Aprotic Lithium-Carbon Dioxide Batteries: Reaction Mechanism and Catalyst Design.

In recent years, the combustion of fossil fuels leads to the release of a large amount of CO2 gas, which induces the greenhouse effect and the energy crisis. To solve these problems, researchers have turned their focus to a novel Li-CO2 battery (LCB). LCB has received much attention because of its high theoretical energy density and reversible CO2 reduction/evolution process. So far, the emerging LCB still faces many challenges derived from the slow reaction kinetics of discharge products. In this review, the latest status and progress of LCB, especially the influence of the structure design of cathode catalysts on the battery performance, are systematically elaborated. This review summarizes in detail the existing issues and possible solutions of LCB, which is of high research value for further promoting the development of Li-Air battery.

Waste-derived iron catalyzed bio-electro-Fenton process for the cathodic degradation of surfactants.

The application of waste-derived iron for reuse in wastewater treatment is an effective way of utilizing waste and attaining sustainability in the overall process. In the present investigation, bio-electro-Fenton process was initiated for the cathodic degradation of surfactants using waste-iron catalyzed MFC (WFe-MFC). The waste-iron was derived from spent tonner ink using calcination at 600 °C. Three surfactants namely, sodium dodecyl sulphate (SDS), cetyltrimethylammonium bromide, and Triton x-100 were selected as target pollutants. The effect of experimental factors like application of catalyst, contact time, external resistance, and anodic substrate concentration on the SDS degradation was investigated. At a neutral pH, the cathodic surfactants removal efficiency in WFe-MFC was above 85% in a contact time of 180 min with the initial surfactant concentration of ∼20 mg L-1 and external resistance of 100 Ω. The long-term operation using secondary treated real wastewater with unchanged cathode proved that the catalyst was still active to produce effluent SDS concentration of less than 1 mg L-1 in 4 h of contact time after 16 cycles. In a way, the present investigation suggests a potential application for spent tonner ink in the form of Fenton catalyst for wastewater treatment via bio-electro-Fenton MFC.

Crystal Phase-Controlled Modulation of Binary Transition Metal Oxides for Highly Reversible Li-O2 Batteries.

Reducing charge-discharge overpotential of transition metal oxide catalysts can eventually enhance the cell efficiency and cycle life of Li-O2 batteries. Here, we propose that crystal phase engineering of transition metal oxides could be an effective way to achieve the above purpose. We establish controllable crystal phase modulation of the binary MnxCo1-xO by adopting a cation regulation strategy. Systematic studies reveal an unprecedented relevancy between charge overpotential and crystal phase of MnxCo1-xO catalysts, whereas a dramatically reduced charge overpotential (0.48 V) via a rational optimization of Mn/Co molar ratio = 8/2 is achieved. Further computational studies indicate that the different morphologies of Li2O2 should be related to different electronic conductivity and binding of Li2O2 on crystal facets of MnxCo1-xO catalysts, finally leading to different charge overpotential. We anticipate that this specific crystal phase engineering would offer good technical support for developing high-performance transition metal oxide catalysts for advanced Li-O2 batteries.

Simultaneous sulfamethoxazole degradation with electricity generation by microbial fuel cells using Ni-MOF-74 as cathode catalysts and quantification of antibiotic resistance genes.

Antibiotic wastewater presents serious challenges in water treatment. Metal-organic frameworks (MOFs) have received significant attention as promising precursors and sacrificial templates in the preparation of porous carbon-supported catalysts. Herein, we investigated the sulfamethoxazole (SMX) degradation and electrochemical performance of microbial fuel cells (MFCs) that applied as-prepared Ni-MOF-74 and Ni-N-C (Ni-MOF-74 underwent pyrolysis treatment at different temperatures) as air-cathode catalyst. Firstly, the electrocatalytic activity towards oxygen reduction reaction (ORR) of the catalyst was investigated by rotating disk electrode. The results showed that electron transfer number for Ni-MOF-74 was 2.12, while that of 800Ni-N-C was 3.44, which was close to four-electron reduction. Applying Ni-MOF-74 in MFCs, a maximum power density of 446 mW/m2 was obtained, which was close to that of 800Ni-N-C. Besides, using Ni-MOF-74 as cathode catalyst, a chemical oxygen demand removal rate of about 84% was obtained, and the degradation rate of 10 mg/L SMX was 61%. The degradation rate decreased with increasing antibiotic concentration, but the average degradation efficiency increased stepwise. Additionally, the relative abundance of resistant gene sul1 in the reactors of the new catalytic material was about 62% lower than that of sul1 in the control (Pt/C) reactors, and the relative abundance of sul2 was about 73% lower. Moreover, cost assessments related to the catalyst performance are presented. The findings of this study demonstrated that Ni-MOF-74 could be considered as a two-electron transfer ORR catalyst, and offers a promising technique for preparation of Ni-N-C for use as four-electron transfer ORR catalysts. In comparison, Ni-MOF-74 could be a promising ORR catalyst of MFCs for antibiotic degradation.

Surfactant removal from wastewater using photo-cathode microbial fuel cell and laterite-based hybrid treatment system.

Sodium dodecyl sulfate (SDS) is a widely used anionic surfactant, which finds its way to the receiving water body due to the incapability of conventional wastewater treatment systems to completely remove it. A hybrid treatment system consisting of upflow microbial fuel cell (MFC) with titanium dioxide (TiO2) as a photocathode catalyst was developed for treating synthetic wastewater spiked with SDS (10.00 ± 0.46 mg L-1). Effluent from anodic chamber of MFC was passed through raw laterite soil filter followed by the photo-cathodic chamber with TiO2-coated cathode irradiated with the UV spectrum. This hybrid system was operated under varying hydraulic retention time (HRT) in anodic chamber of MFC. The SDS removal efficiency of more than 96% along with organic matter removal efficiency of more than 71% was obtained by this hybrid system at different HRTs. The MFC having cathode coated with TiO2 could generate a maximum power density of 0.73 W m-3 and 0.46 W m-3 at the HRT of 12 h and 8 h, respectively, showing the adverse effect of increased SDS loading rate on the electrical performance of MFC. This investigation highlighted the importance of HRT in anodic chamber of MFC and offered solution for effective removal of surfactant from wastewater.

Full Parametric Study of the Influence of Ionomer Content, Catalyst Loading and Catalyst Type on Oxygen and Ion Transport in PEM Fuel Cell Catalyst Layers.

To advance the technology of polymer electrolyte membrane fuel cells, material development is at the forefront of research. This is especially true for membrane electrode assembly, where the structuring of its various layers has proven to be directly linked to performance increase. In this study, we investigate the influence of the various ingredients in the cathode catalyst layer, such as ionomer content, catalyst loading and catalyst type, on the oxygen and ion transport using a full parametric analysis. Using two types of catalysts, 40 wt.% Pt/C and 60 wt.% Pt/C with high surface area carbon, the ionomer/carbon content was varied between 0.29-1.67, while varying the Pt loading in the range of 0.05-0.8 mg cm-2. The optimum ionomer content was found to be dependent on the operating point and condition, as well as catalyst loading and type. The data set provided in this work gives a starting point to further understanding of structured catalyst layers.

Toward Highly Efficient Electrocatalyst for Li-O2 Batteries Using Biphasic N-Doping Cobalt@Graphene Multiple-Capsule Heterostructures.

For the promotion of lithium-oxygen batteries available for practical applications, the development of advanced cathode catalysts with low-cost, high activity, and stable structural properties is demanded. Such development is rooted on certain intelligent catalyst-electrode design that fundamentally facilitates electronic and ionic transport and improves oxygen diffusivity in a porous environment. Here we design a biphasic nitrogen-doped cobalt@graphene multiple-capsule heterostructure, combined with a flexible, stable porous electrode architecture, and apply it as promising cathodes for lithium-oxygen cells. The biphasic nitrogen-doping feature improves the electric conductivity and catalytic activity; the multiple-nanocapsule configuration makes high/uniform electroactive zones possible; furthermore, the colander-like porous electrode facilitates the oxygen diffusion, catalytic reaction, and stable deposition of discharge products. As a result, the electrode exhibits much improved electrocatalytic properties associated with unique morphologies of electrochemically grown lithium peroxides.

Improved power and long term performance of microbial fuel cell with Fe-N-C catalyst in air-breathing cathode.

Power output limitation is one of the main challenges that needs to be addressed for full-scale applications of the Microbial Fuel Cell (MFC) technology. Previous studies have examined electrochemical performance of different cathode electrodes including the development of novel iron based electrocatalysts, however the long-term investigation into continuously operating systems is rare. This work aims to study the application of platinum group metals-free (PGM-free) catalysts integrated into an air-breathing cathode of the microbial fuel cell operating on activated sewage sludge and supplemented with acetate as the carbon energy source. The maximum power density up to 1.3 Wm-2 (54 Wm-3) obtained with iron aminoantipyrine (Fe-AAPyr) catalyst is the highest reported in this type of MFC and shows stability and improvement in long term operation when continuously operated on wastewater. It also investigates the ability of this catalyst to facilitate water extraction from the anode and electroosmotic production of clean catholyte. The electrochemical kinetic extraction of catholyte in the cathode chamber shows correlation with power performance and produces a newly synthesised solution with a high pH > 13, suggesting caustic content. This shows an active electrolytic treatment of wastewater by active ionic and pH splitting in an electricity producing MFC.

Nanostructured Bimetallic Iron Molybdenum Nitride as a Non-Precious Cathode Catalyst for Li­O2 Batteries.

Herein we report the facile fabrication and electrocatalytic activity of nanostructured bimetallic iron molybdenum nitride (Fe3Mo3N), which was prepared by an ammonolysis process directly towards the solid state mixture of Mo precursor and Fe precursor. The prepared nanostructured Fe3Mo3N presented remarkable electrocatalytic activities towards both oxygen reduction reaction and oxygen evolution reaction in nonaqueous phase, due to the modulation of electronic configuration of catalyst by Fe element and porous structure. Then, lithium-O2 batteries with nanostructured Fe3Mo3N as cathode catalysts were assembled, which show alleviated polarization and enhanced cyclability.

Co(0.85)Se/Multi-Walled Carbon Nanotube Composite as Alternative Cathode Catalyst for Microbial Fuel Cells.

The development of low-cost and high-performance cathode catalyst remains a great challenge for constructing large-scale microbial fuel cells (MFCs). Here, the multi-walled carbon nanotube (MWCNT) supported cobalt selenide (Co0.85Se) composite was synthesized by a simple and effective hydrothermal process for the first time. Compared with uncomposited electrodes such as MWCNTs and Co0.85Se, the as-prepared Co0.85Se/MWCNT composite electrode exhibited significantly improved electrochemical performance and durability. The maximum power density of Co0.85Se/MWCNT composite electrode is 243.6 mW m­2, which is 12.2 fold higher than that of unmodified electrode and more than twice as much as those observed for MWCNTs cathode (114.1 mW m­2) and Co0.85Se cathode (119.8 mW m­2). This work may provide not only the fundamental studies on carbon supported transition-metal selenide but also a new kind of promising alternative electrode in the technology of power generation from MFCs.

Enhancing substrate utilization and power production of a microbial fuel cell with nitrogen-doped carbon aerogel as cathode catalyst.

OBJECTIVES: Catalytic efficiency of a nitrogen-doped, mesoporous carbon aerogel cathode catalyst was investigated in a two-chambered microbial fuel cell (MFC) applying graphite felt as base material for cathode and anode, utilizing peptone as carbon source. RESULTS: This mesoporous carbon aerogel containing catalyst layer on the cathode increased the maximum power density normalized to the anode volume to 2.7 times higher compared to the maximum power density obtained applying graphite felt cathode without the catalyst layer. At high (2 and 3) cathode/anode volume ratios, maximum power density exceeded 40 W m-3. At the same time, current density and specific substrate utilization rate increased by 58% resulting in 31.9 A m-3 and 18.8 g COD m-3 h-1, respectively (normalized to anode volume). Besides the increase of the power and the rate of biodegradation, the investigated catalyst decreased the internal resistance from the range of 450-600 to 350-370 Ω. CONCLUSIONS: Although Pt/C catalyst proved to be more efficient, a considerable decrease in the material costs might be achieved by substituting it with nitrogen-doped carbon aerogel in MFCs. Such cathode still displays enhanced catalytic effect.

Operando 3D Visualization of Migration and Degradation of a Platinum Cathode Catalyst in a Polymer Electrolyte Fuel Cell.

The three-dimensional (3D) distribution and oxidation state of a Pt cathode catalyst in a practical membrane electrode assembly (MEA) were visualized in a practical polymer electrolyte fuel cell (PEFC) under fuel-cell operating conditions. Operando 3D computed-tomography imaging with X-ray absorption near edge structure (XANES) spectroscopy (CT-XANES) clearly revealed the heterogeneous migration and degradation of Pt cathode catalyst in an MEA during accelerated degradation test (ADT) of PEFC. The degradative Pt migration proceeded over the entire cathode catalyst layer and spread to MEA depth direction into the Nafion membrane.

Enhanced Cathode Performance in Pr0.5Sr0.5FeO3-δ of Perovskite Catalytic Materials via Doping with VB Subgroup Elements (V, Nb, and Ta).

Perovskite-style materials are cathode systems known for their stability in solid oxide fuel cells (SOFCs). Pr0.5Sr0.5FeO3-δ (PSF) exhibits excellent electrode performance in perovskite cathode systems at high temperatures. Via VB subgroup metals (V, Nb, and Ta) modifying the B-site, the oxidation and spin states of iron elements can be adjusted, thereby ultimately adjusting the cathode's physicochemical properties. Theoretical predictions indicate that PSF has poor stability, but the relative arrangement of the three elements on the B-site can significantly improve this material's properties. The modification of Nb has a large effect on the stability of PSF cathode materials, reaching a level of -2.746 eV. The surface structure of PSF becomes slightly more stable with an increase in the percentage of oxygen vacancy structures, but the structural instability persists. Furthermore, the differential charge density distribution and adsorption state density of the three modified cathode materials validate our adsorption energy prediction results. The initial and final states of the VB subgroup metal-doped PSF indicate that PSFN is more likely to complete the cathode surface adsorption reaction. Interestingly, XRD and EDX characterization are performed on the synthesized pure and Nb-doped PSF material, which show the orthorhombic crystal system of the composite theoretical model structure and subsequent experimental components. Although PSF exhibits strong catalytic activity, it is highly prone to decomposition and instability at high temperatures. Furthermore, PSFN, with the introduction of Nb, shows greater stability and can maintain its activity for the ORR. EIS testing clearly indicates that Nb most significantly improves the cathode. The consistency between the theoretical predictions and experimental validations indicates that Nb-doped PSF is a stable and highly active cathode electrode material with excellent catalytic activity.

Application of biomimetically synthesized silver nanoparticles as cathode catalyst, quorum-quencher, and anti-biofouling agent for the performance boosting of microbial fuel cell.

A microbial fuel cell (MFC) is a cutting-edge bioelectrochemical technology, which demonstrates power and other valuables recovery while treating wastewater by cultivating electroactive microbes. However, rampant biofilm growth over the cathode surface of air cathode MFC exacerbates the oxidation-reduction reaction rate, triggering a dip in the overall performance of MFC. In this sense, biosynthesized silver nanoparticles (AgNPs) have garnered a plethora of potential applications as cathode catalysts as well as anti-biofouling agent for MFCs without harming nature. The MFC equipped with the mixture of aloe vera and algae (@5 mg/cm2) synthesized AgNPs on cathode generated a maximum power density of 66.5 mW/m2 and chemical oxygen demand removal efficiency of 85.2%, which was ca. 5.6 times and 1.2 times higher compared to control MFC operated without any catalyst on cathode. Thus, this investigation paves the way for using eco-amiable, low-cost bioderived organic compounds to assist MFC in achieving high power output and other valuables with minimal reliance on chemicals.

Cathode Catalyst Layer Design in PEM Water Electrolysis toward Reduced Pt Loading and Hydrogen Crossover.

Reducing the use of platinum group metals is crucial for the large-scale deployment of proton exchange membrane (PEM) water electrolysis systems. The optimization of the cathode catalyst layer and decrease of the cathode Pt loading are usually overlooked due to the predominant focus of research on the anode. However, given the close relationship between the rate of hydrogen permeation through the membrane in an operating cell and the local hydrogen concentration near the membrane-cathode interface, the structural design of the cathode catalyst layer is considered to be of pivotal importance for reducing H2 crossover, particularly in combination with the use of thin (≲50 µm) membranes. In this study, we have conducted a detailed investigation on the cathode structural parameters, covering the Pt wt % of the Pt/C electrocatalyst, the type of carbon support (Vulcan and high surface area carbon, HSAC), and the ionomer content, with a goal to reduce Pt loading to 0.025 mgPt/cm2 while minimizing the rate of cell hydrogen crossover. We found that the electrochemical performance is mainly influenced by the changes in the interfacial contact resistance due to variations in the cathode thickness. Both the Pt wt % in Pt/C and the ionomer content showed a positive correlation with the measured H2 in O2% in the anode outlet, whereas the Pt loading exhibited an opposite trend. The rate of hydrogen crossover was analyzed in relation to the calculated local volumetric current density within the cathode catalyst layer. Based on the obtained hydrogen mass transfer coefficient, a cathode catalyst layer comprising 40 wt % Pt on HSAC support with an ionomer-to-carbon (I/C) ratio of 0.35 was found to be an optimum configuration for achieving a low Pt loading of 0.025 mgPt/cm2 and a reduced rate of hydrogen crossover.

Controllable Regulation of the Oxygen Redox Process in Lithium-Oxygen Batteries by High-Configuration-Entropy Spinel with an Asymmetric Octahedral Structure.

Designing bifunctional electrocatalysts to boost oxygen redox reactions is critical for high-performance lithium-oxygen batteries (LOBs). In this work, high-entropy spinel (Co0.2Mn0.2Ni0.2Fe0.2Cr0.2)3O4 (HEOS) is fabricated by modulating the internal configuration entropy of spinel and studied as the oxygen electrode catalyst in LOBs. Under the high-entropy atomic environment, the Co-O octahedron in spinel undergoes asymmetric deformation, and the reconfiguration of the electron structure around the Co sites leads to the upward shift of the d-orbital centers of the Co sites toward the Fermi level, which is conducive to the strong adsorption of redox intermediate LiO2 on the surface of the HEOS, ultimately forming a layer of a highly dispersed Li2O2 thin film. Thin-film Li2O2 is beneficial for ion diffusion and electron transfer at the electrode-electrolyte interface, which makes the product easy to decompose during the charge process, ultimately accelerating the kinetics of oxygen redox reactions in LOBs. Based on the above advantages, HEOS-based LOBs deliver high discharge/charge capacity (12.61/11.72 mAh cm-2) and excellent cyclability (424 cycles). This work broadens the way for the design of cathode catalysts to improve oxygen redox kinetics in LOBs.

Activated Co in Thiospinel Boosting Li2CO3 Decomposition in Li-CO2 Batteries.

Catalytic reactions mainly depend on the adsorption properties of reactants on the catalyst, which provides a perspective for the design of reversible lithium-carbon dioxide (Li-CO2) batteries including CO2 reduction (CO2RR) and CO2 evolution (CO2ER) reactions. However, due to the complex reaction process, the relationship between the adsorption configuration and CO2RR/CO2ER catalytic activity is still unclear in Li─CO2 batteries. Herein, taking Co3S4 as a model system, nickel (Ni substitution in the tetrahedral site to activate cobalt (Co) atom for forming multiatom catalytic domains in NiCo2S4 is utilized. Benefiting from the special geometric and electronic structures, NiCo2S4 exhibits an optimized adsorption configuration of lithium carbonate (Li2CO3), promoting its effective activation and decomposition. As a result, the Li-CO2 batteries with NiCo2S4 cathode exhibit remarkable electrochemical performance in terms of low potential gap of 0.42 V and high energy efficiency of 88.7%. This work provides a unique perspective for the development of highly efficient catalysts in Li-CO2 batteries.

Multi-metal ferrite as a promising catalyst for oxygen reduction reaction in microbial fuel cell.

Improving catalytic activity of cathode with noble metal-free catalysts can significantly establish microbial fuel cells (MFCs) as a sustainable and economically affordable technology. This investigation aimed to assess the viability of utilizing tri-metal ferrite (Co0.5Cu0.5 Bi0.1Fe1.9O4) as an oxygen reduction reaction (ORR) catalyst to enhance the performance of cathode in MFCs. Trimetallic ferrite was synthesized using a sol-gel auto-combustion process. Electrochemical evaluations were conducted to assess the efficacy of as-synthesized composite as an ORR catalyst, employing electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). This evaluation revealed that the impregnation of bismuth in the Co-Cu-ferrite structure improves the reduction current response and reduces the charge transfer resistance. Further experiments were conducted to test the performance of this catalyst in an MFC. The MFC with tri-metal ferrite catalyst generated a power density of 11.44 W/m3 with 21.4% coulombic efficiency (CE), which was found to be comparable with commercially available 10% Pt/C used as cathode catalyst in MFC (power density of 12.14 W/m3 and CE of 23.1%) and substantially greater than MFC having bare carbon felt cathode without any catalyst (power density of 2.49 W/m3 and CE of 7.39%). This exceptionally inexpensive ORR catalyst has adequate merit to replace commercial costlier platinum-based cathode catalysts for upscaling MFCs.

Bifunctional Catalysts for CO2 Reduction and O2 Evolution: A Pivotal for Aqueous Rechargeable Zn-CO2 Batteries.

The quest for the advancement of green energy storage technologies and reduction of carbon footprint is determinedly rising toward carbon neutrality. Aqueous rechargeable Zn-CO2 batteries (ARZCBs) hold the great potential to encounter both the targets simultaneously, i.e., green energy storage and CO2 conversion to value-added chemicals/fuels. The major descriptor of ARZCBs efficiency is allied with the reactions occurring at cathode during discharging (CO2 reduction) and charging (O2 evolution) which own different fundamental mechanisms and hence mandate the employment of two different catalysts. This presents an overall complex and expensive battery system which requires a concrete solution, while the development and application of a bifunctional cathode catalyst toward both reactions could reduce the complexity and cost and thus can be a pivotal for ARZCBs. However, despite the increasing research interest and ongoing research, a systematic evaluation of bifunctional catalysts is rarely reported. In this review, the need of bifunctional cathode catalysts for ARZCBs and associated challenges with strategies have been critically assessed. A detailed progress examination and understanding toward designing of bifunctional catalyst for ARZCBs have been provided. This review will enlighten the future research approaching boosted performance of ARZCBs through the development of efficient bifunctional cathode catalysts.

2,6-Diaminopyridine-Based Polyurea as an ORR Electrocatalyst of an Anion Exchange Membrane Fuel Cell.

In order to yield more Co(II), 2,6-diaminopyridine (DAP) was polymerized with 4,4-methylene diphenyl diisocyanates (MDI) in the presence of Co(II) to obtain a Co-complexed polyurea (Co-PUr). The obtained Co-PUr was calcined to become Co, N-doped carbon (Co-N-C) as the cathode catalyst of an anion exchange membrane fuel cell (AEMFC). High-resolution transmission electron microscopy (HR-TEM) of Co-N-C indicated many Co-Nx (Co covalent bonding with several nitrogen) units in the Co-N-C matrix. X-ray diffraction patterns showed that carbon and cobalt crystallized in the Co-N-C catalysts. The Raman spectra showed that the carbon matrix of Co-N-C became ordered with increased calcination temperature. The surface area (dominated by micropores) of Co-N-Cs also increased with the calcination temperature. The non-precious Co-N-C demonstrated comparable electrochemical properties (oxygen reduction reaction: ORR) to commercial precious Pt/C, such as high on-set and half-wave voltages, high limited reduction current density, and lower Tafel slope. The number of electrons transferred in the cathode was close to four, indicating complete ORR. The max. power density (Pmax) of the single cell with the Co-N-C cathode catalyst demonstrated a high value of 227.7 mWcm-2.