Nonmetal Atom Doping Induced Orbital Shifts and Charge Modulation at the Edge of Two-Dimensional Boron Carbonitride Leading to Enhanced Photocatalytic Nitrogen Reduction.

Electronic structure, particularly charge state analysis, plays a crucial role in comprehending catalytic mechanisms. This study focuses on metal-free boron carbonitride (BCN) nanosheets as a case study to investigate the impact of heteroatom doping on the charge state of active sites at the edge of two-dimensional (2D) metal-free nanomaterials. Our observations revealed that the doping induces a shift in the frontier py orbital near the Fermi level, accompanied by alterations in its charge state. These changes provide insights into the nitrogen adsorption descriptors and the critical hydrogenation step, ultimately leading to the proposal of a competitive charge transfer mechanism. Additionally, this exploration has led to the screening of five BCN-type structures (P@T1-C1, S@T1-B1, O@T1-B1, P@T1-B1C2, and P@T1-B1C3) with promising nitrogen reduction reaction (NRR) performances. The BCN structure (S@T1-B1) exhibited the lowest NRR overpotential reaching -0.2 V, which is associated with the proposed charge competition mechanism. Furthermore, the investigation delves into the key step hydrogenation mechanism, descriptors, and volcano diagrams of the conformational relationships. In addition, the proposed doping strategy endows the 2D-BCN with more sensitivity toward the solar spectrum, suggesting its application as a potential photocatalyst. Overall, this study establishes a strong foundation for the advancement of nonmetal-atom-doped BCN nanosheets in nitrogen reduction applications, while also providing a versatile framework for fine-tuning edge-site activity within the broader context of two-dimensional photo/electrocatalytic materials.

An Interfacial View of Cation Effects on Electrocatalysis Systems.

The identity of alkali metal cations in the electrolyte of electrocatalysis systems has been recently introduced as a crucial factor to tailor the kinetics and Faradaic efficiency of many electrocatalytic reactions. In this Minireview, we have summarized the recent advances in the molecular-level understanding of cation effects on relevant electrocatalytic processes such as hydrogen evolution (HER), oxygen evolution (OER), and CO2 electroreduction (CO2 RR) reactions. The discussion covers the effects of electrolyte cations on interfacial electric fields, structural organization of interfacial water molecules, blocking the catalytic active sites, stabilization or destabilization of intermediates, and interfacial pHs. These cation-induced interfacial phenomena have been reported to impact the performance (activity, selectivity, and stability) of electrochemical reactions collaboratively or independently. We describe that although there is almost a general agreement on the relationship between the size of alkali cations and the activities of HER, OER, and CO2 RR, however, the mechanism by which the performance of these electrocatalytic reactions is influenced by alkali metal cations is still in debate.

Cylindrical C96 Fullertubes: A Highly Active Metal-Free O2 -Reduction Electrocatalyst.

A new isolation protocol was recently reported for highly purified metallic Fullertubes D5h -C90 , D3d -C96 , and D5d -C100, which exhibit unique electronic features. Here, we report the oxygen reduction electrocatalytic behavior of C60 , C70 (spheroidal fullerenes), and C90 , C96 , and C100 (tubular fullerenes) using a combination of experimental and theoretical approaches. C96 (a metal-free catalyst) displayed remarkable oxygen reduction reaction (ORR) activity, with an onset potential of 0.85 V and a halfway potential of 0.75 V, which are close to the state-of-the-art Pt/C benchmark catalyst values. We achieved an excellent power density of 0.75 W cm-2 using C96 as a modified cathode in a proton-exchange membrane fuel cell, comparable to other recently reported efficient metal-free catalysts. Combined band structure (experimentally calculated) and free-energy (DFT) investigations show that both favorable energy-level alignment active catalytic sites on the carbon cage are responsible for the superior activity of C96 .

Diazonium functionalized fullerenes: a new class of efficient molecular catalysts for the hydrogen evolution reaction.

Considerable efforts are being made to find cheaper and more efficient alternatives to the currently commercially available catalysts based on precious metals for the Hydrogen Evolution Reaction (HER). In this context, fullerenes have started to gain attention due to their suitable electronic properties and relatively easy functionalization. We found that the covalent functionalization of C60, C70 and Sc3N@IhC80 with diazonium salts endows the fullerene cages with ultra-active charge polarization centers, which are located near the carbon-diazonium bond and improve the efficiency towards the molecular generation of hydrogen. To support our findings, Electrochemical Impedance Spectroscopy (EIS), double layer capacitance (Cdl) and Mott-Schottky approximation were performed. Among all the functionalized fullerenes, DPySc3N@IhC80 exhibited a very low onset potential (-0.025 V vs. RHE) value, which is due to the influence of the inner cluster on the extra improvement of the electronic density states of the catalytic sites. For the first time, the covalent assembly of fullerenes and diazonium groups was used as an electron polarization strategy to build superior molecular HER catalytic systems.

Controlling the Interfacial Charge Polarization of MOF-Derived 0D-2D vdW Architectures as a Unique Strategy for Bifunctional Oxygen Electrocatalysis.

The design of alternative earth-abundant van der Waals (vdW) nanoheterostructures for bifunctional oxygen evolution/reduction (OER/ORR) electrocatalysis is of paramount importance to fabricate energy-related devices. Herein, we report a simple metal-organic framework (MOF)-derived synthetic strategy to fabricate low-dimensional (LD) nanohybrids formed by zero-dimensional (0D) ZrO2 nanoparticles (NPs) and heteroatom-doped two-dimensional (2D) carbon nanostructures. The 2D platforms controlled the electronic structures of interfacial Zr atoms, thus producing optimized electron polarization for boron and nitrogen-doped carbon (BCN)/ZrO2 nanohybrids. X-ray photoelectron spectroscopy (XPS) and theoretical studies revealed the key role of the synergistic couple effect of boron (B) and nitrogen (N) in interfacial electronic polarization. The BCN/ZrO2 nanohybrid showed excellent bifunctional electrocatalytic activity, delivering an overpotential (η10) of 301 mV to reach a current density of 10 mA-cm-2 for the OER process and a half-wave potential (E1/2) of 0.85 V vs reversible hydrogen electrode (RHE) for the ORR process, which are comparable to the state-of-the-art LD nanohybrids. Furthermore, BCN/ZrO2 also showed competitive performances for water-splitting and zinc-air battery devices. This work establishes a new route to fabricate highly efficient multifunctional electrocatalysts by tuning the electronic polarization properties of 0D-2D electrochemical interfaces.

Low-dimensional heterostructures for advanced electrocatalysis: an experimental and computational perspective.

Low dimensional electrocatalytic heterostructures have recently attracted significant attention in the catalysis community due to their highly tuneable interfaces and exciting electronic features, opening up new possibilities for effective nanometric control of both the charge carriers and energetic states of several intermediate catalytic species. In-depth understanding of electrocatalytic routes at the interface between two or more low-dimensional nanostructures has triggered the development of heterostructure nanocatalysts with extraordinary properties for water splitting reactions, NRR and CO2RR. This tutorial review provides an overview of the most recent advances in synthetic strategies for 0D-1D, 0D-2D, and 2D-2D nanoheterostructures, discussing key aspects of their electrocatalytic performances from experimental and computational perspectives as well as their applications towards the development of overall water splitting and Zn-air battery devices.

Unravelling the Reaction Mechanisms of N2 Fixation on Molybdenum Nitride: A Full DFT Study from the Pristine Surface to Heteroatom Anchoring.

Transition metal nitrides (TMNs)-based materials have attracted increasing attention in electrochemical nitrogen reduction reaction (eNRR) because of their unique structures and inherent electronic properties. However, the eNRR mechanism on such nitrogen contained catalysts is still unclear, for example, which part of the catalyst act as the active sites, and how to achieve the optimal efficiency is also challenging. In this work, a comprehensive study was conducted to unravel the reaction mechanisms of N2 fixation on molybdenum nitride by using density functional theory (DFT) calculations. The activity and selectivity of eNRR on pristine (001) and (110) Mo5 N6 surfaces as well as few specific numbers of heteroatom-anchored N-terminated surfaces were all evaluated and compared. It was found that the Mo and N atoms on the pristine Mo5 N6 surface were both active for eNRR while following different pathways in mechanism. Moreover, the eNRR catalytic performance of Mo5 N6 could be further boosted by specific metal atoms anchoring, such as single atom, metal dimer, and heterodiatom pair. Finally, a full map of eNRR mechanism on pristine and metal atom-decorated Mo5 N6 surfaces was illustrated. This work not only provides a fundamental understanding of eNRR mechanism on TMNs based materials but also offers powerful strategies towards the rational design of efficient NRR electrocatalysts.

A New Class of Molecular Electrocatalysts for Hydrogen Evolution: Catalytic Activity of M3N@C2n (2n = 68, 78, and 80) Fullerenes.

The electrocatalytic properties of some endohedral fullerenes for hydrogen evolution reactions (HER) were recently predicted by DFT calculations. Nonetheless, the experimental catalytic performance under realistic electrochemical environments of these 0D-nanomaterials have not been explored. Here, for the first time, we disclose the HER electrocatalytic behavior of seven M3N@2n (2n = 68, 78, and 80) fullerenes (Gd3N@Ih(7)-C80, Y3N@Ih(7)-C80, Lu3N@Ih(7)-C80, Sc3N@Ih(7)-C80, Sc3N@D5h(6)-C80, Sc3N@D3h(5)-C78, and Sc3N@D3(6140)-C68) using a combination of experimental and theoretical techniques. The non-IPR Sc3N@D3(6140)-C68 compound exhibited the best catalytic performance toward the generation of molecular hydrogen, exhibiting an onset potential of -38 mV vs RHE, a very high mass activity of 1.75 A·mg-1 at -0.4 V vs RHE, and an excellent electrochemical stability, retaining 96% of the initial current after 24 h. The superior performance was explained on the basis of the fused pentagon rings, which represent a new and promising HER catalytic motif.

Nature-inspired hierarchical materials for sensing and energy storage applications.

Nature-inspired hierarchical architectures have recently drawn enormous interest in the materials science community, being considered as promising materials for the development of high-performance wearable electronic devices. Their highly dynamic interfacial interactions have opened new horizons towards the fabrication of sustainable sensing and energy storage materials with multifunctional properties. Nature-inspired assemblies can exhibit impressive properties including ultrahigh sensitivity, excellent energy density and coulombic efficiency behaviors as well as ultralong cycling stability and durability, which can be finely tuned and enhanced by controlling synergistic interfacial interactions between their individual components. This tutorial review article aims to address recent breakthroughs in the development of advanced Nature-inspired sensing and energy storage materials, with special emphasis on the influence of interfacial interactions over their improved properties.

Co-Cu Bimetallic Metal Organic Framework Catalyst Outperforms the Pt/C Benchmark for Oxygen Reduction.

Platinum (Pt)-based-nanomaterials are currently the most successful catalysts for the oxygen reduction reaction (ORR) in electrochemical energy conversion devices such as fuel cells and metal-air batteries. Nonetheless, Pt catalysts have serious drawbacks, including low abundance in nature, sluggish kinetics, and very high costs, which limit their practical applications. Herein, we report the first rationally designed nonprecious Co-Cu bimetallic metal-organic framework (MOF) using a low-temperature hydrothermal method that outperforms the electrocatalytic activity of Pt/C for ORR in alkaline environments. The MOF catalyst surpassed the ORR performance of Pt/C, exhibiting an onset potential of 1.06 V vs RHE, a half-wave potential of 0.95 V vs RHE, and a higher electrochemical stability (ΔE1/2 = 30 mV) after 1000 ORR cycles in 0.1 M NaOH. Additionally, it outperformed Pt/C in terms of power density and cyclability in zinc-air batteries. This outstanding behavior was attributed to the unique electronic synergy of the Co-Cu bimetallic centers in the MOF network, which was revealed by XPS and PDOS.

Mechanochemically Synthetized PAN-Based Co-N-Doped Carbon Materials as Electrocatalyst for Oxygen Evolution Reaction.

We report a new class of polyacrylonitrile (PAN)-based Co-N-doped carbon materials that can act as suitable catalyst for oxygen evolution reactions (OER). Different Co loadings were mechanochemically added into post-consumed PAN fibers. Subsequently, the samples were treated at 300 °C under air (PAN-A) or nitrogen (PAN-N) atmosphere to promote simultaneously the Co3O4 species and PAN cyclization. The resulting electrocatalysts were fully characterized and analyzed by X-ray diffraction (XRD) and photoelectron spectroscopy (XPS), transmission (TEM) and scanning electron (SEM) microscopies, as well as nitrogen porosimetry. The catalytic performance of the Co-N-doped carbon nanomaterials were tested for OER in alkaline environments. Cobalt-doped PAN-A samples showed worse OER electrocatalytic performance than their homologous PAN-N ones. The PAN-N/3% Co catalyst exhibited the lowest OER overpotential (460 mV) among all the Co-N-doped carbon nanocomposites, reaching 10 mA/cm2. This work provides in-depth insights on the electrocatalytic performance of metal-doped carbon nanomaterials for OER.

Tuning the Intermolecular Electron Transfer of Low-Dimensional and Metal-Free BCN/C60 Electrocatalysts via Interfacial Defects for Efficient Hydrogen and Oxygen Electrochemistry.

The development of low-dimensional (LD) supramolecular materials with multifunctional electrocatalytic properties has sparked the attention of the catalysis community. Herein, we report the synthesis of a new class of 0D-2D heterostructures composed of boron carbon nitride nanosheets (BCN NSs) and fullerene molecules (C60/F) that exhibit multifunctional electrocatalytic properties for the hydrogen evolution/oxidation reactions (HER/HOR) and the oxygen evolution/reduction reactions (OER/ORR). The electrocatalytic properties were studied with varying F:BCN weight ratios to optimize the intermolecular electron transfer (ET) from the BCN NSs to the electron-accepting C60 molecules. The nanohybrid supramolecular material with 10 wt % F in BCN NSs (10% F/BCN) exhibited the largest Raman and C 1s binding energy shifts, which were associated with greater cooperativity interactions and enhanced ET processes at the F/BCN interface. This synergistic interfacial phenomenon resulted in highly active catalytic sites that markedly boosted electrocatalytic activity of the material. The 10% F/BCN showed the highest tetrafunctional catalytic performance, outperforming the OER catalytic activity of commercial RuO2 catalysts with a η10 of 390 mV and very competitive onset potential values of -0.042 and 0.92 V vs RHE for HER and ORR, respectively, and a current density value of 1.47 mA cm-2 at 0.1 V vs RHE with an ultralow ΔGH* value of -0.03 eV toward the HOR process. Additionally, the 10% F/BCN catalyst was also used as both cathode and anode in a water splitting device, delivering a cell potential of 1.61 V to reach a current density of 10 mA cm-2.

Tissue paper-derived porous carbon encapsulated transition metal nanoparticles as advanced non-precious catalysts: Carbon-shell influence on the electrocatalytic behaviour.

Porous carbon encapsulated non-precious metal nanocatalysts have recently opened the ways towards the development of high-performance water remediation and energy conversion technologies. Herein, we report a facile, scalable and green synthetic methodology to fabricate porous carbon encapsulated transition metal nanocatalysts (M@TP: M = Cu, Ni, Fe and Co) using commercial tissue paper. The morphology, crystalline structure, chemical composition and textural properties of the M@TP nanocatalysts were thoroughly characterized. The catalytic activity of the M@TP nanocatalysts was investigated for the degradation of Congo red (CR) via peroxymonosulfate activation. Co@TP-6 was found to be the most active catalyst allowing 97.68% degradation in 30 min with a higher rate constant of 0.109 min-1. The nanocatalysts also displayed a carbon shell thickness-dependent electrocatalytic hydrogen evolution reaction (HER) activity, most likely due to the shielding effect of the carbon layers over the electron transfer (ET) processes at the metal core/carbon interfaces. Remarkably, the Ni@TP-6 electrocatalyst, with the smaller carbon shell thickness, showed the best electrocatalytic performance. They delivered an ultralow onset potential of -30 mV vs RHE, an overpotential of 105 mV at a current density of 10 mA·cm-2 and an excellent electrochemical stability to keep the 92% of the initial current applied after 25000 s, which is comparable with the HER activity of the state-of-the-art Ni-based catalysts.

Fullerenes as Key Components for Low-Dimensional (Photo)electrocatalytic Nanohybrid Materials.

An emerging class of heterostructures with unprecedented (photo)electrocatalytic behavior, involving the combination of fullerenes and low-dimensional (LD) nanohybrids, is currently expanding the field of energy materials. The unique physical and chemical properties of fullerenes have offered new opportunities to tailor both the electronic structures and the catalytic activities of the nanohybrid structures. Here, we comprehensively review the synthetic approaches to prepare fullerene-based hybrids with LD (0D, 1D, and 2D) materials in addition to their resulting structural and catalytic properties. Recent advances in the design of fullerene-based LD nanomaterials for (photo)electrocatalytic applications are emphasized. The fundamental relationship between the electronic structures and the catalytic functions of the heterostructures, including the role of the fullerenes, is addressed to provide an in-depth understanding of these emerging materials at the molecular level.

Tailoring the Interfacial Interactions of van der Waals 1T-MoS2/C60 Heterostructures for High-Performance Hydrogen Evolution Reaction Electrocatalysis.

Fullerene-based low-dimensional (LD) heterostructures have emerged as excellent energy conversion materials. We constructed van der Waals 1T-MoS2/C60 0D-2D heterostructures via a one-pot synthetic approach for catalytic hydrogen generation. The interfacial 1T-MoS2-C60 and C60-C60 interactions as well as their electrocatalytic properties were finely controlled by varying the weight percentages of the fullerenes. 1T-MoS2 platforms provided a novel template for the formation of C60 nanosheets (NSs) within a very narrow fullerene concentration range. The heterostructure domains of 1T-MoS2 and C60 NSs exhibited excellent hydrogen evolution reaction (HER) performances, with one of the lowest onset potentials and ΔGH* values for LD non-precious nanomaterials reported to date.

Tuning of Trifunctional NiCu Bimetallic Nanoparticles Confined in a Porous Carbon Network with Surface Composition and Local Structural Distortions for the Electrocatalytic Oxygen Reduction, Oxygen and Hydrogen Evolution Reactions.

The rational design of multifunctional catalysts that use non-noble metals to facilitate the interconversion between H2, O2, and H2O is an intense area of investigation. Bimetallic nanosystems with highly tunable electronic, structural, and catalytic properties that depend on their composition, structure, and size have attracted considerable attention. Herein, we report the synthesis of bimetallic nickel-copper (NiCu) alloy nanoparticles confined in a sp2 carbon framework that exhibits trifunctional catalytic properties toward hydrogen evolution (HER), oxygen reduction (ORR), and oxygen evolution (OER) reactions. The electrocatalytic functions of the NiCu nanoalloys were experimentally and theoretically correlated with the composition-dependent local structural distortion of the bimetallic lattice at the nanoparticle surfaces. Our study demonstrated a downshift of the d-band of the catalysts that adjusts the binding energies of the intermediate catalytic species. XPS analysis revealed that the binding energy for Ni 2p3/2 band of the Ni0.25Cu0.75/C nanoparticles was shifted ∼3 times compared to other bimetallic systems, and this was correlated to the high electrocatalytic activity observed. Interestingly, the bimetallic Ni0.25Cu0.75/C catalyst surpassed the OER performance of RuO2 benchmark catalyst exhibiting a small onset potential of 1.44 V vs RHE and an overpotential of 400 mV at 10 mA·cm-2 as well as the electrochemical long-term stability of commercial RuO2 and Pt catalysts and kept at least 90% of the initial current applied after 20 000 s for the OER/ORR/HER reactions. This study reveals significant insight about the structure-function relationship for non-noble bimetallic nanostructures with multifunctional electrocatalytic properties.

Improving Electrochemical Hydrogen Evolution of Ag@CN Nanocomposites by Synergistic Effects with α-Rich Proteins.

A graphitic carbon nitride nanostructure has been successfully functionalized by incorporation of different silver contents and subsequent modification with an α-rich protein, namely hemoglobin. Mechanochemistry has been employed, as an efficient and sustainable procedure, for the incorporation of the protein. A complete characterization analysis has been performed following a multitechnique approach. Particularly, XPS data exhibited considerable differences in the C 1s region for the Hb/xAg@CN, ensuring the successful protein anchorage on the surface of the graphitic carbon nitride-based materials. The as-synthesized nanomaterials delivered impressive performance toward hydrogen evolution reactions with an overpotential of 79 mV at a current density of 10 mA/cm2 for Hb/20Ag@CN nanohybrids, which is comparable with the most efficient HER electrocatalysts reported in the literature. The outstanding HER properties were associated with the unique synergistic interactions, quantitatively measured, between AgNPs, Hb tertiary architecture, and the graphitic carbon nitride networks.

Solvent-Free Preparation of 1,8-Dioxo-Octahydroxanthenes Employing Iron Oxide Nanomaterials.

In this study, 1,8-dioxo-octahydroxanthenes were prepared employing a simple, effective and environmentally sound approach utilizing an iron oxide nanocatalyst under solventless conditions. The proposed iron oxide nanomaterial exhibited high product yields, short reaction times and a facile work-up procedure. The synthesized catalyst was also found to be highly stable and reusable under the investigated conditions (up to twelve consecutive cycles) without any significant loss in its catalytic activity.

Boosting the electrochemical oxygen reduction activity of hemoglobin on fructose@graphene-oxide nanoplatforms.

A metal-free oxygen reduction reaction (ORR) electrocatalyst with outstanding performance was obtained through an easy and one-pot synthesis of hemoglobin functionalized fructose@graphene-oxide (GO) nanocomposites. The active pyridinic nitrogen sites of the highly unfolded proteins together with the excellent electronic properties of GO appears to be the main factors causing the improved electrocatalytic activity.