Efficient Electrocatalysts Research Articles

Lycium ruthenicum stem extract mediated green synthesis of MnO2/Mn3(PO4)2 composite nanowire electrocatalyst for oxygen evolution reaction

A composite of manganese oxide (MnO2) and Mn3(PO4)2 decorated nanowires (MnO2/Mn3(PO4)2) was prepared using Lycium ruthenicum stem-extract mediated green synthesis. This composite material functions as an efficient and long-lasting electrocatalyst for water-splitting reactions, which could significantly improve the performance of oxygen evolution reaction (OER). The OER activity of MnO2/Mn3(PO4)2-based nanowires is boosted by blending with a conducting support, such as manganese oxide (MnO2). The x-ray diffraction pattern and Fourier transform infrared data indicate that the nanowires are highly crystalline. The MnO2/Mn3(PO4)2 composite material demonstrates superior stability compared to its individual constituents and generates a current density of 10 mA cm−2 at a low overpotential of 244 mV for OER in alkaline media. This research may lead to the development of MnO2/Mn3(PO4)2 composite materials as electrocatalysts for overall water-splitting reactions.

Construction of Ru-doped Co nanoparticles loaded on carbon nanosheets in-situ grown on carbon nanofibers as self-supported catalysts for efficient hydrogen evolution reaction

Exploring efficient and economical electrocatalysts to replace noble metal electrocatalysts has become a major research focus nowadays. In this paper, Ru-doped Co nanoparticles loaded on carbon nanosheet (CNS) in-situ grown on carbon nanofibers (Ru–Co@CNS/CNFs) were constructed as a self-supporting working electrode for high-efficiency hydrogen evolution. The prepared Ru–Co@CNS/CNFs possessed excellent catalytic activity with only 78 mV overpotential at 10 mA cm−2 current density and good stability with only 102 mV voltage attenuation at 100 mA cm−2 current density for 100 h continuous operation. The excellent catalytic performance could be attributed to the unique microstructure of the nanosheets in-situ grown on the nanofibers, it resulted in a higher Co surface density of 1.28 mg cm−2, indicating more loading of metal to improve catalytic activity of HER, and the formed Ru-doped Co nanoparticles could be evenly distributed on the carbon nanosheets to prevent the aggregation of nanoparticles, which could expose more active sites. Additionally, the density functional theory (DFT) calculations revealed Ru doping could accelerate the dissociation of water, optimize the adsorption energy of hydrogen intermediates and improve the kinetics of the HER reaction. This work provides a new approach to reduce the use of noble metals while improving the catalytic performance of catalysts.

Si-C atomic line achieving efficient electrocatalytic nitrogen reduction reactions

In this study, the concept of a Si-C atomic line (SCAL) featuring fully exposed atomic sites is introduced for the first time, and the SCAL serves as a highly efficient electrocatalyst for nitrogen reduction reactions (NRR). Thanks to the strong binding strength of the Si-C bonds (polar covalent bonds), the SCAL exhibits exceptional structural stability at 298.15 K. With a band gap of 1.86 eV characterized by a semiconductor, SCAL exhibits relatively high conductivity which is advantageous for electrocatalytic processes. N2 is adsorbed on the C sites in an end-on mode due to the most negative adsorption energy (–0.39 eV), and the nature of adsorption is s-p orbital hybridization. Based on the end-on N2 adsorption, the entire NRR pathway is simulated and shows a relatively low energy barrier of 0.50 eV, which is relatively low compared to reported metal-free NRR electrocatalysts. The charge transfer mechanism reveals that the active sites (C atoms) are responsible for charge transfer, while other parts of SCAL act as storage warehouses for charge. Moreover, SCAL demonstrates a preference for NRR over hydrogen evolution reaction (HER), underscoring its excellent electrocatalytic selectivity. This study opens new avenues for designing high-performance catalysts.

Interfacial coupling of Ce-CoSe2 nanoneedle arrays with MXene for efficient overall water splitting

Designing highly effective, low-cost bifunctional electrocatalysts without noble metals for overall water splitting remains a significant challenge. In this work, interfacial coupling of Ce-doped CoSe2 nanoneedle arrays with MXene (Ce-CoSe2/MXene) is developed via the facile hydrothermal and selenization methods. The extensive specific surface area and favorable hydrophilicity of Ti3AlC2, combined with the optimized electronic structure and abundant active sites from Ce-doping and selenization, contribute to the exceptional bifunctional electrocatalytic performance of the Ce-CoSe2/MXene electrode. Specifically, this heterostructure achieves a low hydrogen evolution reaction (HER) overpotential of 34 mV at 10 mA cm−2, an oxygen evolution reaction (OER) overpotential of 279 mV at 100 mA cm−2, and an overall water splitting (OWS) potential as low as 1.45 V at 10 mA cm−2. In-situ Raman spectroscopy reveals that surface reconstruction would improve catalytic activity and stability. Theoretical calculations indicate that the Ce-CoSe2/MXene can improve the adsorption of intermediates and facilitate HER/OER process by lowering the kinetic barrier, thereby enhancing electrocatalytic activity. This research marks a substantial advancement in the development of low-cost, efficient electrocatalysts for overall water splitting.

Coupling Ir single atom with NiFe LDH/NiMo heterointerface toward efficient and durable water splitting at large current density

Developing efficient and robust bifunctional electrocatalysts for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) at large current density is important to facilitate the industrial water splitting. Herein, a promising strategy is presented to couple Ir single atom with NiFe LDH/NiMo heterointerface. IrSA-NiFe LDH/NiMo requires ultralow overpotentials of 139/236 mV and 350/450 mV to deliver large current densities of 500 and 1000 mA cm−2 for HER/OER in 1 M KOH. Moreover, the electrode shows remarkable durability of 10000 cycles and long-term durability at 500 mA cm−2 over 500 h for both HER and OER. The water electrolyzer exhibits a low cell voltage of 1.84 V to attain 500 mA cm−2. The theoretical calculations decipher that the Ir single atom modulates the electronic property of catalyst, which tunes the adsorption strength of the key reaction intermediates and boosts the overall water splitting.

In-situ synthesis to promote surface reconstruction of metal–organic frameworks for high-performance water/seawater oxidation

Metal-organic frameworks (MOFs) have gained tremendous notice for the application in alkaline water/seawater oxidation due to their tunable structures and abundant accessible metal sites. However, exploring cost-effective oxygen evolution reaction (OER) electrocatalysts with high catalytic activity and excellent stability remains a great challenge. In this work, a promising strategy is proposed to regulate the crystalline structures and electronic properties of NiFe-metal-organic frameworks (NiFe-MOFs) by altering the organic ligands. As a representative sample, NiFe-BDC (BDC: C8H6O4) synthesized on nickel foam (NF) shows extraordinary OER activity in alkaline condition, delivering ultralow overpotentials of 204, 234 and 273 mV at 10, 100, and 300 mA cm−2, respectively, with a small Tafel slope of 21.6 mV dec−1. Only a slight decrease is observed when operating in alkaline seawater. The potential attenuation is barely identified at 200 mA cm−2 over 200 h continuous test, indicating the remarkable stability and corrosion resistance. In-situ measurements indicate that initial Ni2+/Fe2+ goes through oxidation process into Ni3+/Fe3+ during OER, and eventually presents in the form of NiFeOOH/NiFe-BDC heterojunction. The unique self-reconstructed surface is responsible for the low reaction barrier and fast reaction kinetics. This work provides an effective strategy to develop efficient MOF-based electrocatalysts and an insightful view on the dynamic structural evolution during OER.

Engineering a Ce Promoter into a Three-Dimensional Porous Mo2C@NC Heterostructure for Hydrogen Evolution Electrocatalysis via Weakening the Mo-H Bond Strength.

The pursuit of highly efficient electrocatalysts for the alkaline hydrogen evolution reaction (HER) is of paramount importance for water splitting. However, it is still a formidable task in Mo2C-based materials because of the agglomeration and strong Mo-H binding of Mo2C units. Herein, a novel CeOCl-CeO2/Mo2C heterostructure nesting within a three-dimensional porous nitrogen-doped carbon matrix has been designed and used for catalyzing HER via simultaneous morphology and heterointerface engineering. As expected, the optimal CeOCl-CeO2(0.2)/Mo2C@3DNC exhibits impressive HER activity, with a low overpotential of 156 mV at a current density of 10 mA cm-2 coupled with a slight Tafel slope of 62.20 mV dec-1. Introducing a Ce promoter, that is CeOCl and CeO2, would endow the interface with an internal electric field and electron redistribution between CeOCl-CeO2 and Mo2C induced by the heterogeneous work function difference. Moreover, experimental investigation and density functional calculations confirm that the CeOCl-CeO2/Mo2C heterointerface can downshift the d-band center of the active Mo center, weakening the strength of the Mo-H coupling. This proposed concept, engineering Ce-based promoters into active entities involved in the heterostructure to modulate intermediate adsorption, offers a great opportunity for the design of superior electrocatalysts for energy conversion.

Beyond S and Se: Electrocatalytic Hydrogen Production by Tellurolate-Bridged Co(III)-Mn(I) Heterodinuclear Complexes.

In the pursuit of efficient electrocatalysts for the hydrogen evolution reaction (HER), a series of manganese and cobalt heterodinuclear complexes have been synthesized and characterized that have a stark resemblance with the [NiFe]-hydrogenase active site structure. Irradiation of [Mn2(CO)10] in the presence of 1.5 eq of [NaEPh] [E = S, Se, Te] followed by reaction with [Cp*CoCl]2 led to the formation of half-sandwiched trichalcogenate-bridged heterodinuclear complexes [{Mn(CO)3}(μ-EPh)3(CoCp*)] [E = S (C1); Se (C2) and Te (C3)]. The reaction of these heterodinuclear trichalcogenate-bridged complexes with [LiBH4·THF] yielded the corresponding dichalcogenate hydride-bridged heterobimetallic complexes [(CO)3Mn(μ-EPh)2(μ-H)(CoCp*)] [E = S (C5); Se (C6) and Te (C7)], which closely imitate the Ni-R intermediate of [NiFe]-hydrogenase. The resultant complexes (C5-C7) displayed impressive H2 production in DMF in the presence of HBF4, whereas the Te-based complex (C7) showcased the highest TON (184 h-1) with an impressive Faradaic efficiency of >98%. The DFT investigations revealed a unique role of bridging chalcogens in catalysis, wherein, depending on the identity of the chalcogen (S, Se, or Te), protonation could occur via two distinct routes. This study represents a rare example of the full trio of S/Se/Te-based heterodinuclear complexes whose electrocatalytic HER activity has been probed under analogous conditions.

Electrocatalytic ammonia synthesis on bimetallic AuPd porous structures

In industry, production of ammonia mainly relies on the intensive Haber-Bosch process, but it consumes high energy with low efficiency and generates a large number of green-house gases. Electrocatalytic nitrogen reduction reaction (ENRR), as an alternative method for fixing N2 under ambient conditions, provides a feasible strategy for sustainable development of N2 cycle storage and utilization of renewable energy. However, traditional nanocatalysts exhibit extremely poor ENRR performance due to low activity of the solid structure and intense hydrogen evolution reactions of single component. Herein, we design and prepare porous gold–palladium nanoalloys (pAuPdNs), which effectively enhance ENRR by the excellent catalytic activity of Au and the significant N2 fixation ability of Pd, as well as the nanoporous structure and synergistic effect between alloy components. The electrochemical results show the NH3 yield of the catalyst is as high as 43.6 μg·h−1·cm−2, and Faradaic efficiency reaches 43.8%, which are superior to the performances of most reported water-based ENRR electrocatalysts. Besides, the selectivity of 95% and stability also exhibit enhancement than numerous reported researches. As compared with solid alloy and porous Au or Pd structures, the superiority of pAuPdNs states the influence of alloying and porous structure. Hence pAuPdNs are proved to be the efficient, stable, and promising electrocatalysts for N2 reduction reaction at ambient temperature and atmospheric pressure.

Macroporous high‐entropy spinel oxide monoliths as efficient oxygen evolution electrocatalyst

AbstractIn this paper, macroporous high‐entropy spinel oxide (HESO) (Fe0.2Ni0.2Co0.2Mn0.2Zn0.2)3O4 monoliths were successfully fabricated via a sol–gel method followed by calcination. Appropriate polyacrylic acid and propylene oxide contents allow the formation of three‐dimensional co‐continuous xerogel monoliths, and the water/glycerol ratio controls the macropore size of monoliths. Subsequent calcination achieves the precipitation of HESO (Fe0.2Ni0.2Co0.2Mn0.2Zn0.2)3O4 with a singular phase and exceptional structural stability. The macroporous HESO (Fe0.2Ni0.2Co0.2Mn0.2Zn0.2)3O4 demonstrates remarkable performance in the oxygen evolution reaction (OER) with an overpotential of 333 mV at 100 mA cm−2 and a Tafel slope of 43.2 mV dec–1, surpassing that of RuO2 (391 mV) under identical conditions. Furthermore, the catalytic stability of the HESO catalyst remains superior even after 24 h of testing. This process offers a promising avenue for the development of macroporous high‐entropy oxide OER catalysts for overall water splitting.

ZnAl2O4 decorated on graphitic carbon nitride (g-CN) composite as efficient electrocatalyst for water oxidation in alkaline medium

The main purpose of this research is to form highly effective and novel electrocatalysts for water splitting procedure, a pivotal step in the generation of sustainable energy. Cost-effective metal oxides exhibited superior benefits compared to alternative materials when used for oxygen evolution reactions (OER) in alkaline electrolyte. Our study focuses on the preparation of ZnAl2O4@g-CN composite by utilizing hydrothermal approach for electrocatalytic water splitting. The electrocatalytic potential of prepared electrocatalyst was observed by a comprehensive series of tests. Numerous electrochemical approaches such as chronoamperometry and electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) were implemented to analyze catalytic procedure and durability in basic medium. The electrocatalytic tests of ZnAl2O4@g-CN composite reveal a remarkable overpotential of 209 mV, enabling the attainment of current density (Cd) 10 mA/cm2. Additionally, the composite shows significantly lower Tafel value (36 mV/dec) and has remarkable durability for 30 h. These characteristics mutually designate that electrocatalyst is well-suited for OER procedure. Therefore, the fabricated composite exhibited excellent efficacy in OER procedure as well as for several other upcoming applications.

Defective PTFE with Dense Active Sites Enabling Rapid H2O2 Production for Efficient Water Purification

AbstractThe electrosynthesis of hydrogen peroxide (H2O2) via two‐electron oxygen reduction reaction (2e−‐ORR) enables high energy utilization and distributed H2O2 production. Rational catalyst design is essential for achieving efficient H2O2 production, in which fluorine‐modified carbon materials hold great potential. However, conventional methods can only induce limited loading of fluorine atoms in carbon‐based catalysts, leading to unsatisfying electrochemical performance. Herein, the design of fluorine‐containing active sites with high density and high 2e−‐ORR selectivity is achieved by loading fluorine‐containing chained polytetrafluoroethylene precursors onto conductive carbon substrates by plasma‐assisted ball milling technique. Consequently, the defect‐rich PTFE@CNTs show a high selectivity of over 95% and a high H2O2 yield of more than 35 mol g−1 h−1. Furthermore, the electrochemical production of H2O2 can be readily integrated with water purification units to decompose contaminants, showing over 80% degradation of multiple dyes within 1 h and over 95% removal ratio of antibiotics within 4 h. In addition, 100% sterilization of staphylococcus aureus is achieved by on‐site accumulating H2O2 in commercial saline for only 30 min. This defect engineering strategy through plasma ball milling provides a promising and universal avenue toward designing highly active and efficient electrocatalysts for 2e−‐ORR as well as other electrochemical processes.

Fabrication of novel FeSe–GO composite: a highly efficient electro-catalyst for oxygen evolution reaction

Fabrication of novel FeSe–GO composite: a highly efficient electro-catalyst for oxygen evolution reaction

Atomic-Dispersed Cu Catalysts for Electrochemical Nitrate Reduction: Coordination Engineering and Fundamental Insights.

The development of Cu-based atomic dispersed catalysts with tailored coordination environments represents a significant step forward in enhancing the electrocatalytic reduction of nitrate to ammonia. By precisely modulating the electronic structures of Cu active centers, the binding strength of the *NO3 intermediates is successfully tuned, thereby substantially improving the catalytic activity toward electrochemical nitrate reduction reaction (eNO3RR). This study reveals that the N4-coordinated Cu single-atom catalyst (Cu-SAC) exhibits superior performance due to its robust interaction with coordinating atoms. Notably, this optimized catalyst achieves a low limiting potential of -0.38V, while the dual-atom system further reduces this value to -0.32V, demonstrating exceptional activity. Detailed electronic structure analysis, including the examination of d-band centers, Bader charges, and projected density of states (PDOS), provides a comprehensive understanding of the origin of this high activity. Specifically, the high and concentrated density of states near the Fermi level plays a crucial role in facilitating the electrocatalytic nitrate reduction process. This work not only offers crucial insights into the underlying mechanisms of eNO3RR but also provides valuable guidelines for the rational design of highly efficient electrocatalysts for this important reaction.

P-d Orbital Hybridization in Ag-based Electrocatalysts for Enhanced Nitrate-to-Ammonia Conversion.

Considering the substantial role of ammonia, developing highly efficient electrocatalysts for nitrate-to-ammonia conversion has attracted increasing interest. Herein, we proposed a feasible strategy of p-d orbital hybridization via doping p-block metals in an Ag host, which drastically promotes the performance of nitrate adsorption and disassociation. Typically, a Sn-doped Ag catalyst (SnAg) delivers a maximum Faradaic efficiency (FE) of 95.5±1.85 % for NH3 at -0.4 V vs. RHE and reaches the highest NH3 yield rate to 482.3±14.1 mg h-1 mgcat. -1. In a flow cell, the SnAg catalyst achieves a FE of 90.2 % at an ampere-level current density of 1.1 A cm-2 with an NH3 yield of 78.6 mg h-1 cm-2, during which NH3 can be further extracted to prepare struvite as high-quality fertilizer. A mechanistic study reveals that a strong p-d orbital hybridization effect in SnAg is beneficial for nitrite deoxygenation, a rate-determining step for NH3 synthesis, which as a general principle, can be further extended to Bi- and In-doped Ag catalysts. Moreover, when integrated into a Zn-nitrate battery, such a SnAg cathode contributes to a superior energy density of 639 Wh L-1, high power density of 18.1 mW cm-2, and continuous NH3 production.

Co-Co6Mo6C2 heterostructure grown on carbon nanofibers as tri-functional electrocatalyst for overall water splitting and rechargeable Zn-air batteries

The advancement of cost-effective and efficient electrocatalysts for the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR) is crucial for the progress of clean energy conversion and storage technologies. In this work, cobalt (Co) and cobalt-molybdenum (Mo) bimetallic carbide (Co6Mo6C2) heterostructure grown on carbon nanofibers (denoted as Co-Co6Mo6C2/CNFs) as tri-functional electrocatalyst were prepared by a four-step method. Benefiting from the electronic structure modulation between the heterostructure to improve the catalytic activity, Co-Co6Mo6C2/CNFs exhibits high catalytic activity for HER (91 mV @ 10 mA cm−2), OER (293 mV @ 10 mA cm−2) and ORR (E1/2=0.80 V). Moreover, Co-Co6Mo6C2/CNFs assembled overall water splitting electrolyzer achieves a current density of 10 mA cm−2 with a battery voltage of only 1.70 V and has long-term durability. Zn-air batteries (ZABs) based on Co-Co6Mo6C2/CNFs has a power density of 156.6 mW cm−2 with good stability. This study contributes to the development of inexpensive and efficient transition metal-based multifunctional electrocatalysts.

Platinum-dependent 2H-to-1T phases conversion of MoS2 nanosheets growing on cross-interlocking porous carbon for boosting hydrogen evolution reaction

Proton exchange membrane water electrolysis (PEMWE) coupled with renewable energy is regarded as a sustainable approach for green hydrogen production. However, the low reserve and high cost of platinum cathode electrocatalysts greatly limit its widespread deployment. Herein, we report a phase conversion strategy to obtain an efficient low-Pt loading electrocatalyst composed of multi-atomic Pt substituted 1T-MoS2 nanosheet grown on a cross-interlocking porous carbon matrix (Pt@1T-MoS2/C). In combination with experimental and theoretical results, the 2H-to-1T phase conversion of MoS2 induced by the Pt substitution is investigated, and the as-formed Pt-S-Mo active site accounts for the excellent hydrogen evolution reaction (HER) performance. Benefiting from the improved electron transfer efficiency and Pt-S-Mo active sites, the Pt@1T-MoS2/C delivers a high mass HER activity of ∼58.9 A·mgPt−1, and an excellent stability of 200 h at 1000 mA∙cm−2 in a practical PEMWE device.

Enhanced water and urea electrolysis at industrial scale current density using self-supported VxNi1-xO trifunctional catalysts

An advance of highly efficient nanostructured electrocatalysts based on non-noble metals for water electrolysis and urea oxidation reaction (UOR) are of great significance for urea-enriched wastewater remediation and producing hydrogen. Herein, we report VxNi1-xO catalysts supported on three-dimensional Ni-foam scaffold for catalytic water and urea electrolysis. VxNi1-xO catalysts show rapid water and urea electrolysis due to enhanced electrochemical surface area (ECSA). Most important of all, the urea oxidation reaction has a lower potential of 1.418V vs RHE as compared to oxygen evolution reaction (1.684 V vs RHE) system to generate 100 mA/cm2. Additionally, a two-electrode cell for bi-functional water electrolysis generates 100 mA/cm2 at a potential of 2.10 V at 20 °C and just 1.86 V at 60 °C temperature due to regulated the adsorption/desorption of intermediates species, enhanced charge and mass transport, and easier desorption of oxygen molecules from the anode. The stability of VxNi1-xO catalyst was measured at 1000 mA/cm2 current density for up to 17 h.

Novel ZnSe@d-Ti3CNTx nanocomposite as efficient bifunctional electrocatalyst for water splitting system

Electrocatalytic water splitting is an environmentally friendly approach for producing hydrogen and oxygen from water. ZnSe@d-Ti3CNTx nanocomposite was synthesized by a hydrothermal approach. The ZnSe@d-Ti3CNTx nanocomposite was examined with several techniques, including Raman, p-XRD, microscopy, SEM/EDS, and XPS spectroscopy. Electrochemical properties were studied by CV, LSV, EIS, and chronoamperometry. As Ti3CN is a conductive material, to improve its electron transport efficiency, ZnSe was incorporated into it, which not only enhances its electrochemical behavior but also prevents it from restacking. By integrating the features of d-Ti3CNTX MXene and ZnSe nanoparticles, the HER and OER performance of the electrocatalyst is improved at low overpotentials of 270 mV and 232 mV, respectively. The ZnSe@d-Ti3CNTx nanocomposite.kept 84 % of its starting current after 50 h at an applied potential of 1.56 V, demonstrating excellent long-term stability. According to the results of this research, the ZnSe@d-Ti3CNTx nanocomposite has the potential to serve as a highly efficient and long-lasting electrocatalytic catalyst for water splitting.

Controlled synthesis of Sn doped Cu–Ni3S2 on Ni foam as efficient electrocatalyst for urea oxidation reaction and oxygen evolution reaction

Hydrogen production technology by urea-assisted electrocatalytic water decomposition has become one of the important means to alleviate carbon emissions and water pollution. In this paper, we first doped Sn and Cu element into the Ni3S2 material by hydrothermal method on the Ni foam support. This Cu–Sn–Ni3S2 material exhibits superior urea (potential of 1.42 V at 100 mA cm−2) and water oxidation (potential of 1.63 V at 100 mA cm−2) properties, which is one of the best electrochemical performance reported up to now. Analysis of experiment demonstrate that the increase in catalytic performance is assigned to faster charge transfer, more exposure of reaction centres and smaller resistance owing to doping of Sn and Cu. Density functional theory (DFT) analysis demonstrates that introduction of Sn and Cu increases the adsorption energy of urea and improves the conductivity of the Cu–Sn–Ni3S2 material, and the co-doping of the two changes the electron state density of the active site, thereby promoting the catalytic performance. This work provides insights into the development of efficient bifunctional electrodes for urea oxidation and oxygen evolution reaction through doping strategies.