Carbonized Eggshell Membrane Research Articles

Carbonized eggshell membranes as highly active co-catalyst with Fe3+/persulfate for boosting degradation of carbamazepine by accelerating Fe3+/Fe2+ cycle

The sluggish Fe3+/Fe2+ cycle greatly limits the effectiveness of the Fe3+-induced persulfate (Fe3+/PS) system for degrading refractory organic pollutants. Coupling Fe3+/PS system with a co-catalyst is a promising strategy to solve this issue. Herein, we report a carbonized eggshell membrane (CESM) as a potential co-catalyst to efficiently drive Fe3+/PS oxidation. The promotion effect of the CESM on the Fe3+/Fe2+ cycle resulted in the improvement in the activity of the Fe3+/PS system to degrade carbamazepine (CBZ), with ∼100 % CBZ removal achieved with low doses of Fe3+ (1.0 mg/L) and PS (100 mg/L). Crucially, a pseudo-first-order rate constant of CESM/Fe3+/PS system was 18- and 28-times that of the Fe3+/PS and CESM/PS systems. Experimental and theoretical findings reveal that the phenolic –OH groups and carbon--center persistent free radicals in CESM are electron donors, while the nitrogen sites function as favorable Fe3+-adsorption sites. The electron transfer in CESM/Fe3+/PS system occurred between a CESM and an attached Fe3+, facilitating the generation of Fe2+ and thus contributing to the continuous activation of PS. The quenching and electron paramagnetic resonance results indicate that active oxygen radicals (O2•−,•OH and SO4•−) and Fe(IV) acted together to realize the efficient CBZ degradation. Moreover, this system exhibited good reusability and environmental adaptability in various real water matrices. The co-catalyst effect of CESM is expected to inspire the exploration of utilization of different waste-biomass-derived organic materials as co-catalysts in the Fe3+/PS system for water purification.

Low-temperature carbonized MXene/protein-based eggshell membrane composite as free-standing electrode for flexible supercapacitors

The demerits of the carbonized eggshell membrane (EM), such as high cost, high brittleness, immutable shape and size, greatly limit its application in demanding supercapacitors as free-standing electrode. Herein, the reconstituted EM (REM) with good flexibility and excellent size-customizability is developed, which is due to their fibrous structure and abundant surface polar groups. Ti3C2 nanosheet (a typical MXene) with ultra-high electrical conductivity and good electrochemical activity is then coated on REM surface, and undergoes a low-temperature carbonization (350 °C) to prepare CREM/T. Multi-functions of Ti3C2 are exhibited: (1) constructing a conductive network on REM surface by randomly stacking to yield a high electrical conductivity of 78.1 S cm−1, (2) being as a protective mold to remain the inherent flexibility and porosity of REM during carbonization, (3) creating nanopores by inducing self-activation, and (4) yielding a large capacitance of 1729 mF cm−2 at 0.5 mA cm−2 and a high rate capability of 82 % after increasing the current density by 50 folds. Furthermore, an all-EM-based supercapacitor is fabricated with REM as the separator and CREM/T as the electrode. It delivers a high energy density of 16.1 μW h cm−2 at 1301 μW cm−2, and shows stable capacitive behaviors during bending.

Eggshell membrane derived nitrogen rich porous carbon for selective electrosorption of nitrate from water

Nitrate (NO3−) is a ubiquitous contaminant in water and wastewater. Conventional treatment processes such as adsorption and membrane separation suffer from low selectivity for NO3− removal, causing high energy consumption and adsorbents usage. In this study, we demonstrate selective removal of NO3− in an electrosorption process by a thin, porous carbonized eggshell membrane (CESM) derived from eggshell bio-waste. The CESM possesses an interconnected hierarchical pore structure with pore size ranging from a few nanometers to tens of micrometers. When utilized as the anode in an electrosorption process, the CESM exhibited strong selectivity for NO3− over Cl−, SO42−, and H2PO4−. Adsorption of NO3− by the CESM reached 2.4 × 10−3 mmol/m2, almost two orders of magnitude higher than that by activated carbon (AC). More importantly, the CESM achieved NO3−/Cl− selectivity of 7.79 at an applied voltage of 1.2 V, the highest NO3−/Cl− selectivity reported to date. The high selectivity led to a five-fold reduction in energy consumption for NO3− removal compared to electrosorption using conventional AC electrodes. Density function theory calculation suggests that the high NO3− selectivity of CESM is attributed to its rich nitrogen-containing functional groups, which possess higher binding energy with NO3− compared to Cl−, SO42−, and H2PO4−. These results suggest that nitrogen-rich biomaterials are good precursors for NO3− selective electrodes; similar chemistry can also be used in other materials to achieve NO3− selectivity.

Novel hierarchical carbon quantum dots-decorated BiOCl nanosheet/carbonized eggshell membrane composites for improved removal of organic contaminants from water via synergistic adsorption and photocatalysis

• Carbonized eggshell membranes (CEMs) were used as bio-templates. • Novel 3D hierarchical carbon quantum dots (CQDs)/BiOCl/CEMs were fabricated. • BiC-0.05 exhibited superior removal efficiency of several organic pollutants. • The removal was boosted by synergistic effect of adsorption and photocatalysis. • The presence of OVs and CQDs account for the boosted photocatalytic activity. A series of carbon quantum dots (CQDs)-decorated BiOCl/carbonized eggshell membrane (CEM) composites were synthesized with CEMs as bio-templates. The obtained composites, especially BiC-0.05, exhibited superior removal efficiencies of several organic pollutants, i.e. tetracycline hydrochloride (TC), Rhodamine B (RhB), and o-nitrophenol (NP). Approximately, 98% of TC was removed after 30 min dark adsorption and subsequent 30 min visible-light-initiated photocatalytic degradation. BiC-0.05 was also utilized to treat actual industrial wastewater and could reduce 73.1% COD, in comparison to 49.9% with the use of BiOCl. The boosted removal efficiencies were achieved by synergistic effect of adsorption and photocatalysis, where cooperative contribution of oxygen vacancies (OVs), CEMs and CQDs enabled faster charge migration and more effective separation of photogenerated charge carriers. Electron spin resonance (ESR) and trapping experimental results showed that superoxide radical ( O 2 − ), along with holes (h + ) and hydroxyl radical ( OH) would take part in photocatalytic degradation process. The intermediates of TC and its possible degradation pathway during the photocatalytic reaction were also studied. Our work developed a novel strategy by integrating carbon nanomaterials derived from bio-waste to design efficient photocatalysts for remediation of organic contaminants via adsorption – photocatalysis synergism and OVs – CQDs cooperation.

Eggshell membrane and expanded polytetrafluoroethylene piezoelectric‐enhanced triboelectric bio‐nanogenerators for energy harvesting

With the growing demand for wearable electronic devices, triboelectric nanogenerators (TENGs) provide an effective solution by harvesting human body motions and converting them into electricity. Tribomaterial is one key element for the output performance and application of TENGs. In this study, biomaterial eggshell membrane (ESM) was investigated for use as a piezoelectric-enhanced positive tribomaterial. ESM not only exhibits excellent piezoelectricity due to the amount of hydrogen bonds, but it is also biocompatible and pollution free. The piezoelectricities of raw eggshell membrane (RESM), heated eggshell membrane (HESM), and carbonized eggshell membrane (CESM) were analyzed and compared. Porous expanded polytetrafluoroethylene (ePTFE) was fabricated and used as a negative tribomaterial in the TENG due to its strong electron-acquisition ability. Pairing ESM with an ePTFE resulted in a novel piezoelectric-enhanced triboelectric bio-nanogenerator (P-TENG) with an excellent energy harvesting ability, high-efficiency output performance, and sensitive human motion monitoring. By comparing ePTFE paired with RESM, HESM, and CESM, the CESM/ePTFE P-TENG showed the best output performance due to CESM's piezoelectric enhancement. This bio-P-TENG as a wearable electric device has great potential in biomedical applications.

A Sensitive Urea Sensor Based NiO Nanoparticles Supported on the 3D Porous Carbonized Eggshell Membrane

Urea (CO(NH2)2) is the main nitrogen-containing substance from the urine of human/animal, which is also an effective and critical indicator in evaluating various metabolic disorders. Urea can decompose naturally to toxic ammonia and nitrates permeating into groundwater, then cause environmental problems and even health issues. Therefore, the detection of urea concentration and decomposition of urea-rich sewage is vitally important in the human health and environmental industries. Urea oxidation reaction (UOR, CO(NH2) 2 + 6OH- → N2 + CO2 + 5H2O + 6e-) has been known as a viable method for renal/liver disease diagnostic detection. Here, we reported nickel oxide (NiO) nanoparticles dressed on the carbonized eggshell membrane (3D NiO/c-ESM) as a modified electrode toward urea detection. The unique network structure of ESM composed of biomacromolecular fibers provides a novel template for the functional groups, also with superior porosity and specific surface area, which can offer multiple transport pathways for both electrons and ions.Consequently, an integrated 3D network composed of NiO nanoparticles anchoring on the carbonized ESM using a mixed method of hydrothermal and pyrolysis. The NiO nanoparticles anchored 3D carbonized network of the catalyst provides more catalytic active sites and enables easy access of reactants to the catalyst surfaces. NiO/c-ESM modified electrode exhibits an outstanding performance for urea determination with a linear range from 0.05 to 2.5 mM, and limit detection of ∼20 µM (3σ). This work offered a green approach for introducing 3D nanostructure through employing biowaste ESMs as templates, providing a typical example for producing new value-added nanomaterials with urea detection.

In-situ growth of TiO2 film on carbonized eggshell membrane as 3D electrode for high-performance lithium storage

3D electrodes have shown extraordinary promise for electrochemical energy storage devices in wearable electronics. However, it is still a significant challenge to rationally design 3D electrode that has the characteristics of lightweight, flexibility, low cost, high performance and miniaturization. In this work, we present a novel design of 3D electrode by directly growing the nanocrystalline TiO2 film on carbonized eggshell membrane. The unique architecture can supply not only a continuous electron transport pathway through an interconnected carbon fibrous network but also an efficient electrolyte flux via an interpenetrating porous network. Besides, nanocrystalline TiO2 film on carbonized eggshell membrane offers a short ion diffusion path in the solid-phase, leading to a rapid kinetic of electrochemical reaction. When tested as an anode for Li-ion battery, TiO2 film in 3D electrode demonstrated excellent electrochemical performance with a large reversible capacity, excellent rate capacity and long life cycling property.

Preparation of TiO<sub>2</sub> Decorated Eggshell Membrane for Photocatalytic Dye Degradation

Pristine ESM was impregnated with TiO2 using the wet chemical method and subsequently calcined at 700 °C. All prepared samples were characterized using Field Emission Scanning Electron Microscope (FESEM), X-ray Diffraction (XRD) and UV-visible Spectrometer. FESEM images indicate the presence of a fibrous network that introduces useful adsorptive and photocatalytic properties for organic pollutants removal from water. The XRD result indicated that the TiO2 nano-composite contained only anatase and rutile phase. Photocatalytic results revealed that the photocatalytic activity of TiO2 increased under visible light irradiation in the presence of the carbonized eggshell membrane. It is found that TiO2-CESM produced the highest photocatalytic degradation of 93 % within 5 hours of irradiation time.

High-performance lithium battery driven by hybrid lithium storage mechanism in 3D architectured carbonized eggshell membrane anode

The increasing demand for large-capacity lithium batteries requires new anode materials satisfying both high capacity and long-life cycles. Here, a free-standing, binder-free, and environmentally friendly carbonized eggshell membrane (CEM) anode with a highly conductive interwoven network is presented for the use in high-performance lithium batteries. Highly porous and naturally doped nitrogen in CEM structure enables a unique hybrid Li storage mechanism where the effective insertion of Li ions and highly uniform Li metal deposition occur without Li dendrites formation. By employing a three-dimensionally architectured CEM anode, an areal capacity as high as 10 mA h cm−2 (357.2 A h L−1 in volumetric capacity) is achieved with an average Coulombic efficiency of 97.6% over 1300 h. The CEM anode also exhibits high Li-ion diffusivity, stable voltage hysteresis, and excellent cycling performance even after 1000 cycles at 0.5C, making it an environmentally sustainable electrode material for high-performance Li-ion batteries.

Nickel Oxide Immobilized on the Carbonized Eggshell Membrane for Electrochemical Detection of Urea

Urea oxidation reaction (UOR) has been known as a viable method for renal/liver disease diagnostic detection. Here, we reported a three-dimensional (3D) nickel oxide nanoparticles dressed carbonized eggshell membrane (3D NiO/c-ESM) as a modified electrode toward urea detection. Several common physical measurements were employed to confirm its structural and morphological information. NiO/c-ESM modified electrode exhibits an outstanding performance for urea determination with a linear range from 0.05 to 2.5 mM, and limit detection of ∼20 μM (3σ). This work offered a green approach for introducing 3D nanostructure through employing biowaste ESMs as templates, providing a typical example for producing new value-added nanomaterials with urea detection.

Low‐Temperature Growth of Hard Carbon with Graphite Crystal for Sodium‐Ion Storage with High Initial Coulombic Efficiency: A General Method

AbstractPractical application of hard carbon materials in sodium‐ion batteries (SIBs) is largely limited by their low initial coulombic efficiency (ICE), which may be improved by increasing the graphitization degree. However, biomass‐derived hard carbon is usually nongraphitizable and extremely difficult to graphitize by direct heating even at 3000 °C. Herein, a general strategy is reported for fabricating hard carbon materials with graphite crystals at 1300 °C promoted by external graphite that serves as a crystal template for the growth of graphite crystals. The graphite crystals enable the contacted pseudographitic domains with a high‐level ordered structure, large domain size, and low defects, leading to an enhanced ICE. The obtained hard carbon materials with graphite crystals, using the carbonized eggshell membranes, and sucrose‐derived microsphere as precursors, achieve very high ICE of 89% and 91% with reversible capacity of 310 and 301 mA h g−1, respectively. Therefore, using external graphite to promote high‐level ordering pseudographitic domains at low temperature is quite useful to improve ICE for SIB applications.

SnO2 Nanosheets Anchored on a 3D, Bicontinuous Electron and Ion Transport Carbon Network for High-Performance Sodium-Ion Batteries.

Here, we demonstrate the in situ growth of SnO2 nanosheets on a freestanding carbonized eggshell membrane (CEM), which provides three-dimensional, bicontinuous electron and ion transport pathways through a massively interconnected carbon fiber skeleton and interpenetrated pore network, respectively. This CEM has other advantages such as the ability to alleviate mechanical stress during cycling as a buffer matrix. When used as an additive-free anode in a sodium-ion battery, SnO2 nanosheets can realize a complete electrochemical reaction and maintain good cycling stability with the help of a CEM. For instance, SnO2 nanosheets delivered a high reversible capacity of 656 mA h g-1 in the 5th cycle at 0.1 A g-1, approaching 98% of its theoretical specific capacity, and maintained a high reversible specific capacity of 420 mA h g-1 after 200 cycles at 0.2 A g-1.

Bio-inspired synthesis of 3-D network of NiO-Ni nanowires on carbonized eggshell membrane for lithium-ion batteries

Composite nanowires incorporating both metal oxide and metal nanoparticles as the basic building units are attracting much attention recently. We report here a facile approach to synthesize 3D networks of 1D nanowires of formed by both NiO and Ni nanoparticle. The composite nanowires were in-situ synthesized on carbonized eggshell membrane. Here, α-Ni(OH)2 nanowire precursor was synthesized on eggshell membrane under mild conditions in a diaphragm-assisted reactor first. Then the precursor was transformed into composite of NiO-Ni nanowires on carbonized eggshell membrane under heat treatment in argon. The eggshell membrane played multiple roles as the substrate to collect the α-Ni(OH)2 nanowire precursor and then as the source of reducing agents to partially reduce Ni2+ to Ni0. When tested for lithium-ion batteries, the composite of 3D networks NiO-Ni nanowires attached on carbonized eggshell membrane demonstrated impressively improved rate and cycling performances, as compared to that of bare NiO nanowires. The idea and method outline here based on bio-inspired synthesis using bio-template to prepare composites could be applied to synthesize other functional materials.

CdS-TiO2 NPs decorated carbonized eggshell membrane for effective removal of organic pollutants: A novel strategy to use a waste material for environmental remediation

Eggshell membrane (ESM), which locates between the egg white and the inner surface of the eggshell, is generally considered as waste; however, it can be utilized in various fields. In this contribution, we report a stable CdS-TiO2 decorated carbonized egg shell membrane (CESM) composite for effective removal of methylene blue (MB). The ESM was utilized as a template for the coating of CdS/titanium tetraisopropoxide at its fibrous network and subsequently sintered at inert atmosphere to produce CdS-TiO2 decorated carbonized eggshell membrane (CdS-TiO2/CESM). The presence of CdS-TiO2 NPs on the CESM fibrous network introduces effective adsorptive and photocatalytic properties for the removal of organic pollutants from water. This study suggests a simple approach to control the pollutant in an eco-friendly way by utilizing a waste material.

Carbonized Eggshell Membranes as a Natural and Abundant Counter Electrode for Efficient Dye‐Sensitized Solar Cells

Carbonized Eggshell Membranes as a Natural and Abundant Counter Electrode for Efficient Dye‐Sensitized Solar Cells

Recycling chicken eggshell membranes for high-capacity sodium battery anodes

As a waste recycling process, pyrolytic eggshell membrane carbonization can produce carbonized eggshell membrane (CEM) materials for sodium battery anodes. The CEM contains a high interconnectivity porous structure of carbon fiber networks with a controllable surface area and nitrogen content. The electrochemical properties of CEM combined with this process have potential applications in providing a new type of sustainable resource for clean energy storage.

Eggshell Membrane-Derived Polysulfide Absorbents for Highly Stable and Reversible Lithium–Sulfur Cells

The carbonized eggshell membrane (CEM) powder with abundant micropores and high porosity is embedded within conventional sulfur cathodes (CEM-S cathodes) as a polysulfide (PS) absorbent for lithium–sulfur batteries. The CEM PS absorbent effectively limits the irreversible active material loss from CEM-S cathodes and prevents the formation of severe inactive agglomerations on the surface of the cathode during cycling. In addition to trapping the migrating PSs, the conductive and porous CEM facilitates efficient electron transport and electrolyte immersion, which ensures successive reactivation and reutilization of the trapped active material. As a result, the CEM-S cathodes with a reasonable sulfur content of 60 wt % exhibit a high capacity retention rate of 85% and a low capacity fade rate of 0.10% per cycle for 150 cycles. Such superior cycle stability suggests that natural starting materials with unique porous structures can be utilized to manufacture high-performance cell components for Li–S cells.

High-Energy, High-Power Lithium-Sulfur Batteries

There is immense interest in developing rechargeable battery systems with high energy density and long cycle life at an affordable cost for portable electronic devices, electric vehicles, and stationary storage of electricity produced by renewable sources like solar and wind. The current lithium-ion technology based on lithium-insertion compound electrodes is limited in energy, so cathodes like sulfur and oxygen have become appealing as they offer an order of magnitude higher capacity and are abundant. The reaction of sulfur with lithium to provide Li2S, invoving two electrons per sulfur, provides a capacity of 1,672 mAh/g, which can enable packaged lithium-sulfur cells with two to three times higher energy density than the current lithium-ion batteries. However, several challenges prevent the practical application of Li-S batteries: high resistivity of sulfur and discharged products, dissolution of intermediate polysulfides, and shuttling effect of polysulfides, which result in low utilization of sulfur and poor cycle life. Significant improvements have been made in recent years, but further improvements and a better understanding of the Li-S batteries are still needed. This presentation will focus on Li-S systems with a carbon interlayer between the cathode and the separator, Li2S cathodes, and polysulfide cathodes.Our group has developed a novel Li-S cell configuration utilizing a bifunctional carbon interlayer between the separator and regular sulfur electrode for improving the cyclability and rate capability. The interlayer effectively decreases the resistance of the sulfur electrode, facilitates the absorption of soluble polysulfide shuttling in the electrolyte, and acts as a second current collector for accommodating the migrating active material from the sulfur electrode. This novel approach not only simplifies the processing without requiring elaborate synthesis of composites and surface chemistry modification, but also improves the rate capability and cycle life. A variety of carbon interlayers have been developed for this approach, including binder-free carbon nanotube (CNT) paper, microporous carbon paper, and naturally abundant materials like carbonized eggshell membranes and plant leaves.Li/dissolved polysulfide batteries have the advantage of utilizing dissolved active material, which could enhance the kinetics of the redox reactions of sulfur. However, the carbon electrode used as a current collector plays a key role in the cell performance. We utilized a binder-free, free-standing CNT paper as the current collector, which can effectively trap the charged and discharged products in amorphous state. The nanoscaled structure of the CNT paper ensures electron and ion access to the active material upon cycling, leading to unprecedented high capacities of 1,400 mAh/g with good cycle life. Other binder-free carbon papers such as carbon nanofiber can also work effectively with this system.Lithium metal or lithiated anodes are required to be used in Li-S batteries since the sulfur cathodes do not have any lithium in the initial stage, which poses a significant safety hazard. Li2S with a theoretical capacity of 1,169 mAh/g, is more desirable as the cathode material than sulfur. However, it is not straightforward to make Li2S cathode because of its high resistivity and reactivity in air. Our group has developed a simple Li2S-CNT sandwiched electrode which can effectively trap the air-sensitive Li2S in the electrode with good electron and ion accessibility. A high capacity of around 800 mAh/g was obtained at a rate of C/10 over 100 cycles. Also, another approach to chemically synthesize Li2S in situ by using a lithiated graphite as a lithium donor to reduce polysulfides will be presented.

Carbonized Eggshell Membrane as a Natural Polysulfide Reservoir for Highly Reversible Li‐S Batteries

Carbonized sucrose-coated eggshell membranes (CSEMs) consisting of natural micropores function well as a polysulfide reservoir in Li/dissolved polysulfide cells. The bottom CSEM current collector encapsulates the active material, while the upper CSEM inhibitor intercepts the migrating polysulfides. This design with CSEM allows the dissolved polysulfides to be localized and the electrochemical reactions within the cathode region to be stabilized, resulting in high discharge capacity, long-term cycle stability, and high sulfur loading.

Carbonized Chicken Eggshell Membranes with 3D Architectures as High‐Performance Electrode Materials for Supercapacitors

AbstractSupercapacitor electrode materials are synthesized by carbonizing a common livestock biowaste in the form of chicken eggshell membranes. The carbonized eggshell membrane (CESM) is a three‐dimensional macroporous carbon film composed of interwoven connected carbon fibers containing around 10 wt% oxygen and 8 wt% nitrogen. Despite a relatively low surface area of 221 m2 g−1, exceptional specific capacitances of 297 F g−1 and 284 F g−1 are achieved in basic and acidic electrolytes, respectively, in a 3‐electrode system. Furthermore, the electrodes demonstrate excellent cycling stability: only 3% capacitance fading is observed after 10 000 cycles at a current density of 4 A g−1. These very attractive electrochemical properties are discussed in the context of the unique structure and chemistry of the material.