Barrier For Electron Transfer Research Articles

Fe3 cluster-anchored monolayer MoS2 for direct deoxygenation of phenol: Catalyst design and activation mechanism

This study introduces a novel Fe3@MoS2 catalyst for the direct deoxygenation of phenol, key to lignin’s catalytic conversion into aromatic hydrocarbon bio-oil. Through density functional theory (DFT) calculations, we have dissected the electron transfer and activation barrier for the CO bond’s direct cleavage over the Fe3 cluster. A pivotal activation mechanism was uncovered, characterized by the formation and occupation of d-π* orbitals, which facilitates electron transfer from Fe3′s d orbital to phenol’s CO π* orbital. This enhanced catalytic activity is revealed to stem from the spin polarization and the reduced oxidation state of the Fe3 cluster, as corroborated by DOS and Bader charge analysis. Moreover, the study compares the performance of Fe3@MoS2 with that of heterogeneous active sites, such as 3Fe@MoS2 and Fe-3@MoS2, and finds that the homogeneous active site of Fe3@MoS2 is more favorable for phenol DDO in terms of both kinetic and thermodynamic aspects.

Building a highly concentration responsive optical thermometer via tunable electron transfer pathways supported by intervalence charge transfer states

The thermal-coupled levels (TCLs) of lanthanides have attracted great attention in the field of optical thermometer, offering an efficient method to achieve non-contect temperatuer feedback in complex environment. However, the iner 4f electrons are shielded, which becomes the core obstacle in improving the sensing performance. This issue is now circumvented by constructing an electron transfer pathway between Tm3+(1D2) and Eu3+(5D0) configurations. As a result, the electron transfer barrier is related to the relative temperature sensitivity, giving an insight into the modulation mechanism. Compared to the conventional TCLs systems, the relative temperature sensitivity of this strategy is highly concentration-responsive, increasing from 5.56 to 10.1 % K−1 as the Eu3+ molar concentration rises from 0.3 to 0.5 mol%. This work reveals the inner emission mechanism based on IVCT-supported emission mode, and presents the highly adjustability of sensing performance.

Accelerating ion diffusion kinetics with an intensified interfacial electric field for efficient hybrid capacitive deionization

The interfacial electric field (IEF) represents a cutting-edge strategy for enhancing ion diffusion kinetics, pivotal in various technological applications. Despite its extensive use, the mechanisms and strategies for regulating IEF remain underexplored. In this study, we enhanced the IEF in a MnO2-x/g-C3N4 (CN) heterostructure by engineering oxygen vacancies in MnO2, which increased the work function difference between MnO2 and CN. The increased work function difference effectively lowers the energy barrier for electron transfer at the heterostructure interface, thereby intensifying the IEF. The enhanced IEF subsequently provides a more potent driving force, facilitating ion movement within the electrode materials during the desalination process. The modified MnO2-x/CN heterostructure demonstrates a notable salt removal capacity of 45.5 mg g−1 and an impressive salt removal rate of 4 mg g−1 min−1, under an operational voltage of 1.2 V in a 500 mg/L NaCl solution. This research not only deepens our understanding of IEF modulation in materials but also sets the stage for the development of high-performance electrodes for hybrid capacitive deionization systems.

Contact-Electro-Catalysis Through Electret Behavior to Facilitate Electron Transfer.

Contact-electro-catalysis (CEC) usually uses polymer dielectrics as its catalysts under mechanical stimulation conditions, which although has a decent catalytic dye degradation effect still warrants performance improvement. A carrier separation promotion strategy based on an internal electric field by polarization can effectively improve ferroelectric material performance in photocatalysis and piezocatalysis. Therefore, carrier separation as a necessary process of CEC also can be promoted and is largely expected to improve CEC performance theoretically. However, the carrier separation enhancement by the internal electric field strategy has not been achieved in the CEC experiment yet, because of the difficulty of building an internal electric field in an inert polymer dielectric. Herein, a polytetrafluoroethylene (PTFE) dielectric was charged through an electret process, which was believed to establish an internal electric field for CEC catalysts proved by KPFM, XPS, and triboelectric nanogenerator voltage output analysis. The fastest degradation rate of methyl orange reached over 90% at 1.5 h, while the hydroxyl free radical (•OH) yield of the PTFE electret was nearly three times that of the original PTFE. Density functional theory (DFT) calculations verified that the potential barrier of interatomic electron transfer between PTFE and H2O was reduced by 37% under the internal electric field. The electret strategy used herein to optimize the PTFE catalyst provides a base for the use of other general plastics in CEC and facilitates the production of easily prepared, easily recyclable, and inexpensive polymer dielectric catalysts that can promote large-scale pollutant degradation via CEC.

Carbon Nanotubes as Controllable Electric-Field-Induced Bipolar Electrodes for Efficient Water Purification.

Advanced oxidation processes (AOPs) are the most efficient water cleaning technologies, but their applications face critical challenges in terms of mass/electron transfer limitations and catalyst loss/deactivation. Bipolar electrochemistry (BPE) is a wireless technique that is promising for energy and environmental applications. However, the synergy between AOPs and BPE has not been explored. In this study, by combining BPE with AOPs, we develop a general approach of using carbon nanotubes (CNTs) as electric-field-induced bipolar electrodes to control electron transfer for efficient water purification. This approach can be used for permanganate and peroxide activation, with superior performances in the degradation of refractory organic pollutants and excellent durability in recycling and scale-up experiments. Theoretical calculations, in situ measurements, and physical experiments showed that an electric field could substantially reduce the energy barrier of electron transfer over CNTs and induce them to produce bipolar electrodes via electrochemical polarization or to form monopolar electrodes through a single particle collision effect with feeding electrodes. This approach can continuously provide activated electrons from one pole of bipolar electrodes and simultaneously achieve "self-cleaning" of catalysts through CNT-mediated direct oxidation from another pole of bipolar electrodes. This study provides a fundamental scientific understanding of BPE, expands its scope in the environmental field, and offers a general methodology for water purification.

Covalent copper-organic frameworks with light-activable catalytic centers as smart artificial enzymes for highly sensitive and wide-range biocatalytic diagnosis

As a popular sensing method, colorimetric biosensing has the advantages of convenient operation, low cost, fast response, and easy readout. However, due to the complex structure of nanomaterials, low catalytic activity, and unclear catalytic mechanisms, constructing efficient, stable, and specific artificial biocatalysts for colorimetric biosensing is still a challenge. In this study, to propose a new colorimetric biosensing system, we synthesize three different types of copper cyclic trinuclear unit-based 2D copper-organic frameworks (CuOFs) with covalent structures and light-activable catalytic centers to serve as smart artificial enzymes for highly sensitive and wide-range biocatalytic diagnosis. By varying the light absorption centers, CuOFs with different band structures, light absorption capacity, photoelectron transfer efficiency, and electron-hole pair separation efficiency can be obtained. Of the three covalent CuOFs, tris(4-aminophenyl)amine (Tpa)-Cu3 exhibited the widest light absorption range, the narrowest band gap, the smallest electron transfer barrier, and the best-photoinduced charge separation efficiency, which was conducive to improving the light capture ability and eventually improving the photocatalytic properties. Further tests demonstrated that Tpa-Cu3 exhibited the best peroxidase-like activity under visible light irradiation, which could effectively diagnose the glucose and common antioxidants with a wider detection range and lower detection limit than many previously reported biocatalytic materials. We expect this design will provide new insights into enzyme-like organic framework materials and unique systems for high-sensitive and wide-range colorimetric detection for future biocatalytic applications.

Improving the performance and stability of inverted perovskite solar cell modules by cathode interface engineering

Perovskite solar cells (PSCs) represent a highly promising photovoltaic technology wherein a low-work function metal cathode is essential for efficient electron collection. The effectiveness of PSCs is significantly enhanced by a well-designed cathode interface layer (CIL). Characterized by their simple structure and impressive modification capabilities, small-molecule CILs hold considerable commercial potential for advancing the performance of PSCs. Herein, we synthesized a conjugated small-molecule CIL, named FY1, for modulating the cathode interface of inverted PSCs to enhance the power conversion efficiency (PCE) and long-term stability. FY1 not only optimized the molecule/metal contact to reduce traps but also uniformly improved the efficiency and speed of extracting photogenerated electrons, facilitating their effective extraction at the cathode interface. FY1 modification reduced the work function of Ag, subsequently lowering the energy barrier for electron transfer from the electron transport layer to the external cathode metal. By employing FY1 as a CIL, a record-high PCE of 23.72 % and a fill factor of 82.3 % were achieved in inverted PSCs. Furthermore, FY1 modification increased the PCE of PSC modules with an active area of 14 cm2 to 21.8 %; after continuous illumination for 850 h, it retained approximately 98.5 % of the initial efficiency. These findings show that FY1 can assist in unlocking the full potential of this emerging photovoltaic technology.

Constructing Interfacial Charge Transfer Channels and Electric Field in Violet Phosphorus-Based van der Waals Heterojunction for Phototherapy of Periodontitis.

Periodontitis, a chronic oral disease instigated by bacteria, severely compromises human oral health. The prevailing clinical treatment for periodontitis involves mechanical scraping in conjunction with antibiotics. Phototherapy is employed to rapidly remove the bacteria and achieve periodontitis treatment, effectively circumventing the adverse effects associated with traditional therapies. Constructing 2D/2D van der Waals (VDW) heterojunctions is a key strategy for obtaining excellent photocatalytic activity. Herein, a 2D/2D violet phosphorus (VP)/Ti3C2 VDW heterojunction is designed using an interfacial engineering strategy. By constructing an electron transport "bridge" (P-Ti bond) at the heterogeneous interface as an effective transfer channel for photogenerated carriers, a compact monolithic structure between the VP and Ti3C2 phases is formed, and the spatial barrier for electron transfer at the interface is eliminated. Meanwhile, the strong directional built-in electric field induced by the intensive electron-coupling effect at the heterogeneous interface served as an internal driving force, which greatly accelerates the exciton dissociation and charge transfer in the photocatalytic process. These excited photogenerated electrons and holes are trapped by O2 and H2O on the surfaces of Ti3C2 and VP, respectively, and are subsequently catalytically converted to antibacterial reactive oxygen species (ROS). The VP/Ti3C2 VDW heterojunction eradicated 97.5% and 98.48% of Staphylococcus aureus and Escherichia coli, respectively, by photocatalytic and photothermal effects under visible light for 10 min. The VP/Ti3C2 nanoperiodontal dressing ointment effectively attenuated inflammatory response, reduced alveolar bone resorption, and promoted periodontal soft and hard tissue repair. Its periodontitis therapeutic effect outperforms the clinically used Periocline.

Synthesis of Monodispersed Pd Nanoparticles and Ultrathin Twisty Pd Nanowire Networks for Electrooxidation of Ethanol.

In recent years, preparing precious metal catalysts with a controllable morphology has become a hot research topic for researchers. In this study, monodispersed palladium (Pd) nanoparticles (NP) and ultrathin Pd twisty nanowire networks (TNN) were synthesized in a solvothermal system using N,N-dimethylformamide (DMF) and oleylamine (OAm) as solvents, Transmission electron microscopy (TEM) images reveal the successful synthesis of nanoparticles and ultrathin TNN microstructures. Electrochemical data show that the current densities of Pd-NP and Pd-TNN for the ethanol oxidation reaction (EOR) reach 1878 mA mg-1 and 1765 mA mg-1, respectively. Compared to commercial Pd/C, Pd-TNN and Pd-NP exhibit better catalytic stability, lower electron transfer barriers, and more resistance to catalyst poisoning. Temperature, pH value, and ethanol concentration are all favorable for the EOR. According to the experimental data, the mechanism of enhanced electrocatalytic activity of Pd-NP and Pd-TNN catalysts for ethanol oxidation is discussed. This paper presents a method for preparing catalysts with stabilized structures to develop Pd-based catalysts for electrocatalytic oxidation reactions.

Boosting the internal electron transfer of two-dimensional hybrid perovskites via fluorination of organic cation towards enhanced photocatalytic hydrogen production

Two-dimensional (2D) organic-inorganic hybrid perovskites have emerged as promising candidates for photocatalytic hydrogen production due to their unique optoelectronic properties. However, the organic cations in the interlayer of 2D perovskites generally retard the internal charge transfer due to the large interlayer van der Waals barrier for electron transfer, which defines the imperative to engineering the organic entity. Herein, taking phenethylammonium lead iodide (PEA2PbI4) as a typical example, we show that by substituting the hydrogen with fluorine atom in the para-position of the phenyl group, the internal electron transfer was promoted remarkably. The improved electron transfer is ascribed to the introduction of fluorine with strong electronegativity, which leads to interlayer polarization and almost zero-potential barrier between the organic layers. Consequently, 4-FPEA2PbI4 exhibits ca. 8.2 times higher photocatalytic H2 evolution activity than PEA2PbI4. This work establishes a paradigm for optimizing the photocatalytic properties of 2D hybrid perovskites by engineering the organic cations.

In-situ reactivation and reuse of micronsized sulfidated zero-valent iron using SRB-enriched culture: A sustainable PRB technology

Sulfidated zero-valent iron (S-ZVI) is an attractive material of permeable reactive barriers (PRBs) for the remediation of contaminated groundwater. However, S-ZVI is prone to be passivated due to the oxidation of reactive and conductive iron sulfide (FeSx) shell and the formation of inactive and non-conductive ferric (hydr)oxides, which serve as electron transfer barriers to hinder the electron flow from Fe° core to contaminants. This study thus proposed a novel approach for in-situ reactivation and reuse of micronsized S-ZVI (S-mZVI) in PRB using sulfate-reducing bacteria (SRB) enriched culture to realize long-lasting remediation of Cr(VI)-contaminated groundwater. S-mZVI were passivated after reactions with Cr(VI) due to the formation of electron transfer barriers (mainly inactive and non-conductive Fe(III) (hyd)oxides, which increased the polarization resistance from 16.38 to 27.38 kΩ cm2 and hindered the electron transfer from the Fe° core. Interestingly, the passivated S-mZVI was efficiently reactivated by providing the SRB-enriched culture and organic carbon within 12 h, and the Cr(VI) removal capacity of S-mZVI in the three use cycles increased to 37.4 mg Cr/g, which was 2.1 times higher than that of the virgin S-mZVI. After biological reactivation, the Rp of reactivated S-mZVI decreased to 12.30 kΩ cm2. SRB-mediated reactivation removed the electron transfer barriers via biotic and abiotic reduction of Fe(III) (hyd)oxides. Especially, the microbial Fe(III) reduction mediated by FmnA-dmkA-fmnB-pplA-ndh2-eetAB-dmkB protein family enhanced the Fe2+ release from the surface and the subsequent re-formation of reactive and conductive FeSx shell. A long-term PRB column test further demonstrated the feasibility of in-situ biological reactivation and reuse of S-mZVI for enhanced Cr(VI)-contaminated groundwater remediation. Within 64 days, the Cr(VI) removal capacity of S-mZVI in the four use cycles increased by 3.2 times, compared to the virgin one. The bio-reactivation using the SRB-enriched culture and sulfate locally-available in groundwater will reduce the chemical and maintenance costs associated with the frequent replacement of reactive ZVI-based materials. The PRB technology based on the bio-renewable S-mZVI can be a sustainable alternative to the conventional PRBs for the long-lasting and low-cost remediation of groundwater contaminated by oxidative pollutants.

21.2% GaAs Solar Cell Using Bilayer Electron Selective Contact

GaAs remains one of the crucial materials for solar cell applications as it boasts the world's highest efficiency single‐junction solar cells. However, their high cost limits their widespread terrestrial applications. Traditional GaAs solar cells require a complex stack of doped junctions, which can only be grown using epitaxy, which is a very costly technique. Herein, a nonepitaxial bilayer of ZnO and TiO2 as electron‐selective contact is studied. It is shown that a bilayer selective contact can achieve very high performance through interface band engineering and a reduction of the barrier for electron transfer. 21.2% efficient solar cells is achieved, with Voc of 1.04 V, Jsc of 26.13 mA cm−2, and a fill factor of 77.8%. The Voc reported in the article is comparable to the highest Voc reported for substrate‐based GaAs solar cells of 1.075 V. An experimental loss analysis shows that the device is mainly limited by series and shunt resistance and reflection losses, both of which can further be minimized by optimization of the fabrication process. The results presented will be very useful for the further development of cheaper GaAs solar cells, whereas the bilayer selective contact concept can be implemented for other kinds of solar cells.

Efficient Electron Transfer through Interfacial Water Molecules across Two-Dimensional MoO3 for Humidity Sensing.

Resistive humidity sensors are required in flexible and integrated devices. Two-dimensional MoO3 offers a large interface area, enabling the modulation of its electrical properties over a wide range. In this study, 2D MoO3 was synthesized via liquid-phase exfoliation for humidity-sensing tests. In terms of high sensitivity, negligible hysteresis, linearity, and stability, the humidity-sensing performance of MoO3 is superior to those of other materials. The sensitivity reaches 9794 Ω/RH at 25 °C. The sensing mechanism of MoO3 was investigated by using impedance spectra and voltage-current scans under different humidity levels. The results indicate that the resistance change of MoO3 due to humidity originates from the interfacial conductance. Interfacial H2O adsorption induces efficient conducting paths via hydrogen bonding, decreases the potential barrier for electron transfer, and supplies additional electron states to the valence bands. In this study, electronic humidity sensing was investigated in depth, and a new perspective was proposed for electronic humidity sensing.

Enhanced Al‐Storage Performance by Electronic Properties Optimization and Structural Customization in MOF‐Derived Heterostructure

AbstractChalcogenide cathodes with multi‐electron transfer characteristics are indispensable to aluminum‐ion batteries (AIBs). Nevertheless, their grievous capacity degradation and sluggish reaction kinetics remain fundamental challenges for the practical application. Herein, a Cu2S/Ni3S2 multiphase structure within the metal‐organic frame (MOF) derived carbon decoration layer (CNS@MC) is constructed to elevate the intrinsic electronic properties of chalcogenide cathode and realize high‐performance AIBs. The existence of outer carbon layer and strong orbital interaction at inner heterointerfaces eliminates the bandgap and arises more electrons at Fermi level, efficiently reducing the energy barrier for electron transfer and achieving high reactivity within cathodes. The CNS@MC also presents a strong electronic interaction with active solvent groups, which is beneficial to capture Al3+ and facilitate the three‐electron charge‐storage reactions. Experimental results demonstrate that the tailored CNS@MC cathode possesses superior redox kinetics due to the sufficient surface area and rapid Al‐ion diffusion during cycling. Meanwhile, the robust CNS@MC delivers ultra‐high electrochemical stability (131.1 mAh g−1 over 3500 cycles) with high coulombic efficiency and outstanding rate performance. This work offers new opportunities for optimizing the intrinsic properties of the chalcogenide electrodes based on MOF derivatives and heterostructure, providing novel thoughts for designing high‐performance AIBs.

Thermal suppression of charge disproportionation accelerates interface electron transfer of water electrolysis.

The sluggish electron transfer kinetics in electrode polarization driven oxygen evolution reaction (OER) result in big energy barriers of water electrolysis. Accelerating the electron transfer at the electrolyte/catalytic layer/catalyst bulk interfaces is an efficient way to improve electricity-to-hydrogen efficiency. Herein, the electron transfer at the Sr3Fe2O7@SrFeOOH bulk/catalytic layer interface is accelerated by heating to eliminate charge disproportionation from Fe4+ to Fe3+ and Fe5+ in Sr3Fe2O7, a physical effect to thermally stabilize high-spin Fe4+ (t2g3eg1), providing available orbitals as electron transfer channels without pairing energy. As a result of thermal-induced changes in electronic states via thermal comproportionation, a sudden increase in OER performances was achieved as heating to completely suppress charge disproportionation, breaking a linear Arrhenius relationship. The strategy of regulating electronic states by thermal field opens a broad avenue to overcome the electron transfer barriers in water splitting.

The Electronic Structure of Transition Metal (TM) Oxides for the Oxygen Evolution Reaction: The Critical Role of TM 3d Hole State

Electrolysis of water to produce hydrogen and oxygen is a promising pathway for the storage of renewable energy in form of chemical fuels. The efficiency of the overall process is usually limited by the sluggish kinetics of the oxygen evolution reaction (OER) due to a complex four-electron/proton transfer mechanism. Therefore, the most crucial step for water electrolysis to become a widespread industrial process is to develop efficient electrocatalysts capable of driving the OER at a low overpotential.[1,2] In this talk, I will summaries the key electronic features that induces high catalytic activity towards the oxygen evolution reaction of trivalent transition metal (TM) oxides with perovskite structure, such as LaCoO3 [3] and LaFeO3.[4] The partial substitution of La for Sr in LaTMO3 results in the oxidation of TM3+ to TM4+ and substantially enhances OER catalytic activity. A comprehensive X-ray spectroscopic study, based on in-situ XPS and XAS, reveals a strong correlation of the enhanced OER catalytic activity with the presence of cations in the 4+ oxidation state. Increasing the concentration of TM cations in the 4+ oxidation state leads to a more covalent TM–O bond due to higher TM 3d–O 2p orbital hybridization and shifts the energy position of the valence band (VB) closer to the Fermi level (E F). Such an electronic modulation optimizes the surface adsorption energetics of *OH intermediates, contributing to faster OER kinetics. Furthermore, the oxidation of TM3+ to TM4+ creates a new unoccupied state (hole state) below the conduction band, associated with the formation of TM 3d empty electronic states. This hole states reduce the energy barrier for electron transfer associated with the OER, as illustrated in the figure below, thereby facilitating charge transfer at the interface during the reaction.Figure 1: Key electronic features of transition metal (TM) oxides for the oxygen evolution reaction

Sulfur vacancies-induced electron delocalization effect of cobalt sulfide for enhanced catalytic activation of peracetic acid and norfloxacin degradation

Antibiotics have attracted widespread attention due to their potential risks to human health and environment. In this study, a heterogeneous advanced oxidation process (AOP) of peracetic acid (PAA) activation by cobalt material was developed to degrade a typical antibiotic, norfloxacin (NOR). Cobalt sulfide materials with sulfur vacancies (CoSx) were synthesized through a two-step hydrothermal process. The optimized material (CoSx-2) could efficiently activate PAA system, achieving 91.8% NOR degradation in 5 min. The Co(II)/Co(III) species in CoSx was key to activating PAA, as Co(II) initiated the reaction and Co(III) activation caused the production of CH3C(=O)OO• species. Moreover, the presence of sulfur vacancies (VS) led to the generation of hydroxyl radicals (•OH) and singlet oxygen (1O2) via chain reactions with CH3C(=O)OO•. Density functional theory (DFT) calculations reveal the contribution of VS to enhanced catalytic PAA activation, as the lower work function (5.76 eV), higher adsorption energy (-3.43 eV), bridge effect of delocalized electrons and shifted d-band center are achieved to reduce the energy barrier for electron transfer during catalytic reaction. In addition, DFT calculation on Fukui index further explains that 18 N and 21 N are reactive sites of NOR for electrophilic attack, leading to primary degradation pathways of C–N cleavage, defluorination, dealkylation and hydroxylation. This study gives a new perspective on the regulation of material structure for efficient activation of PAA and promotes the practical application of heterogenous PAA-based AOPs for emerging contaminants removal in water treatment process.

Insights into Selective Mechanism of NiO-TiO2 Heterojunction to H2 and CO.

The construction of p-n heterojunctions has become a widely adopted strategy for achieving the selective detection of reducing gases, including H2 and CO. Nevertheless, the elucidation of the gas selectivity mechanism at the nanoscale remains elusive. First-principle calculations provide an attractive avenue for comprehending the influence of coordination structures on gas-sensitive selectivity, thereby unveiling the structure-activity relationship of p-n heterojunction sites. In this study, we investigate the selective adsorption behavior of H2 and CO on a NiO-TiO2 heterojunction using density functional theory. The results of d-band center analysis confirm that the NiO-TiO2 heterojunction with adsorbed oxygen significantly enhances the adsorption stability of reducing gases. Intriguingly, our calculations reveal that H2 has a higher affinity for adsorbed oxygen on the heterojunction surface compared to that of CO, corresponding to a lower H2 adsorption energy. Density of states (DOS) results indicate that the NiO-TiO2 heterojunction, with preadsorbed oxygen, exhibits ultrahigh selectivity with an n-type gas-sensitive response to H2, effectively eliminating the cross-sensitivity observed with CO, as confirmed by gas-sensitive characterization research. The sensing mechanism of the NiO-TiO2 heterojunction's selective detection of H2 without interference from CO can be visually explained by electron transfer and potential barrier changes, paving the way for future developments in novel, selective gas-sensitive materials.

In Situ Insertion of Silicon Nanowires into Hollow Porous Co/NC Polyhedra Enabling Large-Current-Density Hydrogen Evolution Electrocatalysis.

N-doped carbon (NC)-encapsulated transition metal (TM) nanocomposites are considered as alternatives to Pt-based hydrogen evolution reaction (HER) electrocatalysts; however, their poor electron transfer and mass diffusion capability at high current densities hinder their practical application. Herein, an oriented coupling strategy for the in situ grafting of ultrafine Co nanoparticle-embedded hollow porous C polyhedra onto Si nanowires (Co/NC-HP@Si-NWs) is proposed to address this concern. Experimental investigations reveal that the intimate coupling between the Si-NW and Co/NC nanocage forms a multithreaded conductive network, lowering the energy barrier for internal electron transfer. When functionalized as an HER electrocatalyst in 0.5m H2 SO4 , Co/NC-HP@Si-NWs deliver overpotentials as low as 57 and 440mV at 10 and 500mA cm-2 , respectively, which are much better than those of the pristine Co/NC-HP. Moreover, Co/NC-HP@Si-NWs show an outstanding cycle durability of 24h at 10 and 500mA cm-2 . The findings of this study are expected to inspire revolutionary work on the development of Si-mediated TM-based electrocatalysts for the HER.

Mechanistic insights into photo-assisted DMF cleavage mediated by charge transfer reaction

Mechanistic insights into the synthetically-valued metal-free sustainable N,N-dimethylamination of perfluoroarenes have been investigated. Density functional theory (DFT) and time-dependent DFT (TD-DFT) have been applied to provide details regarding photo-assisted cleavage of N, N-dimethylformamide (DMF) for the valued N, N-dimethylamination reaction. The radical reaction mediated by the electron transfer process causes DMF cleavage, which is responsible for the amination reaction. It was found that the energy barrier for the ground state reaction is thermally prohibitive. On the other hand, visible-light irradiation activates the electron-donor properties of DMF and acceptor properties of perfluoronaphthalene (PFN), so that the energy barrier for electron transfer reduces to ∼ 14 kcal/mol. The redistribution of the electronic charge between the DMF and PFN generates an imbalance of charge on the overall molecule. These events prompt the relocation of extraneous charges to some antibonding molecular orbitals so that one of the C-F bonds in PFN gets weakened and is easily broken. The reductive cleavage of the C-F bond enables the radical ions to react quickly to afford the amination products, which eventually deactivate to the ground state.