footprint of SPEs. Compared with other materials, carbon black was the least impactful on the environment. On the other hand, copper and waste-derived CNTs (WCNTs) showed low impacts except for terrestrial ecotoxicity and human toxicity (non-cancer) potentials. In comparison to commercial CNTs (CCNTs), WCNTs demonstrated lower environmental footprint and comparable voltammetric performance in heavy metal detections, justifying the substitution of CCNTs with WCNTs in commercial applications. In conclusion, a combination of carbon black or WCNTs EMs with ceramic, glass or paper SMs represents the most environmentally friendly SPE configurations for voltammetric sensor arrangement.

In situ catalytic reforming of plastic pyrolysis vapors using MSW incineration ashes.

The valorization of municipal solid waste incineration bottom and fly ashes (IBA and IFA) as catalysts for thermochemical plastic treatment was investigated. As-received, calcined, and Ni-loaded ashes prepared via hydrothermal synthesis were used as low-cost waste-derived catalysts for in-line upgrading of volatile products from plastic pyrolysis. It was found that both IBA and air pollution control IFA (APC) promote selective production of BTEX compounds (i.e., benzene, toluene, ethylbenzene, and xylenes) without significantly affecting the formation of other gaseous and liquid species. There was insignificant change in the product distribution when electrostatic precipitator IFA (ESP) was used, probably due to the lack of active catalytic species. Calcined APC (C-APC) demonstrated further improvement in the BTEX yield that suggested the potential to enhance the catalytic properties of ashes through pre-treatment. By comparing with the leaching limit values stated in the European Council Decision, 2003/33/EC for the acceptance of hazardous waste at landfills, all the ashes applied remained in the same category after the calcination and pyrolysis processes, except the leaching of Cl- from the ESP, which was around the borderline. Therefore, the use of ashes in catalytic reforming application do not significantly deteriorate their metal leaching behavior. Considering its superior catalytic activity towards BTEX formation, C-APC was loaded with Ni at 15 and 30 wt%. The Ni-loading favored an increase in overall oil yield, while reducing the gas yield when compared to the benchmark Ni loaded ZSM catalyst. However, Ni addition also caused the formation of more heavier hydrocarbons (C20-C35) that would require post-treatment to recover favorable products like BTEX.

Weakening the strong Fe-La interaction in A-site-deficient perovskite via Ni substitution to promote the thermocatalytic synthesis of carbon nanotubes from plastics.

The variation of metal-support interaction (MSI) plays a key role in the synthesis of carbon nanotubes (CNTs) based on chemical vapor deposition process. This work concentrates on weakening the interaction of Fe-La in an A-site-deficient perovskite (La0.8FeO3-δ) via Ni partial substitution. After reductive treatment, the catalysts were employed for thermocatalytic synthesis of CNTs from plastics. Following the structural, morphological and chemical changes, the catalytic activities of the reductive La0.8NixFe1-xO3-δ (H-LNxF1-x, x = 0, 0.15, 0.5, 0.85) were correlated with the degree of MSI. Compared with H-LF sample, the H-LN0.15F0.85 sample exhibited the highest catalytic activity, which was attributable to the highest surface coverage of metals as well as the synergistic effect of Fe and Ni species. The yield of CNTs produced from low density polyethylene was 1.44 g/gcatalyst over the H-LN0.15F0.85 sample, which was much higher than that over H-LF sample (0.38 g/gcatalyst).

Near real-time analysis of para-cresol in wastewater with a laccase-carbon nanotube-based biosensor.

Para-Cresol is a water-soluble organic pollutant, which is harmful to organisms even at low concentrations. Therefore, it is important to rapidly detect the p-cresol in wastewater as well as natural water. In this work, a new, simple and stable biosensor was developed for on-site quantitatively determination and near real-time monitoring p-cresol in wastewater. The new biosensor was designed and fabricated using a screen-printed carbon electrode (SPCE) modified by waste-derived carbon nanotubes (CNTs) immobilized with laccase (LAC). The fabrication processes and performance of the biosensors were systematically characterized and optimized by Fourier transform infrared spectroscopy (FTIR), field emission scanning electron microscope (FESEM), transmission electron microscopy (TEM) and electrochemical methods. With improved conductivity, the proposed biosensor could provide the direct quantitation of p-cresol. The linear range of the biosensor is 0.2-25 ppm of p-cresol with a detection limit of 0.05 ppm. Additionally, the biosensor exhibited high reproducibility, stability and reusability during the validation. More importantly, the biosensor was successfully applied for the rapid detection of p-cresol in environmental lab wastewater under the interference of metal ions and other organics, and the results were consistent with high-performance liquid chromatography (HPLC). Finally, the biosensor with a portable potentiostat was approved as an easy-to-use, sensitive and inexpensive platform that could provide near real-time monitoring of p-cresol concentration in wastewater during Fenton oxidation treatment process.

Taguchi optimization design of diameter-controlled synthesis of multi walled carbon nanotubes for the adsorption of Pb(II) and Ni(II) from chemical industry wastewater.

Herein, Taguchi L9 orthogonal array was used for the first time to optimize synthesis of diameter-controlled multi walled carbon nanotubes (MWCNTs). The nanoadsorbents, MWCNTs5-15 nm and MWCNTs16-25 nm were applied for Pb(II) and Ni(II) ion removal from paint, battery and electroplating wastewater. The results indicated successful synthesis of MWCNTs with diameter distribution ranges of 5-15 nm and 16-25 nm. The synthetized smaller diameter MWCNTs5-15 nm revealed higher Brunauer-Emett-Teller (BET) surface area of 1306 ± 5 m2/g compared to larger diameter MWCNTs16-25 nmwith the surface area of 1245 ± 4 m2/g. They demonstrated excellent adsorption of Pb(II) and Ni(II) ions within the permissible concentration proposed by WHO at pH, contact time, adsorbent dosage and temperature of 5, 60 min, 30 mg/L and 50 °C, respectively. Particularly, MWCNTs5-15 nm possessed high adsorption capacity of 215.38 ± 0.03 mg/g for Pb(II) and 230.78 ± 0.01 mg/g for Ni(II). Again, the maximum adsorption capacity of 201.35 ± 0.02 and 206.40 ± 0.02 mg/g was achieved for Pb(II) and Ni(II) using MWCNTs16-25 nm. All in all, the adsorption capacity of the nanoadsorbents at the investigated diameter range showed higher efficiency compared to other materials for heavy metals elimination from chemical industrial wastewater.

Cobalt and nitrogen co-doped porous carbon/carbon nanotube hybrids anchored with nickel nanoparticles as high-performance electrocatalysts for oxygen reduction reactions.

Non-precious metal-nitrogen-carbon (MNC) materials have been recognized as alternatives to noble-metal catalysts, such as Au/C, Pt/C and Ru/C. As the precursors of MNC catalysts, carbonized zeolite imidazole frameworks (ZIFs) have been widely studied due to their porosity and the composition of ligands, including carbon and nitrogen. Herein, we successfully synthesize a non-precious metal-based ORR catalyst with nickel nanoparticles anchored on cobalt and nitrogen co-doped porous carbon/carbon nanotubes (Ni/Co-NC), employing ZIF-67 metal-organic frameworks as precursors. The Ni/Co-NC catalyst shows an excellent onset potential of 0.984 V and a half-wave potential of 0.869 V in 0.1 M KOH, comparable to those of commercial Pt/C. The excellent ORR performance of Ni/Co-NC was attributed to the synergistic coexistence of the atomically dispersed metal species coordinated with nitrogen (metal-N sites) and carbon-encapsulated nickel nanoparticles as well as the hierarchical porous structure in the catalyst. In addition, the Ni/Co-NC catalyst possesses outstanding anti-poisoning capacity and long-term duration against methanol crossover in an alkaline environment. The obtained results enable the Ni/Co-NC catalyst to explore potential applications in energy conversion and storage systems.

Interaction between SO2 and NO in their adsorption and photocatalytic conversion on TiO2.

The simultaneous adsorption and photocatalytic conversion of SO2 and NO on P25-TiO2 were studied. In particular, the interaction of SO2 and NO on each other's adsorption and photocatalytic oxidation was discussed. The adsorption of NO on P25 was negligible when comparing to that of SO2, while with the coexistence of NO and SO2 in flue gas, both the adsorption of SO2 and NO were improved. In the presence of water and oxygen, the photocatalytic oxidation efficiency of NO with an efficiency of >69% was observed on irradiated TiO2 surface, which lasted for at least 1000 min. Oxygen was found to have much more important effect than water on the photocatalytic oxidation of NO. In the presence of SO2 however, the photocatalytic process of NO was largely reshaped. The whole process was controlled by the photocatalytic oxidation of SO2. A dramatic efficiency decease (breakthrough of the catalyst bed) was observed for both NO and SO2 due to the catalyst deactivation caused by the poisoning of SO2 oxidation products. Before the breakthrough, the photocatalytic conversion efficiency of NO increased with increasing the SO2 concentration, which was mainly due to the improved NO adsorption in the presence of SO2.

Processing of flexible plastic packaging waste into pyrolysis oil and multi-walled carbon nanotubes for electrocatalytic oxygen reduction.

Flexible plastic packaging waste causes serious environmental issues due to challenges in recycling. This study investigated the conversion of flexible plastic packaging waste with 11.8 and 27.5 wt.% polyethylene terephthalate (PET) (denoted as PET-12 and PET-28, respectively) into oil and multi-walled carbon nanotubes (MWCNTs). The mixtures were initially pyrolyzed and the produced volatiles were processed over 9.0 wt.% Fe2O3 supported on ZSM-5 (400 °C) to remove oxygenated hydrocarbons (catalytic cracking of terephthalic and benzoic acids) that deteriorate oil quality. The contents of oxygenated hydrocarbons were decreased in oil from 4.6 and 9.4 wt.% per mass of PET-12 and PET-28, respectively, to undetectable levels. After catalytic cracking, the oil samples had similar contents of gasoline, diesel and heavy oil/wax fractions. The non-condensable gas was converted into MWCNTs over 0.9 wt.% Ni supported on CaCO3 (700 °C). The type of plastic packaging influenced the yields (2.4 and 1.5 wt.% per mass of PET-12 and PET-28, respectively) and the properties of MWCNTs due to the differences in gas composition. Regarding the electrocatalytic application, both MWCNTs from PET-12 and PET-28 outperformed commercial MWCNTs and Pt-based electrodes during oxygen evolution reaction, suggesting that MWCNTs from flexible plastic packaging can potentially replace conventional electrode materials.