Carbon Electrocatalysts Research Articles

ZIF-67 derived N doped carbon embedded CoxP for superior hydrogen evolution

Abstract Developing a sustainable non-noble hybrid electrocatalyst for effective electrocatalysis is the most crucial task; particularly in sustainable hydrogen energy production in the realm of energy conversion. In this work, effective thermal pyrolysis process followed by phosphorization strategy was employed to prepare and fabricate ZIF-67 (Zeolitic imidazole) assisted Co2P/N doped carbon electrocatalyst for hydrogen evolution reaction (HER). The optimized Co2P/N–C electrocatalyst exhibited hollow porous nanostructures as confirmed from the scanning electron microscopy. The achieved porous nanostructure improved the efficiency of the charge and mass transportation which is confirmed by the BET analysis, has high surface area value of 94.731 m2/g. In addition, a transition metal atom can regulate reactants adsorption and desorption capacity by modulating Co and P electronic configuration. The electrochemical studies of fabricated ZIF-67 derived Co2P/N–C electrode were analyzed using 1.0 M alkaline potassium hydroxide (KOH) medium in 3 electrode system process. Whilst, optimizing the pyrolysis temperature during the phosphorization will remarkably enhance the favourable characteristics of the hydrogen generation. Notably, the optimized ZIF-67 derived Co2P/NC at 350 °C electrode exhibited low overpotential (135 mV) at minimum 10 mA/cm2 and low 120.3 mV/dec Tafel slope. Besides, electrode stability at 10 mA/cm2 current density was verified by chronoamperometry test. Hence, this study furnishes the potential technique for the development of advanced hybrid MOF electrocatalyst as a successful alternative on large scale.

Electrocatalytic activities of iron-supported N-doped porous carbon towards the oxygen/hydrogen evolution reaction

Red mud (RM) disposal has been highly apprehensive due to its environmental impact. The aluminum industry produces large amounts of red mud waste annually, and turning it into a value-added product is a key component of sustainable development. This study combines RM with an N-doped porous carbon (biomass precursor) as an effective electrocatalyst for oxygen evolution and hydrogen evolution reactions (OER and HER). One significant obstacle to anion-exchange membrane (AEM) electrolyzer applications is the development of electrocatalysts that do not require noble metals and are both efficient and effective at HER and OER. The synthesized iron-supported (RM-derived) N-doped porous carbon (RMNPC) exhibits excellent catalytic activities with 276 and 191 mV overpotentials at 10 mA cm−2 for OER and HER, respectively. A two-electrode cell system is designed with an RMNPC/NF electrode as anode and cathode, and it necessitates just 1.82 V to realize 10 mA cm−2 and shows outstanding durability. This study presents a low-cost but effective electrocatalyst for water splitting for renewable hydrogen production, achieving the goal of RM recycling and highlighting the potential of porous carbon electrocatalysts.

Boosting the O2-to-H2O2 Selectivity Using Sn-Doped Carbon Electrocatalysts: Towards Highly Efficient Cathodes for Actual Water Decontamination.

The high cost and often complex synthesis procedure of new highly selective electrocatalysts (particularly those based on noble metals) for H2O2 production are daunting obstacles to penetration of this technology into the wastewater treatment market. In this work, a simple direct thermal method has been employed to synthesize Sn-doped carbon electrocatalysts, which showed an electron transfer number of 2.04 and outstanding two-electron oxygen reduction reaction (ORR) selectivity of up to 98.0 %. Physicochemical characterization revealed that this material contains 1.53 % pyrrolic nitrogen, which is beneficial for the production of H2O2, and -C≡N functional group, which is advantageous for H+ transport. Moreover, the high volume ratio of mesopores to micropores is known to favor the quick escape of H2O2 from the electrode surface, thus minimizing its further oxidation. A purpose-made gas-diffusion electrode (GDE) was prepared, yielding 20.4 mM H2O2 under optimal electrolysis conditions. The drug diphenhydramine was selected for the first time as model organic pollutant to evaluate the performance of an electrochemical advanced oxidation process. In conventional electro-Fenton process (pH 3), complete degradation was achieved in only 15 min at 10 mA cm-2, whereas at natural pH 5.9 and 33.3 mA cm-2, almost overall drug removal was reached in 120 min.

Novel design of hollow carbon nanocage modified with nanotubes as a bifunctional electrocatalyst for high performance Zn–air batteries

Microcavities play a crucial role as microreactors in the transport of molecular/ionic guests and the exposure of active sites, thus significantly influencing the electrocatalytic performance. This study prepares Co/N-codoped hollow carbon (HT-CoN/C) with surface-distributed carbon nanotubes by pyrolysis of PDA-coated Zn/Co bimetallic ZIF (BM-ZIF@PDA). Benefiting from the hierarchical porous structure, high specific surface area (307.17 m2 g−1) and abundant Co clusters, the HT-CoN/C exhibits remarkable bifunctional oxygen electrocatalytic activity with an overpotential of the ORR/OER processes (ΔE = 0.703 V). The density functional theory (DFT) calculations also verify that the configuration of C-coated N-coordinated Co clusters (Co4-Nx) affect the electrocatalytic activity of ORR and OER, illustrating the source of the excellent oxygen electrocatalytic activity of HT-CoN/C. The aqueous rechargeable zinc-air battery (RZAB) using HT-CoN/C as the air electrode is characterized by a superior peak power density (175 mW cm−2), a prolonged cycle life (1230 cycles/410 h at 5.0 mA cm−2) and a high open-circuit voltage (1.47 V). Meanwhile, the flexible solid-state RZAB assembled by the HT-CoN/C also exhibits a higher peak power density (117 mW cm−2) and an excellent bending performance. This work is extremely valuable for the design and synthesis of Co/N co-doped carbon electrocatalysts.

Lignin-derived Fe–N–C electrocatalyst with 3D porous structure for efficient oxygen reduction reaction

Developing low-cost, high-performance oxygen reduction reaction (ORR) catalysts is crucial for the commercialization of fuel cells and zinc-air batteries. Herein, we report a lignin-derived Fe/N co-doped 3D porous carbon electrocatalyst Fe-NLC-1 as an alternative to commercial Pt/C catalysts, which was synthesized by a green and facile in situ carbonization strategy. Fe-NLC-1 exhibits higher oxygen reduction activity with a half-wave potential (E1/2) of 0.90 V vs. RHE than commercial 20 wt% Pt/C (E1/2 = 0.85 V) in the alkaline conditions, as well as excellent methanol tolerance and stability. Furthermore, the Zn-air battery loaded with Fe-NLC-1 exhibits a maximum power density of 125 mW cm−2, an open circuit voltage of 1.477 V, and stable discharge performance, which are comparable or even better than the commercial Pt/C. This study highlights the potential of biomass-derived porous carbon materials for the development of high-performance ORR electrocatalysts.

Achieving over 90% Faradaic Efficiency in Cyclohexanone Oxime Electrosynthesis Using the Cu-Mo Dual-Site Catalyst.

Coupling with the nitrate electroreduction reaction (NitRR), the electrosynthesis of cyclohexanone oxime (CHO, the vital feedstock in the nylon-6 industry) from cyclohexanone provides a promising alternative to the traditional energy consumption process. However, it still suffers from low efficiency because selective production of *NH2OH intermediate from NitRR under large current densities is challenging. We here report a Cu1MoOx/nitrogen-doped carbon (NC) electrocatalyst with high-density Cu-Mo dual sites for NitRR to selectively produce and stabilize *NH2OH, with the subsequent cyclohexanone oximation achieving the highest CHO Faradaic efficiency of 94.5% and a yield rate of 3.0 mol g-1 h-1 at an industrially relevant current density of 0.5 A cm-2. Furthermore, in situ characterizations evidenced that the Cu-Mo dual sites in Cu1MoOx/NC effectively inhibited hydrodeoxygenation of hydroxyl-containing intermediates of NitRR, selectively producing *NH2OH and thus achieving cyclohexanone oximation with high efficiency. This work provides a high-performance catalyst for CHO electrosynthesis from nitrogenous waste, showing promising application potential in industrial production of CHO.

One-step microwave-assisted synthesis of metal-free heteroatom-doped carbon catalyst for H2O2 electrosynthesis

This study reports on a one-step conversion of polyaniline into a metal-free heteroatom-doped carbon electrocatalyst through microwave heating. A high surface area carbonaceous structure forms after a total synthesis time of only 140 s, with the presence of nitrogen and oxygen functional groups, as confirmed by thorough spectroscopic analysis. This catalyst exhibits high activity (onset potential of 0.73 V vs. RHE), selectivity (82 %), and stability (over a 7.5-hour test period) for the electrochemical oxygen reduction reaction towards hydrogen peroxide in alkaline media. Microwave synthesis reduces heating time by 29-fold and energy consumption by 77-fold, while producing materials with high electrocatalytic efficiency comparable to those conventionally prepared at 700°C. The microwave and the conventionally synthesized heteroatom-doped carbon catalysts show similar electrochemical performances, which can be attributed to the presence of nearly identical nitrogen functional groups and surface area in the two samples. In contrast, the microwave and conventionally synthesized samples exhibit significant variations in their oxygen functional groups. These results suggest that nitrogen functional groups are the main active sites for alkaline hydrogen peroxide formation, while oxygen functional groups play a minor role in the catalytic activity. Our work brings a solid contribution to the debate regarding the active centers for hydrogen peroxide formation.

Fabrication of CoM (M= Ni, Cu) alloys modified carbon electrocatalysts by pyrolysis of dual-metal-site metal-organic frameworks for efficient dye-sensitized solar cells

The regulation of interface properties of multi-component transition metals in carbon-based catalyst has been an effective method to boost the electrochemical performance of counter electrode (CE) catalysts for dye-sensitized solar cells (DSSCs). Herein, CoNi-metal-organic framework (MOF) and CoCu-MOF are fabricated through introducing Ni and Cu into the stable Co-MOF, and used as sacrificial precursor in the followed pyrolysis-alloying process. And then, the target product CoM (M=Ni, Cu)/N-doped polyhedron-like carbon (NC) are successfully obtained, in which CoNi and CoCu alloy nanoparticles are uniformly dispersed on the N-doped carbon skeleton. Such MOFs-derived carbon matrix can not only supply as conductive network, but also isolate the alloy nanoparticles to avoid agglomeration, ensuring more effective active sites. Meanwhile, the built-in electric field generated by the Mott-Schottky interface effect of CoM/NCs could regulate the electronic structure inside the catalysts, resulting in faster electron transfer ability. Significantly, the reduced work function due to the introduction of Cu atoms leads to stronger self-driven electron transfer at the heterogeneous interface of CoCu/NC, which helps to improve reaction activity and electrocatalytic efficiency. Among the tested catalysts, CoCu/NC displays a more satisfying power conversion efficiency (PCE) of 7.60 % when assembled into CE of DSSC, also superior to 7.19 % of Pt.

N, F Co-Doped Carbon Derived from Spent Bleaching Earth Waste as Oxygen Electrocatalyst Support.

Affordable nitrogen and fluorine co-doped carbon nanostructure was prepared from the hazardous industrial waste of edible oil refinery, spent bleaching earth (SBE), and used as raw material for obtaining high-performance non-noble metal bifunctional oxygen electrocatalysts. Waste SBE contains 35 % residue non-saturated oil as a carbon source and the assistance of montmorillonite (MMT) as the template. This study converts waste SBE into a fluorine-doped carbon nanostructure through a pyrolysis process followed by removing the aluminosilicate layers of the MMT by HF etching. Furthermore, the impregnation of the support with Co and Fe nitrates readily gives rise to N, F co-doped carbon (NFC) electrocatalysts, as confirmed by XPS analysis. Electrochemical results evidenced that the Co-NFC catalyst proved to be a valuable bifunctional competitor for oxygen reduction reaction and oxygen evolution reaction in alkaline media, showing activity in both reactions and superior stability compared with the Fe-NFC catalyst in accelerated tests. This work offers a straightforward, economical, and eco-friendly strategy for designing N, F co-doped carbon-based electrocatalysts for oxygen reactions in electrochemical devices.

Gaseous Nitric Oxide As Probe Molecule for Fe-N-C ORR Electrocatalysts

Iron nitrogen carbon (Fe-N-C) electrocatalysts remain the most promising platinum group metal-free (PGM-free) catalysts for the oxygen reduction reaction (ORR) in polymer electrolyte fuel cells (PEFCs). Although significant progress has been made in recent years in improving both the ORR activity and stability of the Fe-N-C catalysts, further enhancement in the catalyst durability while maintaining the activity is imperative for the practical applications. One of the major factors that hinders the further enhancement of the catalysts is the lack of clear understanding of the nature of the active sites and density of the active sites in the Fe-N-C catalysts due to the complexity of the Fe-N-C catalysts’ composition and structure. Gaseous nitric oxide was proven to be a suitable probe molecule that can bond to Fe and impede the ORR of the Fe-N-C catalysts. In recent years, we have studied the effects of gas-phase adsorption and desorption of nitric oxide on the redox features and ORR activity on Fe-N-C catalysts synthesized by different methods. We have used various characterization tools to quantify the amount of nitric oxide adsorbed and to identify the adsorption sites and geometry, including electrochemical stripping, temperature programmed desorption, and in situ X-ray techniques. The corresponding results obtained will be summarized in this talk. The implication of these results on the nature of the ORR active sites of the Fe-N-C catalysts will be discussed.AcknowledgementsThis work was supported by the U.S. Department of Energy (DOE), Energy Efficiency and Renewable Energy, Hydrogen and Fuel Cell Technologies Office (HFTO) under the auspices of the Electrocatalysis Consortium (ElectroCat 2.0). This work utilized the resources of the Advanced Photon Source, a U.S. DOE Office of Science user facility operated by Argonne National Laboratory for DOE Office. This work was partially authored by Argonne, a U.S. Department of Energy (DOE) Office of Science laboratory operated for DOE by UChicago Argonne, LLC under contract no. DE-AC02-06CH11357.

Engineering Three-Dimensional Interconnected Pores with Plentiful Edge Sites via a Confined Space for Enhanced Oxygen Reduction.

N-Doped carbon sheets based on edge engineering provide more opportunities for improving oxygen reduction reaction (ORR) active sites. However, with regard to the correlation between porous structural configurations and performances, it remains underexplored. Herein, a silica-assisted localized etching method was employed to create two-dimensional mesoporous carbon materials with customizable pore structures, abundant edge sites, and nitrogen functionalities. The mesoporous carbon exhibited superior electrocatalytic performance for the ORR compared to that of a 20 wt % Pt/C catalyst, achieving a half-wave potential of 0.88 V versus RHE, situating them in the leading level of the reported carbon electrocatalysts. Experimental data suggest that the edge graphitic nitrogen sites played a crucial role in the ORR process. The three-dimensional interconnected pores provided a high density of active sites for the ORR and facilitated the efficient transport of electrons. These unique properties make the carbon sheets a promising candidate for highly efficient air cathodes in rechargeable Zn-air batteries.

Three-dimensional porous structured cobalt- and nitrogen-doped carbon nanotube electrocatalyst derived from cobalt-based zeolitic imidazolate framework nanoleaves for high performance zinc-air battery

The development of efficient and cost-effective electrocatalysts to overcome the intrinsic sluggish kinetics of the oxygen reduction reaction (ORR) in zinc-air batteries is crucial. In this study, we introduce a strategy that integrates a template-assisted synthesis with subsequent thermal treatment to fabricate an active and stable cobalt-based nitrogen-doped carbon electrocatalyst, denoted as Co-N-CNT. The strategy adjusts the disordered architecture of the zeolitic imidazolate framework (ZIF) through the synergistic effect of bimetallic species, restricted the growth of zeolitic imidazolate framework nanoleaves (ZIF-L) using salt templates, and directed the transformation from a two-dimensional blade-like morphology to a three-dimensional multi-tiered composite structure. Notably, the Co-N-CNT-800 sample, synthesized at an optimized pyrolysis temperature of 800 °C, exhibits a half-wave potential of 0.89 V and demonstrates stability with sustained cycling over 21 h, which is comparable to the performance of commercial Pt/C electrocatalysts. Moreover, when employed as the cathode in zinc-air batteries, Co-N-CNT-800 not only surpasses Pt/C in terms of power density but also exhibits long-term charge/discharge stability. This findings offer a viable pathway for the design of active and cost-effective ORR electrocatalysts, holding promise for applications in the electrochemical energy storage and conversion systems.

Customizing pyridinic nitrogen coordination in Ni–N–C for electrocatalytic CO2 reduction towards CO

Nickel anchored N-doped carbon electrocatalysts (Ni–N–C) are rapidly developed for the electrochemical reduction reaction of carbon dioxide (CO2RR). However, the high-performanced Ni–N–C analogues design for CO2RR remains bewilderment, for the reason lacking of definite guidance for its structure-activity relationship. Herein, the correlation between the proportion of nitrogen species derived from various nitrogen sources and the CO2RR activity of Ni–N–C is investigated. The x-ray photoelectron spectroscopy (XPS) spectrum combined with the CO2RR performance results show that pyridinic-N content has a positive correlation with CO2RR activity. Moreover, density functional theory (DFT) demonstrates that pyridinic-N coordinated Ni–N4 sites offers optimized free energy and favorable selectivity towards CO2RR compared with pyrrolic-N. Accordingly, Ni–Na–C with highest pyridinic-N content (ammonia as nitrogen source) performs superior CO2RR activity, with the maximum carbon monoxide faradaic efficiency (FECO) of 99.8% at −0.88 V vs. RHE and the FECO surpassing 95% within potential ranging of −0.88 to −1.38 V vs. RHE. The building of this parameter for CO2RR activity of Ni–N–C give instructive forecast for low-cost and highly active CO2RR electrocatalysts.

Design of high-performance wood-derived N-doped ECR electrocatalysts based on Marcus theory

Electrochemical reduction of CO2 over wood-derived metal-free N-doped carbon electrocatalysts provides a new route for converting CO2 into value-added fuels However, it is a challenge to efficiently design and screen high-performance electrocatalysts. In this paper, we combined the Marcus equation with the theory of thermal-kinetic correlation to successfully predict the optimal N-C doping ratio. Poplar wood -derived 3D N-doped graphitized carbon with optimal N doping content (pyridine-N 1.87 at%, pyrrole-N, 1.52 at%), high specific surface area (471.2 m2 g−1), and abundant nanopores were successfully obtained with the assistance of melamine (N source), which exhibited a high ECR activity of 86.78 % at a low applied potential of −0.71 V (vs. RHE) and long-term stability of at least 10 cycles. This extends the application of the Marcus equation and improves new ideas for the future design of high-performance electrocatalysts.

Electronic Structure Regulation of MnCo2O4 via Surface‐Phosphorization Coupling to Monolithic Carbon for Oxygen Electrocatalysis in Zn–Air Batteries

AbstractAn urgent challenge to the development of rechargeable Zn–air batteries (RZABs) is the highly active, durable, and low‐cost catalysts for oxygen reduction reaction and oxygen evolution reaction (ORR and OER). Herein, a carbon‐based monolithic catalyst is designed via anchoring P‐modified MnCo2O4 inverse spinel nanoparticles on biomass‐derived carbon (P‐MnCo2O4@PWC). The introduction of surface P atoms regulates the electronic structures and valences of metal atoms by adjusting the coordination fields by (P‐O)δ– and Metal‐P. The optimization of the adsorption behavior of key intermediates facilitates the activation and conversion of reaction species. The monolithic structure is beneficial to the construction of a three‐phase interface for efficient mass transfer and high electrical conductivity. The P‐MnCo2O4@PWC catalyst displays outstanding bifunctional catalytic properties with a thin ΔE (the difference between the OER potential at 10 mA cm–2 and the ORR halfwave potential) of 0.66 V. The RZAB with P‐MnCo2O4@PWC as cathode delivers an exceptional peak power density (160 mW cm–2) and remarkable cycle life (over 1200 cycles), overcoming those with noble metal counterparts. This research provides a promising general surface‐phosphorization way to the design of carbon electrocatalysts and the high‐value utilization of biomass.

Fe, Cu-decorated carbon material produced from ionic liquids as resourceful electrocatalyst for water splitting

The quest for highly efficient, stable, and economically viable bifunctional electrocatalysts is of paramount relevance for advancing in water splitting for the hydrogen energy sector, particularly in facilitating hydrogen (HER) and oxygen evolution evolution (OER) as cathodic and anodic reaction, respectively. In this study, two ionic liquids containing transition metal Fe or Cu, as well as a mixture of these ionic liquids, were used as precursors to synthesize Fe-, Cu-, and Fe,Cu-decorated carbon materials through simple, straightforward, and inexpensive carbonization processes. Comprehensive characterization via SEM-EDS, TEM, XRD, and XPS established the formation of Fe3O4 and Cu2O species. These materials were systematically evaluated for OER and HER in alkaline electrolyte. Fe,Cu-decorated carbon electrocatalyst exhibited favorable performance for OER, including a low onset potential, and reaching 10 and 50 mA cm−2 at overpotential values of 325 mV and 364 mV, respectively. Notably, grafting both Fe and Cu in the material further augmented its electrocatalytic properties, underscoring the enhanced potential of transition metal-decorated carbon materials for OER applications.

Efficient electroreduction of CO2 into CO in flow cell with a metal-free ternary-doped porous carbon

Herein, a series of metal-free N, P, and Se ternary-doped porous carbon electrocatalysts, referred as "SePNC" as metal-free electrocatalysts, was prepared. This study shows that, the optimal electrocatalyst of SePNC-1050, which prepared at 1050 ℃, has high CO selectivity with Faraday efficiency of 94.8% for CO, and a byproduct of 5.2% H2. After continuous electrolysis for 12 h, the Faraday efficiency and current density remained relatively high, around 95.9% and 80.2% of the initial values, respectively, indicating it has long-term operation stability. This mainly due to the synergistic effect of doped N, P, and Se, as well as the high specific surface area of SePNC-1050 (970.0 m2g−1). This work would provide a good reference to develop high-performance metal-free CO2 reduction reaction (CO2RR) electrocatalysts in future.

Recent Progress and Prospects of Manganese–Nitrogen–Carbon Electrocatalysts for Oxygen Reduction Reaction

Recent Progress and Prospects of Manganese–Nitrogen–Carbon Electrocatalysts for Oxygen Reduction Reaction

Deciphering the Role of Native Defects in Dopant‐Mediated Defect Engineering of Carbon Electrocatalysts

AbstractDoping–dedoping chemistry lays the cornerstone for converting heteroatom dopants into intrinsic defects as the emerging active sites of carbon catalysts, but the defect content is yet hindered by inadequate doping efficiencies. Comprehending crucial factors behind the doping of pristine carbon and their correlation to the catalytic properties of dedoped carbon is thus of high significance. Here, the overlooked impact of native defects in pristine carbon on dopant‐mediated defect engineering of carbon catalysts is explicitly unveiled. Intact fullerene (C60), C60‐derived carbon, and carbon black in distinct pentagon/edge defect states are employed as respective precursors to undergo a nitrogen doping–dedoping treatment. Theoretical and experimental evidence consistently indicates that native pentagons change the preferred N doping site from the edge to the basal plane, leading to a substantially higher doping level. Importantly, in addition to pentagons from the removal of zigzag‐edged pyridinic N, N dopants in in‐plane pentagons are more easily dedoped than those in hexagons, generating even more pentagons in a new pentagon–heptagon–pentagon structure as oxygen reduction active sites. The optimized defect‐rich carbon gives an outstanding half‐wave potential of 0.834 V (0.846 V for Pt/C) via the four‐electron pathway, excellent long‐term durability, and prospective applicability in zinc–air batteries.

Amine-Functionalized Metal-Free Nanocarbon to Boost Selective CO2 Electroreduction to CO in a Flow Cell.

Highly efficient electrochemical CO2-to-CO conversion is a promising approach for achieving carbon neutrality. While nonmetallic carbon electrocatalysts have shown potential for CO2-to-CO utilization in H-type cells, achieving efficient conversion in flow cells at an industrial scale remains challenging. In this study, we present a cost-effective synthesis strategy for preparing ultrathin 2D carbon nanosheet catalysts through simple amine functionalization. The optimized catalyst, NCNs-2.5, demonstrates exceptional CO selectivity with a maximum Faradaic efficiency of 98% and achieves a high current density of 55 mA cm-2 in a flow cell. Furthermore, the catalyst exhibits excellent long-term stability, operating continuously for 50 h while maintaining a CO selectivity above 90%. The superior catalytic activity of NCNs-2.5 is attributed to the presence of amine-N active sites within the carbon lattice structure. This work establishes a foundation for the rational design of cost-effective nonmetallic carbon catalysts as sustainable alternatives to metals in energy conversion systems.