Duckweed derived nitrogen self-doped porous carbon materials as cost-effective electrocatalysts for oxygen reduction reaction in microbial fuel cells

Cost-effective metal-free electrocatalysts for oxygen reduction reaction were incredible significance of improvement about microbial fuel cells. In this research, a novel nitrogen self-doped porous carbon material is effectively inferred with KOH activation from a natural and renewable biomass, duckweed. Self-doped nitrogen in carbon matrix of nitrogen-doped porous carbon at 800 °C provides abundant active sites for oxygen reduction and improves the oxygen reduction kinetics significantly. Moreover, the porous structure of nitrogen-doped porous carbon at 800 °C encourages the transition of electrolyte and oxygen molecules throughout the oxygen reduction reaction. Oxygen on the three-phase boundary is reduced to water according to a four-electron pathway on nitrogen-doped porous carbon electrocatalyst. The single-chamber microbial fuel cell with nitrogen-doped porous carbon as electrocatalyst achieves comparable power density (625.9 mW m⁻²) and better stability compared to the commercial Pt/C electrocatalyst. This simple and low-cost approach provides a straightforward strategy to prepare excellent nitrogen-doped electrocatalyst derived from natural and renewable biomass directly as a promising alternate to precious platinum-based catalysts in microbial fuel cells.     

Iron carbide and iron phosphide embedded N-doped porous carbon derived from biomass as oxygen reduction reaction catalyst for microbial fuel cell

The splendid activity of oxygen reduction reaction (ORR) catalyst can greatly promote the power generation of air cathode microbial fuel cell (AC-MFC). Here, benefiting from the rich P element in radish, Fe₃C and Fe₂P incorporated N-doped porous carbon (Fe₃C/Fe₂P@NC-N₄Fe₂) are prepared with the assistance of NH₄Cl through carbothermal reduction method without adding P resources. As expected, Fe₃C/Fe₂P@NC-N₄Fe₂ possesses excellent ORR performance, in which Fe₃C and Fe₂P furnish abundant ORR active sites and the porous structure in N-doped carbon matrix can facilitate mass transfer. Moreover, the AC-MFC assembled with Fe₃C/Fe₂P@NC-N₄Fe₂ as cathodic ORR catalyst exhibits superior power output performance with the maximum power density of 948.9 mW m^?2, which is 1.03 times of that of 20 wt% Pt/C catalyst. Therefore, Fe₃C/Fe₂P@NC-N₄Fe₂ should be a viable ORR catalyst to replace Pt/C catalyst in the application in AC-MFC.     

Design of Fe and Cu bimetallic integration on N and F co-doped porous carbon material for oxygen reduction reaction

At present, fuel cell is considered to be one of the most ideal application technologies of hydrogen energy. In order to develop fuel cells on a large scale and in a sustainable way, low platinum or non-platinum oxygen reduction catalyst has become a research hotspot. In this work, a kind of doped carbon-based catalyst MPFe₁Cu₁-850 is prepared by high temperature synthesis. The catalyst has an ultra-thin lamellar porous structure. In an acidic medium, the MPFe₁Cu₁-850 displays good oxygen reduction reaction (ORR) activity (ΔE_1/2 = 0.725 V). In addition, it shows better stability (91%) and higher methanol tolerance than that of commercial Pt/C catalyst. In our catalyst MPFe₁Cu₁-850, the contents of nitrogen, iron and copper are 10.31 at.%, 0.51 at.%, and 0.50 at.%, respectively. This work shows that high N content, and the proper ratio of iron to copper (Fe:Cu = 1:1), are conducive to the enhancement of ORR activity.     

Astragali Radix-derived nitrogen-doped porous carbon: An efficient electrocatalyst for the oxygen reduction reaction

The development of biomass-derived nitrogen-doped porous carbons (NPCs) for the oxygen reduction reaction (ORR) is important for sustainable energy systems. Herein, NPCs derived from Astragali Radix (AR) via a cost-effective strategy are reported for the first time. The as-prepared AR-950-5 catalyst shows a stacked layer-like structure and porosity. Notably, the optimized AR-950-5 delivers catalytic activity comparable to that of commercial Pt/C (C-Pt/C), with high onset potential, positive half-wave potential and large limiting current density. It also displays superior long-term stability and methanol tolerance for ORR. This work will pave the way for a new approach in the development of highly active and low-cost NPCs for fuel cells.     

Poison tolerance of non-precious catalyst towards oxygen reduction reaction

Oxygen reduction reaction (ORR) plays an important role in microbial fuel cell (MFC) performance. But the poison ions in wastewater may have a considerable effect on the activity of ORR catalysts. In this paper, we herein investigated the effect of typical NH₄⁺ and S^2? ions on the activity of different ORR catalysts, such as biomass derived carbon (bamboo charcoal (BC)), nitrogen doped graphene (N-G), iron/nitrogen co-doped graphene (Fe/N-G) and Pt/C catalysts. The results showed that the ORR catalytic activity was decreased in the presence of both NH₄⁺ and S^2? ions. In detail, the NH₄⁺ ion only had a slight and similar effect on the catalysts. However, the effect of S^2? on catalyst activity was much more negative, compared to that of NH₄⁺. Notably, the BC, N-G and Fe/N-G catalysts exhibited a higher poison tolerance than Pt/C, indicating that BC, N-G and Fe/N-G catalysts could serve as poison tolerance ORR catalysts in both of NH₄⁺ and S^2? condition.     

FeNx nanoparticles embedded in three-dimensional N-doped carbon nanofibers as efficient oxygen reduction reaction electrocatalyst for microbial fuel cells in alkaline and neutral media

Herein, an approach is reported for the fabrication of 3D carbon nanofibers (CNFs) wrapped by carbon nanotubes (CNT) with graphitic carbon-encased FeNx nanoparticles originated from metal–organic frameworks (MOFs). It is found that Fe-FeNx@N-CNT/CNFs exhibits outstanding catalytic activity towards ORR, whose half-wave potential are 0.89 V and 0.87 V in alkaline and neutral environments, respectively, much higher than MOF-based catalysts reported so far and commercial Pt/C. When the obtained cathode catalysts are loaded in MFCs for power generation test, the experimental consequences show that the Fe-FeNx@N-CNT/CNFs cathode exhibits a supernal power density of 742.26 mW·m^?2 and output current density of 3241 mA·m^?2 which are comparable to Pt/C. The splendid ORR catalytic performance is mainly attributable to the three-dimensional structure of carbon nanofibers and the active sites of Fe-Nx. These result in a higher graphitization degree beneficial for electronic mobility, high specific surface area, benign mesoporous nanostructure and excellent mass transfer capability. The strategy provides a new scheme to devise and research Fe-Nx electrocatalysts with MOF-based for the conversion of clean and environment-friendly energy.     

Fe and N co-doped carbon derived from melamine resin capsuled biomass as efficient oxygen reduction catalyst for air-cathode microbial fuel cells

Cathode oxygen reduction reaction (ORR) performance is crucial for power generation of microbial fuel cells (MFCs). The current study provides a novel strategy to prepare Fe/N-doped carbon (Fe/N/C) catalyst for MFCs cathode through high temperature pyrolyzing of biomass capsuling melamine resin polymer. The obtained Fe/N/C can effectively enhance activity, selectivity and stability toward 4 e^– ORR in pH neutral solution. Single chamber MFC with Fe/N/C air cathode produces maximum power density of 1166 mW m⁻², which is 140% higher than AC cathode. The improved performance of Fe/N/C can be attributed to the involvement of nitrogen and iron species. The excellent stability can be attributed to the preferential structure of the catalyst. The moderate porosity of the catalyst facilitates mass transfer of oxygen and protons and prevents water flooding of triple-phase boundary where ORR occurs. The biomass particles encapsulated in the catalyst act as skeletons, which prevents catalyst collapse and agglomeration.     

Biomass-derived N-doped porous activated carbon as a high-performance and cost-effective pH-universal oxygen reduction catalyst in fuel cell

Nitrogen (N) doped porous activated carbons (TGC-T) derived from tofu gel are prepared through a facile, economic and eco-friendly method. The as-prepared TGC-900 possesses high specific surface area (651.78 m² g⁻¹) and homogeneous doping N (Content of N: 5.52 at.%). Reasonably, TGC-900 exhibits excellent oxygen reduction reaction (ORR) activity, stability and methanol resistance in neutral, alkaline and acidic medium. Moreover, TGC-900 also shows outstanding ORR performance in the application of microbial fuel cell (MFC) with the highest output voltage (544 ± 6 mV) and maximum power density (977 ± 32 mW m⁻²). Inspiringly, four single-chamber air cathode MFCs (AC-MFCs) in series can drive a light-emitting diode (LED) to work is firstly reported which further provides a more intuitively method to evaluate the performance of generating electricity for MFCs. Thus, the high performance and cost-effective ORR catalyst TGC-900 is expected to apply in the field of fuel cells.     

S,N co-doped graphene quantum dots decorated TiO2 and supported with carbon for oxygen reduction reaction catalysis

Sluggish kinetics and catalyst instability in oxygen reduction reaction are the central issues in fuel cell and metal-air battery technologies. For that, highly active, stable, and low-cost non-platinum based electrocatalysts for oxygen reduction reaction are an immediate requirement in fuel cell and metal-air battery technologies. A new composite (S,N-GQD/TiO₂/C-800) is synthesized, made of sulfur (S) and nitrogen (N) co-doped graphene quantum dot (GQD) with TiO₂. This composite is supported on carbon on heating at 800 °C under N₂ atmosphere and is explored for oxygen reduction reaction (ORR) catalyst. The synthesized composite S,N-GQD/TiO₂/C-800, shows outstanding catalytic activity with an onset potential of 0.91 V and a half-wave potential of 0.82 V vs. RHE, an alkaline medium. The Tafel slope of the catalyst is 61 mV dec^?1. The catalyst is an excellent methanol tolerant and shows good stability in an alkaline medium. The excellent ORR activity of S,N-GQD/TiO₂/C-800 is ascribed to well-built interactivity between the S,N-GQD/TiO₂, and the carbon support. The unique structure offers advantages, with outstanding electrical conductivity, high surface area, and excellent charge transfer kinetics between the doped GQD and TiO₂ interface and subsequently from the carbon surface to the S,N-GQD/TiO_2.     

Waste wine mash-derived doped carbon materials as an efficient electrocatalyst for oxygen reduction reaction

Oxygen reduction reaction (ORR) is a core reaction of fuel cell and metal-air cell. In recent years, it has been a hot topic to study non-precious metal catalysts for ORR. Herein, we have used waste wine mash-derived carbon, melamine and ferric chloride to prepare a Fe- and N- co-doped carbon catalyst. The specific surface area of the catalyst is up to 1066.6 m² g⁻¹. And its wave potential is 15 mV higher than that of commercial Pt/C catalyst. The ORR on our catalyst followed a four-electron pathway; and it has high stability and high impressive immunity to methanol. After continuous oxygen reduction of 30,000s, the retention rate is 90%.     

Non-Pt catalyst as oxygen reduction reaction in microbial fuel cells: A review

Oxygen Reduction Reactions (ORR) are one of the main factors of major potential loss in low temperature fuel cells, such as microbial fuel cells and proton exchange membrane fuel cells. Various studies in the past decade have focused on determining a method to reduce the over potential of ORR and to replace the conventional costly Pt catalyst in both types of fuel cells. This review outlines important classes of abiotic catalysts and biocatalysts as electrochemical oxygen reduction reaction catalysts in microbial fuel cells. It was shown that manganese oxide and metal macrocycle compounds are good candidates for Pt catalyst replacements due to their high catalytic activity. Moreover, nitrogen doped nanocarbon material and electroconductive polymers are proven to have electrocatalytic activity, but further optimization is required if they are to replace Pt catalysts. A more interesting alternative is the use of bacteria as a biocatalyst in biocathodes, where the ORR is facilitated by bacterial metabolism within the biofilm formed on the cathode. More fundamental work is needed to understand the factors affecting the performance of the biocathode in order to improve the performance of the microbial fuel cells.     

A glassy carbon electrode modified with tailored nanostructures of cobalt oxide for oxygen reduction reaction

Herein we report on various surface morphological characteristics of the synthesized cobalt oxide (Co₃O₄) nanostructures obtained by means of facile one-step hydrothermal method for oxygen reduction reaction (ORR). The synthesized nanostructures of Co₃O₄ were adequately characterized by field emission scanning electron microscopy (FESEM) fitted with Energy-dispersive X-ray spectroscopy (EDX) elemental mapping, X-ray diffraction (XRD) and Raman techniques. The electrochemical studies were carried out to analyse the performance of as-synthesized catalysts for ORR by cyclic voltammetry (CV), and chronoamperometric (CA) techniques. A higher electrocatalytic response was observed for Co₃O₄ nanocubes compared with all the other controlled electrodes by CV with a current density of 0.69 mA/cm² at a potential value of −0.46 V. The as-synthesized material showed adequate tolerance against methanol observed by CV in the presence of 0.5 M methanol, and good stability when compared with commercial Pt/C catalyst using the CA technique.     

PtFe alloy catalyst supported on porous carbon nanofiber with high activity and durability for oxygen reduction reaction

To reduce the high cost of oxygen reduction reaction (ORR) catalyst and improve the performance of the proton exchange membrane fuel cell (PEMFC), low-Pt or non-Pt catalysts have been studied in recent years. In this paper, PtFe alloy nanoparticles are loaded on porous carbon nanofiber (PCNF) via one-step modified glycol reduction method by adjusting solution pH. On the surface of PCNF, PtFe alloy nanoparticle can be uniformly dispersed with a narrow particle size distribution. The catalyst Pt_4.8Fe/PCNF prepared in pH = 7 solution with PCNF as carbon support exhibits better ORR performance, which shows even 18 mV higher onset potential than that of commercial catalyst Pt/C (Johnson Matthey, JM20). Moreover, comparable durability is also obtained through accelerated durability test (ADT) test after 2000 cycles. The excellent performance of Pt_4.8Fe/PCNF catalyst may attribute to the structural and electronic effects of transition metal in the PtFe alloy. The rough surface and porous structure of PCNF is also supposed to be beneficial for performance improvement.     

Templating synthesis of hierarchically meso/macroporous N-doped microalgae derived biocarbon as oxygen reduction reaction catalyst for microbial fuel cells

N-doped carbons have been hailed as cost effective catalysts for the large-scale commercialization of microbial fuel cells (MFCs). In this paper, we developed a hierarchically meso/macroporous N-doped biocarbon by templating approach using Chlorella pyrenoidosa as precursor. The results showed that graphitic-N was the dominating functional group contributing to oxygen reduction reaction (ORR) performance. In addition, the role of pore structure was identified and the results suggested that mesopores exhibited a nearly linear correlation with limiting current density and half-wave potential, while electrochemical surface area almost linearly varied with macropores in the carbon materials. These results implied that mesopores play a dominating role in facilitating ion and oxygen supply and creating accessible active sites for ORR, while macropores mainly served as an electrolyte buffering reservoir shortening the electrolyte diffusion distances in the prepared catalysts. The optimized meso/macro pore structure enhanced the accessibility of the active sites and facilitated the mass transport of ion and oxygen, and consequently improved ORR performance of catalyst. The as-prepared catalyst exhibited a remarkably higher power generation than that of the commercial Pt/C in MFCs. This paper offered an insight into the effect of pore structure on the ORR performance of catalysts, and also provided an alternative avenue for synthesizing meso/macroporous carbon catalysts for the applications of MFCs.     

Melamine-assisted synthesis of paper mill sludge-based carbon nanotube/nanoporous carbon nanocomposite for enhanced electrocatalytic oxygen reduction activity

Developing efficient and cheap electrocatalysts as substitutes for commercial Pt/C in the oxygen reduction reaction(ORR)is extremely necessary. Herein, paper mill sludge (PMS) was utilized to produce iron, nitrogen and sulfur co-doped carbon nanotube/nanoporous carbon nanocomposite (PMS-CNT/C) by pyrolysis. PMS-CNT/C-b, one of as-prepared PMS-CNT/C exhibited excellent oxygen reduction reaction activity with an onset potential of 0.99 V vs. RHE and half-wave potential of 0.77 V vs. RHE, which was similar to the commercial Pt/C catalyst (onset potential of 0.99 V vs. RHE and half-wave potential of 0.76 V vs. RHE). It had longer-term stability and higher methanol tolerance in alkaline medium than Pt/C. Moreover, the new catalyst also exhibited excellent catalytic performance in neutral solution. The energy output of microbial fuel cells loaded with PMS-CNT/C-b catalyst was also higher than that of commercial Pt/C under neutral condition. The excellent ORR performance of PMS-CNT/C-b was due to the carbon nanotube/nanoporous structure and the synergistic effect of abundant N groups, iron nitrides and thiophene-S. The formation of CNTs in the carbon nanotube/nanoporous carbon nanocomposite was mainly attributed to melamine, which was added into PMS and was at first just considered as a nitrogen source to develop N-doped PMS-based catalysis in this work. The synthesis of paper mill sludge-based carbon nanotube/nanoporous nanocomposite and its excellent ORR activity will make the new catalyst a promising cathodic electrocatalyst alternative for fuel cells.     

Phosphorus-doped hierarchical porous carbon as efficient metal-free electrocatalysts for oxygen reduction reaction

Recently, fuel cells and metal-air batteries have attracted extensive attentions. Researching and developing non-noble metal catalyst with high electrocatalytic activity and low cost is one of the important challenges for these energy storage and conversion devices. In this study, phosphorus doped hierarchical porous carbon (P-HPC) has been firstly synthesized via a hard template method. The prepared PHPC possesses a unique porous structure which consists of micropores, mesopores and macropores simultaneously. The electrocatalytic activity of the PHPC toward ORR in KOH solution has been studied and compared with the ordinary structured phosphorus doped carbon (PC) and the commercial Pt/C by means of rotating ring-disk electrode (RRDE) technique. The prepared PHPC exhibits an excellent electrocatalytic performance toward ORR in terms of the electrocatalytic activity, the reaction kinetics, the durability and the methanol tolerance. And the high electrocatalytic activity and durability of PHPC could be attributed to the special hierarchical porous structure. This research demonstrates that the rational design of the microstructures for catalyst plays significant roles in improving the catalytic activity for the ORR.     

Yuba-like porous carbon microrods derived from celosia cristata for high-performance supercapacitors and efficient oxygen reduction electrocatalysts

Here, a novel yuba-like porous carbon microrod is prepared via a simple and facile strategy by using the fluffy fibers of celosia cristata petals (FCCP) as the raw material. The optimized carbon microrod (FCCP-CM-900) possesses unique yuba-like structure, high specific surface area (1680 m² g⁻¹) and large pore volume (0.98 cm³ g⁻¹), and effective nitrogen (∼4.52 at.%) and oxygen (∼5.49 at.%) doping, which can enhance the wettability and conductivity (7.9 S cm⁻¹). As the electrode material for supercapacitor, FCCP-CM-900-based supercapacitor presents high specific capacitance (314.5 F g⁻¹ at 0.5 A g⁻¹) in 6.0 M KOH aqueous electrolyte. The FCCP-CM-900-based symmetrical supercapacitor displays high energy density (18.6 Wh kg⁻¹ at 233.4 W kg⁻¹) and outstanding cycling stability (98% capacitance retention after 10,000 cycles) in 1.0 M Na₂SO₄ electrolyte. In addition, served as oxygen reduction electrocatalyst, the FCCP-CM-900 also exhibits excellent catalytic activity, good durability, together with high methanol tolerance in alkaline electrolyte, which makes it a highly efficient air cathode material toward zinc–air cell.     

Efficient oxygen reduction in a microbial fuel cell based on carbide-derived carbon electrode synthesized using thiourea as the single source of electroconductive heteroatoms and graphitic carbon

A novel one step method was developed to dope nitrogen (N), sulfur (S) and carbon (C) in the Fe nanoparticles-dispersed carbon nanofibers (CNFs) grown over carbide-derived carbon (CDC), using thiourea as the single source of N, S and C. The synthesized N/S-Fe-CNF/CDC electrode was successfully used in a microbial fuel cell (MFC). When tested as the oxygen reduction reaction (ORR) catalyst, the electrode achieved a high current density (2.261 ± 0.002 mA/cm²), high OCP (0.611 ± 0.005 V), high stability upto 400 cycles, response time of ∼11 s, electron transfer number in the range 3.73–4.03, and Tafel slopes of −0.0627 and −0.183 V/dec at low and high current densities, respectively. A first order kinetics and a 4e⁻ pathway were deduced from the ORR analysis. Notably, the fabricated MFC based on the prepared electrode produced a high current density of 1.3887 ± 0.002 mA/cm², high OCP of 0.626 ± 0.005 V and maximum power density of 0.238 ± 0.002 mW/cm², attributed to the synergistic effects of heteroatoms, Fe nanoparticles, and CNFs.     

Synthesis and electrocatalytic properties of M (Fe,Co),N co-doped porous carbon frameworks for efficient oxygen reduction reaction

The exploitation of high efficiency non-precious metal electrocatalysts towards oxygen reduction reaction (ORR) is great significant for large-scale commercialization of next-generation fuel cells. In this work, we designed and fabricated a series of porous carbazole-based N and M (Co, Fe) doped carbon framework catalysts which were obtained by the pyrolysis of a N-rich hypercrosslinked polymers derived from Friedel–Crafts reaction (abbreviated as TSP-HCP-900) followed by the incorporation of metal into the as-resulted N rich carbon (abbreviated as M-TSP-HCP-900, M = Co, Fe). Based on the high specific surface, excellent porosity, large pyridine nitrogen content and synergistic catalytic effects between the N dopants and metal nanoparticles, the M-TSP-HCP-900 exhibited superior ORR catalytic activity. Among them, the Co-TSP-HCP-900 possesses better electrocatalysis, i.e., a high diffusion limiting current density of 4.74 mA cm^?2, half-wave potential of 0.8 V (vs. RHE, the same below) and onset potential of 0.9 V were found, respectively. In addition, this catalyst also discloses an excellent methanol tolerance, better durability and a biased 4e^? reaction pathway, which are comparable to state-of-the-art Pt/C catalysts. Taking advantage of mentioning above, the M-TSP-HCP-900 may hold great potentials as promising alternative of precious metal catalysts for electrochemical energy conversion and storage.