Electrocatalysts for oxygen reduction are a critical component that may dramatically enhance the performance of fuel cells and metal-air batteries, which may provide the power for future electric ...vehicles. Here we report a novel bio-inspired composite electrocatalyst, iron phthalocyanine with an axial ligand anchored on single-walled carbon nanotubes, demonstrating higher electrocatalytic activity for oxygen reduction than the state-of-the-art Pt/C catalyst as well as exceptional durability during cycling in alkaline media. Theoretical calculations suggest that the rehybridization of Fe 3d orbitals with the ligand orbitals coordinated from the axial direction results in a significant change in electronic and geometric structure, which greatly increases the rate of oxygen reduction reaction. Our results demonstrate a new strategy to rationally design inexpensive and durable electrochemical oxygen reduction catalysts for metal-air batteries and fuel cells.
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•Engineered carbon-vacant CN (FCN) using formalin-assisted thermal polymerisation.•FCN achieved complete removal of Tetracycline via sonophotocatalysis within 60 min.•Boosted charge ...separation and extended visible light response over defected FCN.•Adsorption of oxygen molecules on FCN site resulted in abundant reactive species.
Metal-free polymeric graphitic carbon nitride (CN) materials are robust and stable visible-light-driven photocatalysts that have recently piqued interest in photocatalytic applications. Its photocatalytic performance is restricted remarkably due to moderate oxidation ability and fast charge carrier recombination rate. To address these issues, we engineered carbon-vacant CN (FCN) using a facile formalin-assisted thermal polymerization of molten CN precursor in which the carbon vacancies (Cv) were regulated by altering formalin dosage. Consequently, FCN catalysts revealed Cv concentration-dependent sonophotocatalytic degradation of Tetracycline (TC) antibiotics over diverse water matrices. The optimal FCN exhibited complete TC degradation efficiency within 60 min with a synergy index of 1.4, which is approximately 2.6 times higher than that of pristine CN. The enhanced sonophotocatalytic performance was mainly due to the synergistic effect of ultrasound and light irradiation. The Cv formation also resulted in enhanced charge carrier transportation and facilitated oxygen adsorption at the Cv site of FCN - supported by both experimental study and theoretical calculation. Subsequently, FCN generated abundant reactive active oxygen species including, •O2–, as well as indirectly •OH which played a significant role in the degradation pathway and mineralisation of the TC molecules. This study provides insight into understanding the correlation between controllable defects and sonophotocatalytic degradation properties of the self-doped and deficient FCN.
Highlights
O-functionalization at the edges of boron carbonitride induces charge polarization effect on B.
0.1 M HCl serves to preserve the catalyst active site from poisoning effect by electrolyte ...anions.
Experimental and theoretical findings go hand-in-hand towards high yield of ammonia.
Ammonia has been recognized as the future renewable energy fuel because of its wide-ranging applications in H
2
storage and transportation sector. In order to avoid the environmentally hazardous Haber–Bosch process, recently, the third-generation ambient ammonia synthesis has drawn phenomenal attention and thus tremendous efforts are devoted to developing efficient electrocatalysts that would circumvent the bottlenecks of the electrochemical nitrogen reduction reaction (NRR) like competitive hydrogen evolution reaction, poor selectivity of N
2
on catalyst surface. Herein, we report the synthesis of an oxygen-functionalized boron carbonitride matrix via a two-step pyrolysis technique. The conductive BNCO
(1000)
architecture, the compatibility of B-2
p
z
orbital with the N-2
p
z
orbital and the charging effect over B due to the C and O edge-atoms in a pentagon altogether facilitate N
2
adsorption on the B edge-active sites. The optimum electrolyte acidity with 0.1 M HCl and the lowered anion crowding effect aid the protonation steps of NRR via an associative alternating pathway, which gives a sufficiently high yield of ammonia (211.5 μg h
−1
mg
cat
−1
) on the optimized BNCO
(1000)
catalyst with a Faradaic efficiency of 34.7% at − 0.1 V vs RHE. This work thus offers a cost-effective electrode material and provides a contemporary idea about reinforcing the charging effect over the secured active sites for NRR by selectively choosing the electrolyte anions and functionalizing the active edges of the BNCO
(1000)
catalyst.
Widely used precious metal (i.e., Pt, or Pd) electrocatalysts need to be replaced with other cost-effective and earth-abundant materials for economical water splitting applications. Recently, ...two-dimensional (2D) transition metal dichalcogenides (MoS2, VS2, WS2, etc.) have emerged as ideal electrocatalysts for the hydrogen evolution reaction (HER) due to their tunable physicochemical properties and rich catalytic active sites. In this regard, we propose a strategy to achieve improved HER performance of VS2 by fabricating a hybrid material with transition metal (Zn and Cd)-based sulfides. A facile hydrothermal approach is employed to prepare a VS2/ZnS/CdS hybrid catalyst that exhibits remarkable electrocatalytic performance for the HER in acidic media with a small overpotential of 86 mV at 10 mA/cm2 and a Tafel slope of 74.4 mV/dec. This inferred the Volmer–Heyrovsky mechanism with electrochemical desorption of hydrogen as the rate-limiting step. High performance is attributed to the abundance of catalytically active sites and the synergistic interactions between the materials. Theoretical calculations reveal that the VS2/ZnS/CdS hybrid shows favorable HER activity owing to its low hydrogen adsorption free energy of about 0.35 eV. We believe that this work on designing 2D VS2/ZnS/CdS will offer a new pathway to discover an efficient H2 generation electrocatalyst.
Dioxygen adsorption and activation on metal-ligand systems are the key elements for biological oxidative metabolisms and also catalyst design for the oxygen reduction reaction (ORR). We show, through ...first-principles calculations, that similar dioxygen adducts can form on metal-free n-type doped hexagonal boron nitride (h-BN) nanostructures. The density of electron donors determines the charge state of dioxygen, either in superoxo and peroxo, which exactly correlates with the ‘end-on’ and ‘side-on’ configurations, respectively. Activated O2 in the superoxo state shows a better catalytic performance possibly mediating the direct four-electron reduction. The formation of hydrogen peroxide (H2O2) is practically eliminated, and thus we suggest that a surface coated with the n-type doped h-BN can be the basis for an ORR catalyst with increased stability.
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•Oxygen molecular binding on the n-type doped h-BN.•Adsorbed oxygen molecular adsorption state with superoxo or peroxo state on h-BN, without transition metal.•Oxygen reduction reaction free energy profile of the oxygen adsorption state on h-BN.
Using first-principles density functional theory calculations, we used a thin oxide overlayer, such as MgO, on a metal surface as an inverse catalyst for dioxygen reduction. Surface distortions in ...the oxide layer, combined with the tunneling of electron from the underneath metal, activated the adsorbed O2 in the form of a superoxo or peroxo. On the other hand, the thin MgO overlayer readily prevents the π-back-bonding between CO and the metal surface, thereby efficiently mitigating the affinity of the metal surface for CO. The operating potential and overpotential for the oxygen reduction reaction (ORR) process have been estimated for various combinations of thin insulators and metals. The strongest binding intermediate in the overall reaction pathway influenced the overpotential. We show that for a Ag(100)-supported MgO surface, the ORR commences with a low overpotential, which is comparable to that of the Pt(111) surface. This suggests that an optimally chosen insulator–metal overlayer structure can yield a sharply tuned free energy profile for ORR.
The electrocatalytic reduction of CO2 (CO2RR) into value-added hydrocarbons is limited due to high limiting potential (UL) and competing hydrogen evolution reaction (HER). To find the best catalyst ...for CO2 reduction the concept of hydrogen poisoning was not considered in the catalyst screening process. Herein, we present a simple screening method and graphical construction using multiparameter optimization for the design of highly active and selective single-atom catalysts (SAC) using density functional theory calculations. A series of SAC namely, MN4, MBN3 and H@MBN3 (M: metal) are investigated for CO2RR. Our results revealed that MN4 and MBN3 SAC are not favorable for CO2RR due to high UL > −0.85 V and hydrogen poisoning (ΔGH* < 0), respectively. H@MBN3 SAC (stable compounds forming H–B bonds) are identified as efficient catalysts with a low value of UL and significantly hinder the competitive HER. Among these, H@CoBN3 and H@FeBN3 SAC show excellent CO2RR activity with limiting potential −0.30 and −0.44 V respectively for CH4 production and no chance of HER. Scaling relations reveal the importance of *COOH/*CHO binding energy (Eb) as an energy descriptor to evaluate the catalytic performance. This work provides a new theoretical perspective to design a highly selective catalyst for CO2RR.
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•Simple graphical construction is provided to screen the catalyst for selective CO2RR.•The hydrogen poisoning issue is addressed, which blocks the active site.•Hydrogen assisted catalysts (H@MBN3) are designed for highly efficient CO2RR.•The binding energy of *COOH is defined as an energy descriptor for SAC catalyst.
In this work, a novel memory capacitor structure has been presented with AlO
x
/Al
2
O
3
bilayer dielectrics on high mobility Epitaxial-GaAs substrate. We have demonstrated the chemical and ...electrical properties of metal–electrode/AlO
x
/Al
2
O
3
/epi-GaAs-based memory device in detail. Sputter-grown non-stoichiometric AlO
x
has been used for both the charge trapping layer and blocking layer due to its intrinsic charge trapping capability and high bandgap. Ultra-thin tunneling layer of thicknesses 5 nm and 15 nm were prepared by atomic layer deposition technique and memory properties were compared on promising high mobility Epitaxial-GaAs/Ge heterostructure. The proposed device shows excellent charge trapping properties with a maximum memory window of 3.2 V at sweep voltage of ± 5 V, with good endurance and data retention properties. Oxygen-deficient AlO
x
layer acted as a charge trapping layer without any additional blocking layer which is impressive for non-volatile memory application on high mobility epi-GaAs substrate. In addition, density Functional Theory (DFT) has been employed to understand the physical origin of the intrinsic charge trapping defects in AlO
x
dielectric layer.
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•Heteroatoms (B, N) doping to switch the CO oxidation mechanism from ER to LH.•A screening criterion is defined to get an efficient catalyst for CO oxidation.•3B edge doped AGNR is ...identify as an active catalyst following LH mechanism.•Sabatier activity and TOF values of 0.90 and 2.47, respectively.
In heterogeneous catalysis, the LH (Langmuir Hinshelwood) mechanism is more efficient and recommended over any other mechanism adopted for CO oxidation. However, the LH mechanism over a carbon surface is a challenge and is paused to be applied to any carbon surface in practical application. In this work, we carried out density functional theory to study how the incorporation of nitrogen, boron atom (C→N, C→B) and co-doping on graphene nanoribbons can modify the catalytic activity of the surface and the preference between ER (Eley-Ridel) and LH mechanism is explored. Boron plays a crucial role in the adsorption of both CO and O2, whereas nitrogen doping can only activate O2 molecule through altering the triplet ground state. Considering the activation energy for the first CO2 formation and CO binding strength, we have defined a window to identify the operation of the LH mechanism in the catalysis. 3B edge doped AGNR (armchair graphene nanoribbon doped with three boron atoms at its edge) is identified as an active catalyst for the CO oxidation through the LH mechanism, with the SA (Sabatier activity) and TOF (turnover frequency) values of 0.90 and 2.47, respectively. This approach will help to search for metal-free catalysts for the CO oxidation with the efficient LH mechanism.
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