Electron Transfer Channels Research Articles

In-Situ Construction of Atomic-Level Fe-O Bond Bridges within Fe2N/g-C3N4 Heterojunction for Efficient Visible-Light-Driven Photocatalytic H2 Production.

The limited active sites and faster photogenerated electron-hole pair recombination rate of g-C3N4 restrict its application in photocatalytic H2 production. Constructing heterojunctions has been shown to improve the spatial (directional) separation of photogenerated electrons and holes. However, due to interface mismatch in traditional heterojunction structures and a lack of precise electron transport channels, the photocatalytic efficiency is limited. Here, we developed a two-step calcination approach to create an Fe2N/g-C3N4 heterojunction linked by Fe-O bonds (named as Fe-OCN). The newly formed Fe-O bonds within the heterojunction can act as atomic-level interface electron transfer channels, directly transferring the photogenerated electrons of g-C3N4 to the reactive center Fe2N, significantly improving the charge transfer rate and utilization, thus promoting visible-light-driven photocatalytic H2 production. The optimal Fe-OCN achieved a H2 production rate of 5986.29 μmol g-1 h-1 under visible light, 13.44 times higher than that of the OCN due to efficient charge separation and transfer capabilities. This work provides a constructive reference for the design and synthesis of organic-inorganic heterojunction with chemically bonded interfaces, establishing quick electron transfer channels, and achieving targeted electron transfer.

Construction of 0-dimensional silver quantum dot/MoSe2@MXene/3-dimensional porous copper foam composite electrodes with heterogeneous interfaces for synergistic electrocatalytic degradation of antibiotics

This study proposes a novel and efficient Ag quantum dots (QDs)/MoSe2@two-dimensional transition metal carbide/nitride (MXene)/copper foam (CF) composite electrode to address the challenge of electrocatalytic degradation of antibiotics in water. The electrode formed a unique electron donor–acceptor system by loading Ag QDs and heterostructured nanosheets on CF, significantly facilitating charge transfer and segregation at the interface. The catalytically active sites at the edges and defective locations of MoSe2 in conjunction with the two-dimensional MXene structure, which formed an efficient electron transfer channel, promoted the electron transfer from the interior to the surface and accelerated the hydrogen adsorption and reduction reactions. Moreover, the charge redistribution at the interface of Ag QDs and MoSe2@MXene formed interfacial dipoles, increasing the active sites on the catalyst surface and promoting the generation of cathodic atomic hydrogen (H*). Under optimal conditions, the degradation rate of tigecycline (TGC) reached as high as 90.1 % ± 2.4 % within 60 min. The anode-generated OH and HClO, along with the cathode-generated H, further promoted the degradation of TGC through co-catalysis. The degradation pathways were analyzed using density-functional theory (DFT) calculations and liquid chromatography-mass spectrometry (LC-MS) techniques. Moreover, toxicity analysis of the degradation products was carried out to ensure the safety of the treated wastewater discharge. A reflux continuous effluent reactor was also designed to achieve high degradation efficiency and low energy consumption after stable operation, laying the foundation for industrial applications. This technology provides new ideas for the design of green, efficient, stable, and low-consumption electrocatalytic reactors and contributes to a sustainable future environment.

Atomically dispersed Fe-N4 sites in activation of peroxymonosulfate for wastewater purification: Mechanism of non-radical pathways and their quantification

Single-atom catalysts are promising alternatives to homogeneous and heterogeneous catalysts in the advanced oxidation processes for contaminant degradation; however, quantifying the exact contribution of nonradical reactive oxygen species has remained challenging. Herein, Fe single atoms anchored on nitrogen-doped carbonaceous substrates (Fe SAs-N-C) were synthesized for peroxymonosulfate (PMS) activation toward pollutant degradation. Fe SAs-N-C achieved high activity within 30 min, which is 17.20 and 5.08 times higher than those of N-C catalysts without or with Fe nanoparticles, respectively. A synergistic mechanism of singlet oxygen (1O2) and electron transfer for dominating pollutant degradation was revealed. The former contributed 78.50 % while the latter contributed 21.50 % in pollutant elimination. Density functional theory calculations uncovered that the O atom in −SO4 moiety of PMS was adsorbed on the Fe atoms, leading to the OH bond elongation and generating 1O2. While the absorbed O atom in OO bond near to −SO4 moiety of PMS tended to enlarge the OO bond and accelerate the electron transfer. The adsorbed PMS was prone to being decomposed into 1O2 due to a lower energy barrier (0.43 eV) of 1O2 rate-determining step than that of electron transfer (0.95 eV). Fe-N4 sites are both electron transfer channels and 1O2 formation sites. This work provides insights into the quantitative contributions of non-radical active species to pollutant degradation.

Visible-light-driven F/C co-doping g-C3N4 nanosheets for efficient hydrogen evolution: Charge redistribution on C4 delocalized large π bond

Developing photocatalytic hydrogen evolution technology based on graphitic carbon nitride (g-C3N4, CN) has emerged as a potential solution for the future energy shortage in recent years. Herein, carbon (C) and fluorine (F) co-doping graphitic carbon nitride nanosheets (CFCN) were synthesized via a one-pot co-thermal method without introducing any metal element. Exceptional hydrogen production activity (3.87 mmol/h/g) was achieved by CFCN under visible light irradiation, which was 4.2-fold increase compared to the pristine CN. It could be attributed to the large specific surface area (51.59 m2/g) and efficient mass transfer facilitated by the porous sheet-like morphology of CFCN. Additionally, the modification of the band structure and internal charge redistribution were investigated via density functional theory (DFT) calculations, which confirmed there was a unidirectional and fast electron transfer channel from N through the C4 delocalized large π bond to F. This creative research uncovered the pivotal role of F/C co-doping in enhancing photocatalytic hydrogen evolution efficacy, offering cutting-edge insights into the design of sustainable and eco-friendly photocatalysts based on metal-free CN.

Type-II heterojunction In2O3/TiO2 with highly efficient charge separation for boosted photocatalytic NO abatement

Photocatalytic NO degradation often suffers from sluggish charge carrier separation and low selectivity. Herein, a series of In2O3/TiO2 (P25) composites were synthesized to enhance NO abatement. Benefiting from the conspicuous synergistic effect between In2O3 and P25, the In2O3/P25 catalysts demonstrated more than double the NO elimination performance compared to pure P25 and In2O3. The In2O3/P25 sample with 75 wt% In2O3 (In-P25-75) achieved a NO removal efficiency of 51.7 %, higher than reported catalysts (30.0–49.0 %). It was the successful formation of type-II heterostructure that enabled intimate interfacial contact and provided ample electron transfer channels. Moreover, photoluminescence spectra and photoelectrochemical measurement confirmed the improved separation and inhibited recombination of photogenerated charge carriers in In-P25-75, thereby boosting the NO photocatalytic efficiency. ·O2− and ·OH radicals generated by photoinduced electron transfer to the conduction band of P25, along with the induced holes confined to the valence band of In2O3, facilitated the targeted deep oxidation of trace NO into NO3− rather than harmful NO2. This work discloses a promising strategy for the efficient removal of NO from the atmosphere by reducing the emission of hazardous intermediate NO2.

Boosting photocatalytic efficiency and nonlinear optical response of graphitic carbon nitride by infusing carbon nanotubes

Nanostructured materials are widely studied for their light-driven physical and chemical processes, which are key to their potential in photophysical applications. We introduce a one-pot solid-state pyrolysis technique for the synthesis of graphitic carbon nitride/carbon nanotube (g-C3N4/CNT) composites. The formation of the composite was characterized through X-ray diffraction, scanning and transmission electron microscopy, and X-ray photoelectron spectroscopy. Notably, UV-vis diffuse reflectance spectroscopy indicated a reduction in the bandgap of pure g-C3N4 from 2.6 eV to 2.35 eV with the incorporation of 0.5 wt% CNT. The nonlinear optical transmission of the samples was analyzed at 532 nm using the open-aperture Z-scan technique employing 5 ns laser pulses, revealing a twelve-fold increase in the two-photon absorption coefficient (b) for g-C3N4/CNT0.5 compared to pristine g-C3N4. Remarkably, g-C3N4/CNT0.5 showed enhanced photocatalytic efficiency in degrading bisphenol A (BPA), with the kinetic constant (k) being ten times higher than that of pure g-C3N4. The improved photocatalytic performance of g-C3N4/CNT0.5 is attributed to the presence of CNTs, which act as effective electron acceptors and transfer channels, significantly enhancing the separation of photogenerated charge carriers in g-C3N4, as evidenced by the decreased intensity in the photoluminescence spectrum.

Confinement synthesis of few-layer MXene-cobalt@N-doped carbon and its application for electrochemical sensing

Herein, the few-layer Ti3C2Tx nanosheets loaded zeolitic imidazolate framework-67 nanoplates (Ti3C2Tx-ZIF-67) with a unique structure has been synthesized by surfactant control method, and then is employed as the core of precursor. A thin layer of polydopamine as the shell of precursor covered Ti3C2Tx-ZIF-67 forms a micro-nano reactor, leading to the confinement carbonization process. Consequently, a novel sensing material that few-layer Ti3C2Tx nanosheets loaded Co nanoparticles coated N-doped carbon (Ti3C2Tx-Co@NC) is obtained for the non-enzymatic determination of glucose. Owing to the impressive structure, the established glucose sensor based on Ti3C2Tx-Co@NC/glassy carbon electrode exhibits 0.5–100.0 μM of linear detection range and 66.8 nM of detection limit, which tends to detect low concentration of glucose. The synergistic few-layer Ti3C2Tx nanosheets, Co nanoparticles and NC are considered through a series of control experiments. First, few-layer Ti3C2Tx nanosheets provide a good transport channel for electron transfer, resulting in the lower steric hindrance. Second, Co nanoparticles provide active centers for the electrochemical detection. Third, N-doped carbon with conductivity and hydrophilia plays the role of stabilizing material structure to prevent the fragmentation of Ti3C2Tx and the agglomeration of Co nanoparticles. Such work proposes a confined strategy to develop MXene-ZIF-67-derived nanocomposite with high-performance structure.

Boosting Photogenerated Electrons Transfer from FeVO4 to Peroxymonosulfate via Cu Doping for Stable Degradation of Organic Contaminants

Comprehensive SummaryElectron transfer is an important way to activate persulfate. Currently, the electrons for persulfate activation mainly originate from organic contaminants or the catalyst itself, which can lead to selective activation of persulfate or oxidation of the catalyst, respectively, and thus become a bottleneck restricting its application. In this work, Cu−doped FeVO4 (Cu−FVO) was prepared, and the results showed that Cu doping can significantly improve the photocatalytic activity and stability of FVO for peroxymonosulfate (PMS) activation. The optimized Cu−FVO/PMS/light system exhibited a high BPA degradation rate that is 4.3 times higher than that of the FVO/PMS/light. This system manifested a broad applicability to various organic contaminants even with complex matrix. Photoelectrochemical analysis and DFT theoretical calculations revealed that Cu doping boosted the photogenerated charge separation and the adsorption of PMS on FVO. Furthermore, Cu doping led to the establishment of an electron transfer channel from Cu−FVO to PMS, through which photogenerated electrons achieved an efficient PMS activation. Meanwhile, holes were consumed by organic contaminants to avoid the oxidation of catalyst. These collectively enhanced the photocatalytic activity and stability of Cu−FVO, which also maintained high catalytic activity even after 20 cycling degradation reactions.

Chemically bonded to construct S-scheme CNQDs/Bi2WO6 heterostructure: The Bi-N bonds as interfacial electronic channel boosting the efficient photocatalytic CO2 reduction under simulated sunlight

Photoinduced carrier separation efficiency plays a crucial role in determining the photocatalytic activity of photocatalysts, but it remains a challenge to accurately and efficiently control charge separation. Hence, we successfully prepared S-scheme CNQDs/Bi2WO6 heterostructure via a simple hydrothermal method. The theoretical calculations demonstrate that Bi-N bonds at the interface between CNQDs and Bi2WO6 serve as an electron transfer channel to facilitate charge transfer at the atomic level, which plays a vital role in driving the photoreduction of CO2 to CO. Interestingly, S-scheme heterostructure not only remains strong reducing ability of CNQDs, but also significantly reduces the energy barrier of *CO2 *COOH and release the product CO easily. The CO yield of the CNQDs/Bi2WO6 sample (26.24 µmol/g) was 11 times higher than that of the pure Bi2WO6 (2.43 µmol/g) without any sacrificial agents under 300 W xenon lamp. This work highlights the critical role of chemical bonding interfaces in the design of efficient S-scheme heterostructure photocatalysts.

Reversed I1Cu4 single-atom sites for superior neutral ammonia electrosynthesis with nitrate

Electrochemical ammonia (NH3) synthesis from nitrate reduction (NITRR) offers an appealing solution for addressing environmental concerns and the energy crisis. However, most of the developed electrocatalysts reduce NO3- to NH3 via a hydrogen (H*)-mediated reduction mechanism, which suffers from undesired H*-H* dimerization to H2, resulting in unsatisfactory NH3 yields. Herein, we demonstrate that reversed I1Cu4 single-atom sites, prepared by anchoring iodine single atoms on the Cu surface, realized superior NITRR with a superior ammonia yield rate of 4.36 mg h-1 cm-2 and a Faradaic efficiency of 98.5% under neutral conditions via a proton-coupled electron transfer (PCET) mechanism, far beyond those of traditional Cu sites (NH3 yield rate of 0.082 mg h-1 cm-2 and Faradaic efficiency of 36.5%) and most of H*-mediated NITRR electrocatalysts. Theoretical calculations revealed that I single atoms can regulate the local electronic structures of adjacent Cu sites in favor of stronger O-end-bidentate NO3- adsorption with dual electron transfer channels and suppress the H* formation from the H2O dissociation, thus switching the NITRR mechanism from H*-mediated reduction to PCET. By integrating the monolithic I1Cu4 single-atom electrode into a flow-through device for continuous NITRR and in situ ammonia recovery, an industrial-level current density of 1 A cm-2 was achieved along with a NH3 yield rate of 69.4 mg h-1 cm-2. This study offers reversed single-atom sites for electrochemical ammonia synthesis with nitrate wastewater and sheds light on the importance of switching catalytic mechanisms in improving the performance of electrochemical reactions.

Unveiling the photoexcitation mechanism of COF-2CN material: From the perspective of molecular structure

Covalent organic frameworks (D-A COFs) with electron donor–acceptor structures possess electron transfer channels between the donor and acceptor components, making them potential candidates for applications requiring high photocatalytic activity. In this paper, COF-2CN is selected as a representative material, and computational studies are conducted based on density functional theory (DFT) to gain further insight into its excitation mechanism. First, we used first-principles calculations to determine the molecular structure of COF-2CN. The results reveal that the material has a hexagonal pore shape with a pore size of 25.81 Å, and all atoms in the monolayer structure lie in the same plane. Next, we plotted the density of states (DOS) for COF-2CN and determined that the highest occupied molecular orbital (HOMO) energy level is −0.22 eV. Additionally, we calculated the oscillator strengths for the first 100 excited states and selected 8 states with values greater than 0.2 for further analysis. Subsequently, we analyzed the distribution of electron holes in these excited states and found that, in most cases, the electrons and holes are distributed along the edges of the six-membered rings, with the holes having a broader distribution than the electrons. Finally, we simulated the UV–visible absorption spectrum of COF-2CN, finding that maximum light absorption occurs at a wavelength of 466.1 nm, with an intensity of approximately 454,057 L mol−1 cm−1.

Unlocking high-efficiency charge storage: Co-assembled nanoparticles of lignin and polyaniline molecules

Redox-active lignin rich in phenolic hydroxyl groups is an ingenious charge storage material. However, its insulating nature limits the storage/release of electrons and requires the construction of electron transfer channels within it. Herein, nanoparticles (PANI/DKL-NPs) are prepared by co-assembly via π–π interactions between conducting polyaniline (PANI) and demethylated Kraft lignin (DKL) molecules for the first time, and rapid electron transfer inside DKL is achieved. The co-assembled PANI/DKL-NPs consist of interpenetrating structures of PANI and DKL at the molecular scale, and the content of PANI molecules interspersed within them is controllable. Meanwhile, the extensive and abundant mesoporous structure in nanoscale PANI/DKL-NPs facilitates ion transport and electron storage. Based on this favorable microstructure, the specific capacitance of PANI/DKL-NPs at 1 A·g−1 is as high as 532 F·g−1, which is 780 % and 90.68 % higher compared to DKL-NPs and PANI-NPs, respectively. Meanwhile, the rate performance of PANI/DKL-NPs is significantly enhanced than that of DKL-NPs (33.11 %) and comparable to that of PANI-NPs (more than 69 %). Furthermore, the symmetric supercapacitor (PANI/DKL-NPs//PANI/DKL-NPs) assembled from it achieves a high energy density of 27.49 Wh·kg−1 at 400 W·kg−1 power density, and superb flexibility and mechanical stability. Therefore, the co-assembly of DKL and PANI will effectively stimulate the energy storage potential of lignin, providing a practical pathway to promote the development of biopolymers in energy storage.

S-ZVI@biochar constructs a directed electron transfer channel between dechlorinating bacteria, Shewanella oneidensis MR-1 and trichloroethylene

The combination of micron zero-valent iron (mZVI) and microorganisms is an effective method for trichloroethylene (TCE) degradation, but electron transfer efficiency needs improvement. A new chem-bio hybrid process using a composite material (S-ZVI@biochar) was developed, consisting of sulfurized mZVI and biochar as a chemical remover, and Shewanella oneidensis MR-1 and dechlorinating bacteria (DB) as a biological agent for TCE degradation. S-ZVI@biochar showed improved stability, biocompatibility, and TCE removal compared to ZVI and S-ZVI. The hybrid system DB + MR-1 + S-ZVI@biochar exhibited the highest TCE removal efficiency at 96.5% after 30 days, which was 3.7 times higher than that of bare ZVI. The study revealed that the enhanced dechlorination performance was due to improved electron transfer efficiency, adjustment of microbial community structure, and iron recycling. S-ZVI@biochar constructed electron transport channels in the composite system, improving the overall dechlorination capacity. This system shows promise for long-term TCE removal in anaerobic environments.

Computational study on the bifurcation mechanism in the H2CO− + CH3Cl →CH3CH2O + Cl−/H2CO + CH3 + Cl− reaction: The importance of intramolecular vibrational redistributions

We have investigated the bifurcation dynamics of the H2CO− + CH3Cl →CH3CH2O + Cl− (C-substitution channel)/H2CO + CH3 + Cl− (electron transfer channel) reaction using three different molecular dynamics (MD) methods: quasi-classical trajectory (QCT), classical MD, and ring-polymer MD simulations. All MD calculations were performed using the on-the-fly approach at the ab initio molecular orbital theory level. We found that the C-substitution channel is dominant in the classical and ring-polymer MD calculations, while the electron transfer channel is dominant in the QCT calculations. The different bifurcation mechanisms in the types of MD simulations were investigated using supervised machine-learning classification. This difference is attributed to the varying efficiency of the intramolecular vibrational redistribution process among the different MD methods. Thus, in the bifurcation mechanism of the H2CO− + CH3Cl reaction, the bifurcation fractions are primarily determined by the vibrational dynamics occurring in the later stages of the reaction.

Modulation of electron transfer behavior on Fe2P-Co2P/NPC oxygen electrocatalyst by lattice cation substitution engineering and charge transport network design for rechargeable Zn-air batteries

Crystal structure modulation engineering on the lattice scale and charge transport network design on the micro/nano scale work together to endow oxygen electrocatalysts with high reactivity to fully release the capacity of Zn-air batteries (ZABs) as the next-generation green energy storage devices. Metal phosphide-based oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) electrocatalysts with tunable electronic structures, variable valence states, and moderate overpotentials are recognized as the most promising and ideal candidates for air cathodes. The cation substitution strategy overcomes the drawback that single metal phosphides with fewer active sites and high adsorption barriers are not sufficient to achieve satisfactory electrocatalytic performance. In this paper, the Fe2P-Co2P/NPC oxygen electrocatalyst employing lattice cation site substitution engineering and three-dimensional (3D) conductive network encapsulation strategies are constructed to successfully ensure fast electron transfer behavior and safe charge/discharge energy storage. Noteworthy, the presence of Schottky barriers at the interface of the two materials hinders the electron reflux, which promotes a unidirectional flow of electrons, and increases the electron condensation in the OER and ORR processes. Relying on these features, the Fe2P-Co2P/NPC-assembled liquid ZABs achieved power densities, specific capacities, and energy densities of 175.18 mW cm-2, 805.75 mAh gZn-1, and 958.84 Wh kg-1, respectively, and importantly good rate performances and stability were exhibited even under high-current-density operation. The corresponding flexible solid-state ZABs also possesses superior electrochemical activity and mechanical flexibility. This work paves the way for the construction of bifunctional oxygen electrocatalysts with high-speed electron transfer channels, thus advancing the development of wearable electronic devices.

Activation of Bi2MoO6/Zn0.5Cd0.5S charge transfer through interface chemical bonds and surface defects for photothermal catalytic CO2 reduction

The photocatalytic reduction of CO2 to high-value fuels has been proposed as a solution to the energy crisis caused by the depletion of energy resources. Despite significant advancements in photocatalytic CO2 reduction catalyst development, there are still limitations such as poor CO2 adsorption/activation and low charge transfer efficiency. In this study, we employed a defect-induced heterojunction strategy to construct atomic-level interface Cd-O bonds and form Bi2MoO6/Zn0.5Cd0.5S heterojunctions. The sulfur vacancies (VS) formed in Bi2MoO6/Zn0.5Cd0.5S acted as activation sites for CO2 adsorption. While the interfacial stability provided by the Cd-O bonds served as an electron transfer channel that facilitated the movement of electrons from the interface to the catalytic site. The VS and Cd-O bonds simultaneously influence the distribution of charge, inducing the creation of an interface electric field that facilitates the upward displacement of the center of the d-band. This enhances the adsorption of reaction intermediates. The optimized Bi2MoO6/Zn0.5Cd0.5S heterostructure exhibited high selectivity and stability of photoelectrochemical properties for CO, generating 42.97 μmol⋅g−1⋅h−1 of CO, which was 16.65-fold higher than Zn0.5Cd0.5S under visible light drive. This research provides valuable insights for designing photocatalyst interfaces with improved CO2 adsorption conversion efficiency.

Discovery of FeP/Carbon Dots Nanozymes for Enhanced Peroxidase-Like Catalytic and Antibacterial Activity.

Iron phosphide/carbon (FeP/C) serving as electrocatalysts exhibit excellent activity in oxygen reduction reaction (ORR) process. H2O2 catalyzed by peroxidase (POD) is similar to the formation of new electron transfer channels and the optimization of adsorption of oxygen-containing intermediates or desorption of products in ORR process. However, it is still a challenge to discover FeP/C with enhanced POD-like catalytic activity in the electrocatalytic database for biocatalysis. The discovery of FeP/carbon dots (FeP/CDs) nanozymes driven by electrocatalytic activity for enhanced POD-like ability is demonstrated. FeP/CDs derived from CDs-Fe3+ chelates show enhanced POD-like catalytic and antibacterial activity. FeP/CDs exhibit enhanced POD-like activities with a specific activity of 31.1 Umg-1 that is double higher than that of FeP. The antibacterial ability of FeP/CDs nanozymes with enhanced POD-like activity is 98.1%. The antibacterial rate of FeP/CDs nanozymes (250µgmL-1) increased by 5%, 15%, and 36% compared with FeP, Fe2O3/CDs, and Cu3P/CDs nanozymes, respectively. FeP/CDs nanozymes will attract more efforts to discover or screen transition metal phosphide/C nanozymes with enhanced POD-like catalytic activity for biocatalysis in the electrocatalytic database.

Ultrafast carrier dynamics triggered by Ga-S bond in GaZnON/CdS heterojunction for efficient photocatalytic hydrogen evolution

Constructing heterojunction has been regarded as a valid strategy of photocatalysts to promote the catalytic process. However, beyond the possible synergistic advantage from the component catalysts, the understanding of the interface effect on the photocatalytic process within heterojunction remains challenging. Herein, we prepare a novel GaZnON/CdS heterojunction photocatalyst via a robust electrostatic assembly method. The sulfur atoms in CdS are found to occupy the nitrogen vacancy over the GaZnON surface to form interfacial Ga-S bonds, which is proved as electron-transfer channel between CdS and GaZnON to realize efficient photo-induced carrier separation. The dynamic study quantificationally reveals interfacial electron transfer with a fast transfer rate of 143.8 ns−1. Thereby, the optimal composite photocatalyst reached an impressive hydrogen evolution rate of 14.76 mmol g-1h−1, as well as an impressive AQY of 36.1 % (450 nm). This work expounds the ultrafast carrier dynamics underlying interface bonds within heterojunction for weakened photo-induced carrier recombination.

Breaking the scaling relations of effective CO2 electrochemical reduction in diatomic catalysts by adjusting the flow direction of intermediate structures.

The electrocatalytic carbon dioxide reduction reaction (CO2RR) is a promising approach to achieving a sustainable carbon cycle. Recently, diatomic catalysts (DACs) have demonstrated advantages in the CO2RR due to their complex and flexible active sites. However, our understanding of how DACs break the scaling relationship remains insufficient. Here, we investigate the CO2RR of 465 kinds of graphene-based DACs (M1M2-N6@Gra) formed from 30 metal atoms through high-throughput density functional theory (DFT) calculations. We find that the intermediates *COOH, *CO, and *CHO have multiple adsorption states, with 11 structural flow directions from *CO to *CHO. Four of these structural flow directions have catalysts that can break the linear scale relationship. Based on the adsorption energy relationship between *COOH, *CHO and *CO, we propose the concepts of linear scaling, moderate breaking, and severe deviation regions, leading to the establishment of new descriptors that identify 14 catalysts with potential superior performance. Among them, ZnRu-N6@Gra and CrNi-N6@Gra can reduce CO2 to CH4 at a low limiting potential. We also discovered that DACs have independent bidirectional electron transfer channels during the adsorption and activation of CO2, which can significantly improve the flexibility and efficiency of regulating the electronic structure. Furthermore, through machine learning (ML) analysis, we identify electronegativity, atomic number, and d electron count as key determinants of catalyst stability. This work provides new insights into the understanding of the DAC catalytic mechanism, as well as the design and screening of catalysts.

Molten Salt Synthesis of Ti3C2/Cu Cocatalyst for Enhanced TiO2 Photocatalytic CO2 Reduction

AbstractPhotocatalytic reduction of CO2 is considered as a crucial pathway towards achieving sustainable energy and environmental goals. Nonetheless, attaining efficient CO2 conversion poses significant challenges, primarily due to the slow dynamics of charge carriers and the high activation energy required to break C=O bonds. In this study, a novel strategy involving Lewis acid molten salt etching is investigated to engineer a titanium oxide (TiO2)‐based photocatalysts with dual electron transfer channels (i. e., Ti3C2/Cu), which targets the photoreduction of CO2 to CO and CH4. Thanks to the dual electron transfer channels presented in the cocatalysts (Ti3C2/Cu), in conjunction with the numerous heterogeneous interfaces between TiO2 and the Ti3C2/Cu cocatalysts, this hybrid catalyst not only reduces charge transfer resistance but also accelerates the dynamics of photogenerated charge carriers. Consequently, the TiO2/Ti3C2/Cu hybrid catalyst demonstrates an exceptional photocatalytic CO2 reduction rate of 13.67 μmol g−1 h−1, with a total utilized photoelectron number (UPN) of 102.34 μmol g−1 h−1. which is 3.99‐fold higher than that of unmodified TiO2. This research provides a new approach for the preparation of dual cocatalysts through a one‐step molten salt synthesis process.