Large Charge Transfer Research Articles

Adsorption of Greenhouse Decomposition Products on Ag2O-SnS2 and CuO-SnS2 Surfaces.

In this paper, based on density functional theory, the adsorption mechanism and gas sensitivity of Ag2O/CuO-modified SnS2 were analyzed. The results were analyzed according to the adsorption energy, total density of states, partial density of states, and frontier molecular orbital theory. The results show that the adsorption of all gas molecules is exothermic. NH3, Cl2, and C2H2 gases are chemisorbed on the modified SnS2 surfaces. After gas adsorption, the energy gap of the base changes by more than 10%, which fully shows that the conductivity changes greatly after gas adsorption, which can be reflected in the macroscopic resistance change. Ag2O–SnS2 is suitable as a gas sensor for NH3 gas sensors in terms of moderate adsorption distance, large adsorption energy, charge transfer, and frontier molecular orbital theory, while CuO–SnS2 is more suitable as a C2H2 gas sensor.

Ab initio random structure searching and catalytic properties of copper-based nanocluster with Earth-abundant metals for the electrocatalytic CO2-to-CO conversion

Understanding the effect of nano-structuring and metal doping on the properties of copper-based clusters is crucial to developing effective catalysts for the electrochemical conversion of CO2 to value-added chemicals. We present a computational approach based on density functional and random structure searching to investigate the structures of mono- and bi-bimetallic nanoclusters, the activation of CO2 on the catalyst, and the mechanism of CO2 dissociation. We have applied this approach to predict the structure and catalytic properties of Cun (n = 1–55) and (Cu-M)m (M = Fe, Sn, Zn with 1 ≤ m ≤ 27) nanoclusters. We also considered the CO2 activation and conversion on the low index Cu and Cu-M (100) surfaces, and high-symmetry (icosahedral) and core-shell Cu-M clusters. The most stable clusters are low-symmetry pure copper clusters with an amorphous character. Also, these clusters have higher catalytic activity than Cu (100) and high-symmetry icosahedral nanoclusters. In both pure copper and bimetallic systems, the physiosorbed state of CO2 is the most stable and energy is required to activate the molecule. The stabilization of the chemisorbed state occurs in systems such as Cu-Fe where there is delocalization of orbitals around the Fermi level, causing the large charge transfer from the catalyst to CO2. We have also conducted calculations of the free energy profiles of the CO2-to-CO conversion and the competitive hydrogen evolution reaction. The CO2 reduction reaction is dominant over the hydrogen evolution reaction on the Cu randomly generated cluster due to the lower potential limiting step. Among other considered bimetallic, the core@shell models also display good catalytic activity and selectivity towards the CO2 reduction reaction. This work identifies insightful structure-property relationships for CO2 activation, highlighting the influence of size and composition on the CO2 activation and intermediate stability in designing catalytic cupper-based mono- and bi-metallic clusters for the CO2 reduction reaction.

Electrostatic self-assembly combined with microwave hydrothermal strategy: construction of 1D/1D carbon nanofibers/crystalline g-C3N4 heterojunction for boosting photocatalytic hydrogen production

g-C3N4 (CN) has been widely explored as a visible light photocatalyst. Nevertheless, the low structural ordering of CN suffers from high-density defects that resulting in poor charge separation efficiency. Therefore, increasing the crystallinity of CN is considered to be an efficient approach to enhance its photocatalytic activity. However, crystalline g-C3N4 (CCN) synthesized via ionothermal method exhibits one-dimensional (1D) nanorod structure and is prone to agglomerate due to its high surface energy, giving rise to unsatisfactory performance improvement. Herein, the 1D carbon nanofibers/crystalline g-C3N4 heterojunction photocatalyst (CNF/CCN) is obtained through electrostatic self-assembly combined with microwave heating strategy. The CNF/CCN sample shows an enhanced photocatalytic H2 evolution rate (HER) of 6398 µmol g−1 h−1, which is up to 16.0 and 2.6 times of CN and CCN, respectively. The enhanced HER performance of CNF/CCN is attributed to the improved crystallinity of CN, promoted visible light utilization, large specific surface area and efficient charge transfer across the interface between CNF and CCN. This work conveys a simple and general method for crystallinity and activity enhancement for a wide range application of CN.

High performance ambipolar semiconductor of pyridine-capped diketopyrrolopyrrole-porphyrin oligomers: Roles of thiophen substitution and oligomer length

Series of seven donor-acceptor pyridine-capped diketopyrrolopyrrole − 5,15-diacetylenyl-10,20-diaryl-porphyrinato zinc oligomers nPyDPP-PAr [n = 1–3, Ar = methyl-benzothiophene (BT) or methyl thiophene (T) or methylbenzene (B)] were designed. Density functional theory calculations were performed to theoretically study the molecular geometry, electronic structure, and charge transport properties of the seven donor-acceptor compounds. The effects of oligomer length and different Ar groups on the crystal packing mode and charge transport properties were systematically studied. Thiophen substitution reduces the electron injection barrier, diminishes the reorganization energy, enlarges the charge transfer integral, and therefore shows three-to-one role for ambipolar semiconductor with large charge transfer mobility. Extending the π-conjugated backbone not only improves the semiconductor performance, but also makes the ambipolar performance more balanced. 3PyDPP-PT and 3PyDPP-PBT show high hole/electron transfer mobility as high as 8.28/7.90 cm2 V−1 s−1 and 9.00/9.79 cm2 V−1 s−1, respectively.

Sensing properties of nonmetal doped blue phosphorene toward NO and NO2 molecules: A first‐principles study

AbstractFirst‐principles calculations based on density functional theory (DFT‐D2 method) are adopted to systematically investigate the structure stability and sensing properties of NO and NO2 adsorbed on single nonmetals (B, C, and Si) and double nonmetals (1B1C, 1C1Si, and 1B1Si) doped blue phosphorene. The results show the chemisorption of the gas molecules absorbed on single nonmetal doped blue phosphorene with large adsorption energy, charge transfer, and small adsorption distance. Similarly, for gas molecules absorbed on double nonmetal doped blue phosphorene, while NO interaction with 1C1Si co‐doped blue phosphorene is weak. There is a strong hybridization between gas molecules and doped substrates due to the enhancing interaction, resulting in an increasing adsorption ability for gas molecules. We find that the conductivity and work function change caused by nonmetal doping is the main reason for improving the sensitivity of gas molecules, which shows more possibilities for practical gas sensor applications. Therefore, nonmetal doped blue phosphorene provides a new direction for detecting NO and NO2 in the gas sensing field.

Insight into the Contact Impedance between the Electrode and the Skin Surface for Electrophysical Recordings.

To obtain a performance improved dry electrode for bioelectrical activity detection is still a challenge, which is mainly due to the poor fundamental understanding on the impedance of the electrode–skin interface. Herein, the impedance between the electrode and the skin interface of three types of electrodes, which are the wet electrode, semidry electrode, and dry electrode, is investigated with electrochemical impedance spectroscopy combined with the spectra fitting technique. The parameters of performance duration, potential, and frequency associated with the impedance are explored for these three types of electrodes. The overall impedance is roughly constant within the performance duration and the potential applied in this study. Along with the frequency decreases, the impedance of the dry electrode reduces faster and is more complicated compared with the other two types of electrodes. Moreover, the results computed with the equivalent circuits show that the charge transfer resistance is additionally present compared to the wet and semidry electrodes. This large and additional charge transfer resistance may explain its relatively poorer electrophysiological properties.

A silicate-loaded MgAl LDH self-healing coating on biomedical Mg alloys for corrosion retardation and cytocompatibility enhancement

Clinical application of magnesium (Mg) alloys such as bone fracture fixation is hindered by the fast degradation rate under physiological conditions. In this work, a magnesium‑aluminum layered double hydroxide coating intercalated with silicate (LDH-SiO3) is fabricated on the anodized AZ31B Mg alloy by a hydrothermal technique and anion exchange process to tailor the corrosion rate and cytocompatibility. The LDH-SiO3 coating comprising a porous outer layer and compact inner layer adheres strongly to the anodized Mg alloy substrate. Electrochemical tests reveal that the LDH-SiO3 coating reduces the corrosion current density by 266 times to 0.8 ± 0.1 μA cm−2 in addition to yielding a large charge transfer resistance of 4.98 × 104 Ω cm2 in the simulated body fluid (SBF), revealing decreased corrosion because of inhibition of diffusion of aggressive ions through the compact and adherent inner LDH layer on the Mg alloy substrate. Immersion tests in SBF for 360 h reveal that the LDH-SiO3 coating mitigates corrosion propagation, Mg release, hydrogen evolution, and pH variation, indicating the notable long-term protection ability resulting from the self-healing LDH-SiO3 coating after localized corrosion occurs on the Mg alloy substrate. The self-healing mechanism mainly stems from SiO32− released from the LDH coating in conjunction with Mg leaching during natural degradation, resulting in the formation of Mg silicate precipitate that covers the corroded areas. Biologically, the LDH-SiO3 coating enhances attachment and proliferation of MC3T3-E1 pre-osteoblasts suggesting good cytocompatibility stemming from the favorable outcome including inhibited Mg leaching and alkalization as a result of the LDH-SiO3 coating. The self-healing LDH-SiO3 coating is very promising in expanding the clinical application of Mg-based implants by offering a viable approach to control corrosion and improve cytocompatibility.

Precise regulation of CO2 packing pattern in s-block metal doped single-layer covalent organic frameworks for high-performance CO2 capture and separation

The development of high-performance CO2 capture and separation adsorbents is critical to alleviate the deteriorating environmental issues. Herein, six s-block metal doped single-layer polymeric tetraoxa[8]circulene (SBM-TOCs, SBM = Li, Na, K, Be, Mg, and Ca) were introduced as potential CO2 capture and separation adsorbents via precise regulation of CO2 packing patterns. Structural analyses showed that Li-TOC, Na-TOC, K-TOC, and Ca-TOC were screened with high cohesive energies ranging from 7.02 to 7.08 eV/atom and moderate formation energies ranging from –2.92 to –1.41 eV, guaranteeing their structural stabilities for CO2 capture and separation. Electronic structure analyses confirmed the large charge transfer and strong covalent bonding characters between the SBMs and direct-connected O atoms, thus constructing a favorable gas adsorption environment. Li-TOC exhibited an ultrahigh CO2 adsorption capacity of 10.78 mmol/g at 298 K and 1.0 bar, which was superior to previously reported Li-doped adsorbents. At 298 K and 1.0 bar, the selectivity of CO2 over N2/CH4 in Li-TOC reached up to ∼ 516 and ∼ 821, respectively. Polarity regulation analyses showed that SBMs had a more positive effect on the framework affinity for CO2 than N2/CH4 via both coulomb and van der Waals interactions. Space regulation analyses showed that strong interactions between the electropositive SBMs and the electronegative O atoms of CO2 facilitated vertical CO2 configurations and compact distributions, thereby rendering a multilayer CO2 adsorption and enhancing the CO2 adsorption capacity. Results of this work highlighted SBM-TOCs as ultrahigh-performance adsorbents for CO2 capture and separation over N2/CH4, and demonstrated that the precise regulation of CO2 packing pattern was an effective strategy to achieve high-performance gas capture and separation.

A density functional theory study on the water aggregation behaviour of fatty acid-based anionic surface active ionic liquids

The hydrogen bond interactions between methyl-imidazolium cation (MIM+) and fatty acid anions (CmHnCOO–, where m = 1–6; n-3–13) of ionic liquids are studied in both gas phase and water phase using density functional theory. The structural properties show that the presence of N–H···O and C–H···O hydrogen bonds between [MIM]+ and [CmHnCOO]– (m = 1–6; n-3–13) ionic liquids. From the vibrational frequency analysis, it was found that the hydrogen bond interaction between [MIM]+ and [CmHnCOO]– (m = 1–6; n-3–13) ionic liquids are red-shifted in frequency. The natural bond orbital analysis show that the N–H···O hydrogen bond associated with the large charge transfer which has the higher stabilization energy (i.e. E(2) ~ 38 kcal/mol). Further, the cation/anion–water cluster (H2O)1–3 interactions show that the water molecules are preferred to interact with anions. In the case of ionic liquid–water cluster interaction, the water molecules occupies the interstitial space between cation and anion of ionic liquids which results in weakening the cation–anion interaction.

Monolayer Sc2CF2 as a Potential Selective and Sensitive NO2 Sensor: Insight from First-Principles Calculations.

Two-dimensional materials with excellent surface–volume ratios and massive reaction sites recently have been receiving attention for gas sensing. With first-principles calculations, we explored the performance of monolayer Sc2CF2 as a gas sensor. We investigated how molecule adsorption affects its electronic structure and optical properties. It is found that a large charge transfer quantity happens between Sc2CF2 and NO2, which results from the fact that the lowest unoccupied molecular orbital (LUMO) of NO2 is below the valence band maximum (VBM) of Sc2CF2. Moreover, the MD simulation shows that NO2 can adsorb on the Sc2CF2 surface stably at room temperature. We explored the effect of biaxial strain on the adsorption energy and charge transfer quantity of each system, and the results show that the biaxial strain can enhance both the adsorption energy and charge transfer quantity of the NO2 system and thus can improve the sensitivity of Sc2CF2 in detecting the NO2 molecule. Furthermore, we investigated the adsorption behavior and charge transfer of polar polyatomic molecules at the Sc2CF2 surface with h-BN as a substrate, and the results demonstrate that the h-BN substrate can hardly modify the main results. Our result predicts that Sc2CF2 can be a promising selective and sensitive sensor to detect the NO2 molecule, and could also give a theoretical guide for other terminated MXenes used for gas sensors or detectors.

Ultrastable Interfacial Contacts Enabling Unimpeded Charge Transfer and Ion Diffusion in Flexible Lithium-Ion Batteries.

Deteriorating interfacial contact under mechanical deformation induces large cracks and high charge transfer resistance, resulting in a severe capacity fading of flexible lithium‐ion batteries (LIBs). Herein, an oxygen plasma treatment on a polymer separator combined with high‐speed centrifugal spraying to construct ultrastable interfacial contacts is reported. With the treatment, abundant hydrophilic oxygen‐containing functional groups are produced and ensure strong chemical adhesion between the separator and the active materials. With single walled carbon nanotubes (SWCNTs) sprayed onto the active materials, a dense thin film is formed as the current collector. Meanwhile, the centrifugal force caused by high‐speed rotation together with van der Waals forces under fast evaporation produces a much closer interface between the current collector and the active materials. As a result of this ultrastable interfacial interaction, the integrated electrode shows no structural failure after 5000 bending cycles with the charge‐transfer resistance as low as 35.8% and a Li‐ion diffusion coefficient nearly 19 times of the untreated electrode. Flexible LIBs assembled with these integrated electrodes show excellent structural and electrochemical stability, and can work steadily under various deformed states and repeated bending. This work provides a new technique toward rational design of electrode configuration for flexible LIBs.

Acid etching halloysite loaded cobalt boride material for supercapacitor electrode application

Inexpensive and eco-friendly cobalt boride@etched halloysite (CoB@eHal) composites with excellent electrochemical performances were fabricated by a facile combination of acid etching and chemical liquid-phase reduction. The highly conductive CoB nanoparticles were tightly combined with etched halloysite in a loaded manner. Owing to the open channels of etched halloysite after acid etching and the loading of intermetallic CoB, the CoB@eHal-12 composite exhibited a relatively large specific surface and low charge transfer resistance. The charge storage mechanism belonged to redox pseudocapacitance, and the contribution of pseudocapacitance in the whole charge storage process is 67.9%. The optimized CoB@eHal-12 demonstrated satisfactory specific capacitance of 266.9 F g−1 at 0.5 A g−1, outstanding rate capacity and unexceptionable cycling stability of approximately 84.7% retention over 10,000 continuous charge-discharge cycles. Furthermore, an asymmetric supercapacitor was constructed by using the CoB@eHal-12 as a cathode and activated carbon (AC) as an anode. The obtained CoB@eHal-12//AC device delivered a maximum energy density of 17.0 W h kg−1 with a power density of 200.2 W kg−1, and a satisfactory life cycle.

DFT insights into the adsorption mechanism of five-membered aromatic heterocycles containing N, O, or S on Fe(1 1 0) surface

Understanding the interaction of five-membered aromatic heterocycles with Fe(110) surface is crucial to the design of novel inhibitors against the corrosion of iron and steel. Herein, we report a detailed study of the adsorption properties and the bonding mechanism of pyrrole, furan, and thiophene on Fe(110) surface employing density functional theory (DFT) calculations. In the most stable adsorption geometries, the adsorbates lie flat at the hollow site and form covalent bonds with surface Fe atoms. The chemisorptions are demonstrated by large adsorption energies and charge transfers from Fe(110) to the adsorbates. Taking vdW corrections into account in the DFT calculations has a minimal effect on the adsorption geometries whereas it significantly increases the adsorption energies. The energetic and structural analysis demonstrates large molecular distortion induced by the adsorbate–surface interaction, and thiophene experiences the least molecular distortions, thereby having the largest adsorption energy among the adsorbates. The electronic structure analysis reveals that the electronic interactions of pyrrole, furan, and thiophene and Fe(110) are due to the overlaps of the frontier molecular orbitals with Fe-3dz2 and Fe-(3dxz + 3dyz) states. The charge transfer between the adsorbates and Fe(110) are elucidated by the charge density difference plot and Bader charge analysis.

Effect of doping and vacancy defect on the sensitivity of stanene toward HCN

The adsorption behaviour of HCN molecule on a modified stanene substrate is investigated using first-principles calculation. The large adsorption distance, small adsorption energy and low charge transfer indicated that HCN molecule exhibits a weak physical adsorption mechanism on stanene. After introducing dopant and vacancy defects in the stanene substrate, the adsorption mechanism of HCN transformed into chemisorption. The significantly increased adsorption energy suggested that the interaction between the doped substrate and HCN was enhanced. Interestingly, the Cr-doped system not only exhibited a large charge transfer but also an intense magnetic performance. Our calculation results may provide useful information for fabricating stanene-based sensors. Highlights The adsorption of HCN on intact stanene is physical adsorption. The adsorption of HCN on vacancy defect stanene is chemisorption. The Cr doped vacancy-defected stanene is suitable for the HCN gas sensor.

Density Functional Theory Study of B, N, and Si Doped Penta-Graphene as the Potential Gas Sensors for NH3 Detection.

Designing a high-performance gas sensor to efficiently detect the hazardous NH3 molecule is beneficial to air monitoring and pollution control. In this work, the first-principles calculations were employed to investigate the adsorption structures, electronic characteristics, and gas sensing properties of the pristine and B-, N-, P-, Al-, and Si-doped penta-graphene (PG) toward the NH3, H2S, and SO2 molecules. The results indicate that the pristine PG is insensitive to those toxic gases due to the weak adsorption strength and long adsorption distance. Nevertheless, the doping of B, N, Al, and Si (B and Al) results in the transition of NH3 (H2S and SO2) adsorption from physisorption to chemisorption, which is primarily ascribed to the large charge transfer and strong orbital hybridizations between gas molecules and doping atoms. In addition, NH3 adsorption leads to the remarkable variation of electrical conductivity for the B-, N-, and Si-doped PG, and the adsorption strength of NH3 on the B-, N-, and Si-doped PG is larger than that of H2S and SO2. Moreover, the chemically adsorbed NH3 molecule on the N-, B-, and Si-doped PG can be effectively desorbed by injecting electrons into the systems. Those results shed light on the potential application of PG-based nanosheets as reusable gas sensors for NH3 detection.

Coloring and Bleaching Properties of 500–1000 nm‐Thick Electrochromic Tungsten Oxide Films Deposited by Reactive Direct Current Magnetron Sputtering

Amorphous tungsten oxide films are prepared on indium tin oxide/glass substrates using reactive magnetron sputtering and their electrochromic (EC) properties are investigated. To achieve the densely colored films, samples of 500 and 1000 nm thickness are deposited with different pumping speeds and oxygen flow rates at Ar 3 Pa atmosphere. The as‐deposited films are similarly transparent (≈80%), but their EC properties vary depending on the deposition conditions and strongly on film thickness. The 500 nm‐thick samples have a transmittance of 4–8% in the colored state, which recover well in the bleached state. In contrast, the 1000 nm‐thick films have very low transmittance (<1%) in the colored state but are not completely recovered. Among 1000 nm‐thick films, large pumping speed and a large oxygen flow rate condition result in comparatively better recoverability. The cyclic voltammograms of 500 nm films show small and balanced charge transfer, while those of 1000 nm films reveal large and unbalanced charge transfer. These indicate that more ions are intercalated into the 1000 nm samples but are not completely deintercalated. These findings contribute to the development of EC applications for light shielding.

Treatment of hazardous organic amine wastewater and simultaneous electricity generation using photocatalytic fuel cell based on TiO2/WO3 photoanode and Cu nanowires cathode

Organic amines are regarded as high toxic, refractory chemicals due to the great damage on human body, and ecosystem. The treatment of organic amine wastewater involves the removal of total nitrogen and toxic organics simultaneously, which is one of the biggest difficulties in wastewater treatment. In this study, hazardous organic amine wastewater was purified by a photocatalytic fuel cell (PFC) with efficient nitrogen removal and organic degradation, and its chemical energy was recovered simultaneously based on hydroxyl radical (HO·) and chlorine radical (Cl·) reaction in a novel TiO2/WO3 and 3D Cu nanowires modified Cu foam (CuNWs/CF) system. TiO2/WO3 heterojunction as photoanode provided rapid charge separation and good stability, and the composite of poly-Si enhanced the light harvest and charge transfer. HO· played critical role in degrading organic amines, while Cl· was responsible for selectively oxidizing amine group or NH4+ to N2. Besides, trace amount of NO2− and NO3− formed by over-oxidation was eliminated on CuNWs/CF cathode due to large specific surface area and fast charge transfer. Moderate Cl− concentration and initial pH had vital influence on strengthening Cl· and HO· generation in the system, and the optimal conditions were 50 mM NaCl and pH = 7. For methylamine, ethylamine and dimethylamine wastewater, the system showed total nitrogen removal efficiency of 94.93%, 91.81%, 93.10% and total organic carbon removal of 58.47%, 53.57%, and 56.71% within 2 h, respectively. Moreover, the corresponding maximum power densities of 2.49, 2.40, 2.27 mW cm−2 were also generated, respectively. The study proposes an efficient, sustainable method for the treatment of hazardous organic amine wastewater and simultaneous energy recovery.

Can We Predict Interface Dipoles Based on Molecular Properties?

We apply high-throughput density functional theory calculations and symbolic regression to hybrid inorganic/organic interfaces with the intent to extract physically meaningful correlations between the adsorption-induced work function modifications and the properties of the constituents. We separately investigate two cases: (1) hypothetical, free-standing self-assembled monolayers with a large intrinsic dipole moment and (2) metal–organic interfaces with a large charge-transfer-induced dipole. For the former, we find, without notable prior assumptions, the Topping model, as expected from the literature. For the latter, highly accurate correlations are found, which are, however, clearly unphysical.

Synthesis of bilayer borophene.

As the nearest-neighbour element to carbon, boron is theoretically predicted to have a planar two-dimensional form, named borophene, with novel properties, such as Dirac fermions and superconductivity. Several polymorphs of monolayer borophene have been grown on metal surfaces, yet thicker bilayer and few-layer nanosheets remain elusive. Here we report the synthesis of large-size, single-crystalline bilayer borophene on the Cu(111) surface by molecular beam epitaxy. Combining scanning tunnelling microscopy and first-principles calculations, we show that bilayer borophene consists of two stacked monolayers that are held together by covalent interlayer boron-boron bonding, and each monolayer has β12-like structures with zigzag rows. The formation of a bilayer is associated with a large transfer and redistribution of charge in the first boron layer on Cu(111), which provides additional electrons for the bonding of additional boron atoms, enabling the growth of the second layer. The bilayer borophene is shown to possess metallic character, and be less prone to being oxidized than its monolayer counterparts.

Triple-atom catalysts 3TM-GYs (TM = Cu, Fe, and Co; GY = graphyne) for high-performance CO2 reduction reaction to C1 products

Atomically dispersed catalysts are promising materials for alleviating greenhouse effect and reproducing valuable chemical products through electrochemical CO2 reduction reaction (CO2RR). Here, earth-abundant triple transition metals (TM = Cu, Fe, and Co) anchored on graphyne (3TM-GY) were evaluated in CO2RR to C1 products by using density functional theory. Structural analyses showed that 3TM-GYs had high cohesive energy ranging from 6.91 to 6.98 eV/atom, and large binding energy ranging from 2.28 to 5.95 eV, guaranteeing structural stability in CO2RR. Electronic structure analyses confirmed the evident orbital overlap and large charge transfer between the triple TM atoms and direct-connected C atoms. The unique triangular TM trimer on GY facilitated the “point-to-point” activation of CO2 with large adsorption energy and distinctly bent configuration, providing a favorable adsorption and initial activation environment in CO2RR. 3Cu-GY exhibited a prior CO2 reduction product of CH4 with a low limiting potential of −0.41 V and high selectivities over other C1 products of 102 – 108, which surpassed the vast majority of atomically dispersed electrocatalysts. When applied potential was increased, CO2RR on 3Cu-GY had a great advantage in the high-throughput reaction processes toward HCOOH and CH4, whereas that on 3Fe-GY/3Co-GY had a great advantage toward high-reduction degree products of CH3OH and CH4. Moreover, hydrogen evolution reaction was severely inhibited, and CO2RR exhibited an overwhelming advantage over HER. This work demonstrated that graphyne was a suitable substrate material for constructing favorable coordination environment anchoring triple atom, and highlighted the advance of triple-atom catalysts for high-performance CO2RR.