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Palladium hydrides (PdHx) are pivotal in both fundamental research and practical applications across a wide spectrum. PdHx nanocrystals, synthesized by heating in dimethylformamide (DMF), exhibit remarkable stability, granting them widespread applications in the field of electrocatalysis. However, this stability appears inconsistent with their metastable nature. The substantial challenges in characterizing nanoscale structures contribute to the limited understanding of this anomalous phenomenon. Here, through a series of well-conceived experimental designs and advanced characterization techniques, including aberration-corrected scanning transmission electron microscopy (AC-STEM), in situ X-ray diffraction (XRD), and time-of-flight secondary ion mass spectrometry (TOF-SIMS), we have uncovered evidence that indicates the presence of C and N within the lattice of Pd (PdCxNy), rather than H (PdHx). By combining theoretical calculations, we have thoroughly studied the potential configurations and thermodynamic stability of PdCxNy, demonstrating a 2.5:1 ratio of C to N infiltration into the Pd lattice. Furthermore, we successfully modulated the electronic structure of Pd nanocrystals through C and N doping, enhancing their catalytic activity in methanol oxidation reactions. This breakthrough provides a new perspective on the structure and composition of Pd-based nanocrystals infused with light elements, paving the way for the development of advanced catalytic materials in the future.
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The activity-stability trade-off relationship of oxygen reduction reaction (ORR) is a tricky issue that strikes the electrocatalyst population and hinders the widespread application of fuel cells. Here neoteric biphase Pd nanosheets that are structured with ultrathin two-dimensional crystalline Pd inner cores and ≈1 nm thin atomic-hybrid RhOx/Pd amorphous skins, named c/a-Pd@PdRh NSs, for disentangling this trade-off dilemma for alkaline ORR are developed. The superthin amorphous skins significantly amplify the quantity of flexibly low-coordinated atoms for electrocatalysis. An in situ selected oxidation of the top-surface Rh dopants creates atomically hybrid RhOx/Pd disorder surfaces. Detailed energy spectra and theoretical simulation confirm that these RhOx/Pd interfaces can arouse a surface charge redistribution, causing significant electron deficiency and lowered d-band center for surface Pd. Meanwhile, anticorrosive Rh/RhOx species can thermodynamically passivate the neighboring Pd atoms from oxidative dissolution. Thanks to these amplified interfacial effects, the biphase c/a-Pd@PdRh NSs simultaneously exhibit a superhigh ORR activity (5.92 A mg-1, 22.8 times that of Pt/C) and an outstanding long-lasting stability after 100k cycles of accelerated durability test, showcasing unprecedented electrocatalysts for breaking the activity-stability trade-off relationship of ORR. This work paves a bran-new strategy for designing high-performance electrocatalysts through creating modulated amorphous skins on low-dimensional nanomaterials.
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Breaking atomic monogeneity of catalyst surfaces is promising for constructing synergistic active centers to cope with complex multi-step catalytic reactions. Here, we report a defect-derived strategy for creating surface phosphorous vacancies (P-vacancies) on nanometric Rh2 P electrocatalysts toward drastically boosted electrocatalysis for alkaline hydrogen oxidation reaction (HOR). This strategy disrupts the monogeneity and atomic regularity of the thermodynamically stable P-terminated surfaces. Density functional theory calculations initially verify that the competitive adsorption behavior of Had and OHad on perfect P-terminated Rh2 P{200} facets (p-Rh2 P) can be bypassed on defective Rh2 P{200} surfaces (d-Rh2 P). The P-vacancies enable the exposure of sub-surface Rh atoms to act as exclusive H adsorption sites. Therein, the Had cooperates with the OHad on the peripheral P-sites to effectively accelerate the alkaline HOR. Defective Rh2 P nanowires (d-Rh2 P NWs) and perfect Rh2 P nanocubes (p-Rh2 P NCs) are then elaborately synthesized to experimentally represent the d-Rh2 P and p-Rh2 P catalytic surfaces. As expected, the P-vacancy-enriched d-Rh2 P NWs catalyst exhibits extremely high catalytic activity and outstanding CO tolerance for alkaline HOR electrocatalysis, attaining 5.7 and 14.3â times mass activity that of p-Rh2 P NCs and commercial Pt/C, respectively. This work sheds light on breaking the surface atomic monogeneity for the development of efficient heterogeneous catalysts.
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Colloidal quantum confined semiconductor-metal heterostructures are promising candidates for solar energy conversion because their light absorbing semiconductor and catalytic components can be independently tuned and optimized. Although the light-to-hydrogen efficiencies of such systems have shown interesting dependences on the morphologies of the semiconductor and metal domains, the mechanisms of such dependences are poorly understood. Here, we use Pt tipped 0D CdS quantum dots (with â¼4.6 nm diameter) and 1D CdS nanorods (of â¼13.8, 27.8, 66.6, and 88.9 nm average rod lengths) as a model system to study the distance-dependence of charge separation and charge recombination times and their impacts on photo-driven H2 production. The H2 generation quantum efficiency increases from 0.2% ± 0.0% in quantum dots to 28.9% ± 0.4% at a rod length of 28 nm and shows negligible changes at longer rod lengths. The half-life time of electron transfer from CdS to Pt increases monotonically with rod length, from 0.7 ± 0.1 in quantum dots to 170.2 ± 29.5 ps in the longest rods, corresponding to a slight decrease in electron transfer quantum efficiency from 92% to 81%. The amplitude-weighted average lifetime of charge recombination of the electron in Pt with the hole in CdS increases from 4.7 ± 0.4 µs in quantum dots to 149 ± 34 µs in 28 nm nanorods, and the lifetime does not increase further in longer rods, resembling the trend in the observed H2 generation quantum efficiency. Our result suggests that the competition of the charge recombination process with the hole removal by the sacrificial electron donor plays a dominant role in the observed nanorod length dependent overall light driven H2 generation quantum efficiency.
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Enhancing the catalytic activity of Ru metal in the hydrogen oxidation reaction (HOR) potential range, improving the insufficient activity of Ru caused by its oxophilicity, is of great significance for reducing the cost of anion exchange membrane fuel cells (AEMFCs). Here, we use Ru grown on Au@Pd as a model system to understand the underlying mechanism for activity improvement by combining direct in situ surface-enhanced Raman spectroscopy (SERS) evidence of the catalytic reaction intermediate (OHad) with in situ X-ray diffraction (XRD), electrochemical characterization, as well as DFT calculations. The results showed that the Au@Pd@Ru nanocatalyst utilizes the hydrogen storage capacity of the Pd interlayer to "temporarily" store the activated hydrogen enriched at the interface, which spontaneously overflows at the "hydrogen-deficient interface" to react with OHad adsorbed on Ru. It is the essential reason for the enhanced catalytic activity of Ru at anodic potential. This work deepens our understanding of the HOR mechanism and provides new ideas for the rational design of advanced electrocatalysts.
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Amorphous metals and alloys are promising candidates for superior catalysts in many catalytic and electrocatalytic reactions. It is of great urgency to develop a general method to construct amorphous alloys and further clarify the growth mechanism in a wet-chemical system. Herein, inspired by the conservation of energy during the crystallization process, amorphous PdCu nanoalloys have been successfully synthesized by promoting the chemical potential of the building blocks in solution. Benefiting from the abundant active sites and enhanced corrosion resistance, the synthesized amorphous PdCu nanostructures exhibit superior catalytic activity and durability over the face-centered cubic one in formic acid decomposition reaction. More importantly, the successful fabrications of amorphous PdFe, PdCo, and PdNi further demonstrate the universality of the above strategy. This proposed strategy is promising to diversify the amorphous family.
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Electromagnetic radiation and noise pollution are two of the four major environmental pollution sources. Although various materials with excellent microwave absorption performances or sound absorption properties have been manufactured, it is still a great challenge to design materials with both microwave absorption and sound absorption abilities due to different energy consumption mechanisms. Herein, a combination strategy based on structural engineering was proposed to develop bi-functional hierarchical Fe/C hollow microspheres composed of centripetal Fe/C nanosheets. Both of the interconnected channels created by multiple gaps among the adjacent Fe/C nanosheets and the hollow structure have positive effects on the absorbing performances by promoting the penetration of microwaves and acoustic waves and prolonging action time between microwave energy and acoustic energy with materials. In addition, a polymer-protection strategy and a high-temperature reduction process were applied to keep this unique morphology and further improve the performances of the composite. As a result, the optimized hierarchical Fe/C-500 hollow composite exhibits a wide effective absorption bandwidth of 7.52 GHz (10.48-18.00 GHz) at only 1.75 mm. Furthermore, the Fe/C-500 composite can effectively absorb sound wave in the frequency of 1209-3307 Hz, basically including part of the low frequency range (<2000 Hz) and most of the medium frequency range (2000-3500 Hz), and has 90% absorption of sound at 1721-1962 Hz. This work puts new insight into the engineering and development of microwave absorption-sound absorption-integrated functional materials with promising applications.
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High-entropy alloys (HEAs) have been attracting extensive research interests in designing advanced nanomaterials, while their precise control is still in the infancy stage. Herein, we have reported a well-defined PtBiPbNiCo hexagonal nanoplates (HEA HPs) as high-performance electrocatalysts. Structure analysis decodes that the HEA HP is constructed with PtBiPb medium-entropy core and PtBiNiCo high-entropy shell. Significantly, the HEA HPs can reach the specific and mass activities of 27.2â mA cm-2 and 7.1â A mgPt -1 for formic acid oxidation reaction (FAOR), being the record catalyst ever achieved in Pt-based catalysts, and can realize the membrane electrode assembly (MEA) power density (321.2â mW cm-2 ) in fuel cell. Further experimental and theoretical analyses collectively evidence that the hexagonal intermetallic core/atomic layer shell structure and multi-element synergy greatly promote the direct dehydrogenation pathway of formic acid molecule and suppress the formation of CO*.
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Water oxidation is one of the most challenging steps in CO2 photoreduction, but its influence on CO2 photoreduction is still poorly understood. Herein, the concept of accelerating the water oxidation kinetics to promote the CO2 photoreduction is realized by incorporating supramolecular porphyrin nanosheets (NS) into the C3 N4 catalyst. As a prototype, porphyrin-C3 N4 based van der Waals heterojunctions with efficient charge separation are elaborately designed, in which the porphyrin and C3 N4 NS serve as the water oxidation booster and CO2 reduction center, respectively. Theoretical calculations and relevant experiments demonstrate that the added porphyrin NS reverses the rate-limiting step in the water oxidation while reducing its energy barrier, thus resulting in faster reaction kinetics. Therefore, the optimal sample shows excellent performance in visible-light-driven CO2 reduction with a maximum CO evolution rate of 16.8 µmol g-1 h-1 , which is 6.8 times that of the C3 N4 NS and reaches the current state of the art for C3 N4 -based materials in CO2 photoreduction. Overall, this work throws light that accelerating water oxidation kinetics can effectively improve the CO2 photoreduction efficiency.
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The antimony chalcogenide crystals are composed of quasi-one-dimensional [Sb4X6]n ribbons, which lead to strong anisotropic optical and electronic properties. An attempt to exploit photoconductivity anisotropy in the device fabrication may introduce a rewarding strategy to propel the development of the antimony chalcogenide solar cells. To achieve this, understanding of the dynamic evolution of the photoconductivity anisotropy is required. Here, the photoconductivities along different lattice directions in an antimony selenide single crystal are investigated by time-resolved terahertz spectroscopy. We find that electron trapping results in a variation of the photoconductivity anisotropy accompanied by a decrease in the photoconductivity magnitude, while electron-hole recombination only reduces the magnitude but does not affect the anisotropy. Therefore, measuring the temporal evolution of photoconductivity anisotropy can provide a wealth of information regarding the nature of the photocarrier and also render a probe to selectively evaluate the photoconductivity decay mechanisms.
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Owing to their unique electromagnetic properties and structure anisotropy, two-dimensional (2D) magnetic metal flakes are attracting special attention for applications as microwave absorption materials. However, the conductive network formed by the connected metal flakes may lead to impedance mismatching and reduced performance. In this study, a facile and rational strategy was developed to fabricate yolk-shell-structured 2D flaky Fe/void/C composites by using α-Fe2O3 hexagonal flakes as the template, followed by the coating of polydopamine (PDA) on the composite surface and calcination under H2/Ar. The volume shrinkage from Fe2O3 to Fe and PDA to carbon led to the formation of several irregular holes in Fe flakes and void space between the Fe cores and carbon cages. The thickness of carbon cages of the composites can be tailored by the simple modulation of the synthetic parameters. As a result of the synergistic effects of multiple chemical components, the shape anisotropy of iron flakes, and unique yolk-shell structures, the optimized sample exhibited excellent microwave absorption properties. With a matching thickness of only 1.6 mm, the strongest reflection loss (RL) was up to -27.80 dB at 14.72 GHz, and the effective absorption bandwidth (EAB, RL < -10 dB) reached 6.40 GHz (11.60-18.00 GHz), which can cover the whole Ku-band. This study provides a novel approach to adjust and balance the permeability and permittivity of 2D magnetic metal flakes, which may promote the practical applications of flaky magnetic metal materials in microwave absorption.
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Pd-based electrocatalysts are considered to be a promising alternative to Pt in anion-exchange membrane fuel cells (AEMFCs), although major challenges remain. Most of the Pd-based electrocatalysts developed for the sluggish oxygen reduction reaction (ORR) have been exclusively evaluated by rotating disk electrode (RDE) voltammetry at room temperature, rather than in membrane electrode assemblies (MEAs), making it challenging to apply them in practical fuel cells. We have developed a series of carbon-supported novel PdHx nanosheets (PdHx NS), which displayed outstanding ORR performance in room-temperature RDE tests. Specifically, a sample synthesized at 190 °C displayed a mass activity of 0.67 A mg-1 and a specific activity of 1.07 mA cm-2 at 0.95 V vs RHE, representing the highest reported value among Pd-based ORR electrocatalysts in alkaline media and higher than Pt-based catalysts reported in the literature. Furthermore, we employed PdHx NS and commercial Pd/C as model catalysts to systematically study the effects of temperature on their ORR activity in RDE measurements and subsequently evaluated their performance in MEA testing. Our observations indicate/demonstrate how oxidative stability affected the ORR performance of Pd-based electrocatalysts, which provided some critical insights into future ORR catalyst development for alkaline fuel cell applications.
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Oxígeno , Paladio , Catálisis , Estrés OxidativoRESUMEN
Dual-active-sites atomically coupled on ultrafine 1D nanowires (NWs) can offer synergic atomic heterojunctions (AHJs) and high atomic-utilization toward multipurpose and superior catalysis. Here, ≈2-nm-thick PtIr/IrOx hybrid NWs are elaborately synthesized with equilibrated Pt/IrOx AHJs as high-efficiency bifunctional electrocatalysts for overall water splitting. Mechanism studies reveal the atomically coupled Pt-IrOx dual-sites are favorable for facilitating water dissociation, alleviating the binding of H* on Pt sites and inversely regulating the *OH adsorption and oxidation on bridge Ir-Ir sites. By simply equilibrating the Pt-IrOx ratio, the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) can be substantially accelerated. In particular, Pt-rich PtIr/IrOx -30 NWs attain 11-fold enhancements for HER compared to Pt/C in 1.0 m KOH, while IrOx -rich PtIr/IrOx -50 NWs express about five times mass activity referring to Ir/C for OER. Remarkably, the ratio-optimized PtIr/IrOx NWs electrode couple achieves a durably continuous H2 production under a substantially low cell voltage.
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Nanocables , Catálisis , Electrodos , Hidrógeno , Oxígeno , AguaRESUMEN
Research of detection of low molecular weight compounds on human health and biological systems become increasingly important. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS), a soft ionization equipment, is a rapid, reliable, high-sensitivity, high-throughput and simple test instrument. However, the application of MALDI-TOF MS in the analysis of small molecules (<500 Da) has become a great challenge because of the interference from the conventional matrices in low mass region when using conventional matrices. In this research, tricobalt tetraoxide (Co3O4) nanocrystals with rich surface hydroxyl groups were synthesized and served as novel matrices for the detection of small molecules by MALDI-TOF MS. In comparison with conventional organic matrices, the use of as-prepared Co3O4 nanocrystal matrices showed little matrix background interference, good reproducibility and high signal intensity in the analyses of amino acids, harmful additives and pesticide residues. For the detection of most amino acids, Co3O4 nanocrystal matrices have good detection performance both in the positive and negative ion modes and have a unique decarboxylation peak in the positive ion mode, which is conducive to the identification of amino acids. In addition, Co3O4 nanocrystals are completely feasible to test triadimefon, pirimicarb and other pesticide residues, as well as additives such as bisphenol A and melamine in the positive ion mode. It is also feasible to detect small molecule compounds in practical samples using Co3O4 nanocrystals as matrices. We believe the work provides an alternative approach for the detection of small molecules and expands the application scope of Co3O4 nanocrystals.
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Nanopartículas , Residuos de Plaguicidas , Aminoácidos , Cobalto , Humanos , Óxidos , Reproducibilidad de los Resultados , Espectrometría de Masa por Láser de Matriz Asistida de Ionización Desorción/métodosRESUMEN
Decreasing the metal catalyst size into nanoclusters or even single atom is an emerging direction of developing more efficient and cost-effective photocatalytic systems. Because the catalyst particle size affects both the catalyst activity and light driven charge separation efficiency, their effects on the overall photocatalytic efficiency are still poorly understood. Herein, using a well-defined semiconductor-metal heterostructure with Pt nanoparticle catalysts selectively grown on the apexes of CdS nanorods (NRs), we study the effect of the Pt catalyst size on light driven H2 generation quantum efficiency (QEH2). With the increase of the Pt catalyst size from 0.7 ± 0.3 to 3.0 ± 0.8 nm, the QEH2 of CdS-Pt increases from 0.5 ± 0.2% to 38.3 ± 5.1%, by nearly 2 orders of magnitude. Transient absorption spectroscopy measurement reveals that the electron transfer rate from the CdS NR to the Pt tip increases with the Pt diameter following a scaling law of d5.6, giving rise to the increase of electron transfer efficiency at larger Pt sizes. The observed trend can be understood by a simplified kinetic model that assumes the overall efficiency is the product of the quantum efficiencies of charge separation (including hole transfer, electron transfer, and hole scavenging) and water reduction steps, and for CdS-Pt NRs, the quantum efficiencies of electron transfer and water reduction steps increase with the Pt sizes. Our findings suggest the importance of improving the quantum efficiencies of both charge separation and catalysis in designing efficient semiconductor-metal hybrid photocatalysts, especially in the regime of small metal particle sizes.
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Ethanol is a promising liquid clean energy source in the energy conversion field. However, the self-poisoning caused by the strongly adsorbed reaction intermediates (typically, CO) is a critical problem in ethanol oxidation reaction. To address this issue, we proposed a joint use of two strategies, alloying of Pt with other metals and building Pt/metal-oxide interfaces, to achieve high-performance electrocatalytic ethanol oxidation. For this, a well-designed synthetic route combining wet impregnation with a two-step thermal treatment process was established to construct PtSn/SnOx interfaces on carbon nanotubes. Using this route, the alloying of Pt-Sn and formation of PtSn-SnOx interfaces can simultaneously be achieved, and the coverage of SnOx thin films on PtSn alloy nanoparticles can be facilely tuned by the strong interaction between Pt and SnOx . The results revealed that the partial coverage of SnOx species not only retained the active sites, but also enhanced the CO anti-poisoning ability of the catalyst. Consequently, the H-PtSn/SnOx /CNT-2 catalyst with an optimized PtSn-SnOx interface showed significantly improved performances toward the ethanol oxidation reaction (825â mA mgPt -1 ). This study provides deep insights into the structure-performance relationship of PtSn/metal oxide composite catalysts, which would be helpful for the future design and fabrication of high-performance Pt-based ethanol oxidation reaction catalysts.
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The formimidoyltransferase cyclodeaminase (FTCD) gene encodes an enzyme required for the catabolism of histidine and tetrahydrofolate (THF). Previous studies showed that FTCD plays a role as a tumour suppressor gene in hepatocellular carcinoma (HCC). It is unknown whether the restoration of functional FTCD may exhibit an anti-tumour effect on HCC. This study constructed a delivery system based on hollow mesoporous organosilica nanotheranostics (HMON) capable of efficiently loading Mn ions and FTCD plasmids. This study showed that the Mn-doped and FTCD-loaded nanoparticles (HMON@Mn-PEI@FTCD) could efficiently induce the expression of FTCD and achieve enhanced magnetic resonance imaging. In vitro results demonstrated that the upregulation of FTCD induced by HMON@Mn-PEI@FTCD nanoparticles dramatically reduced intracellular THF levels, inhibited of NADPH/NADP+ and GSH/GSSG ratios, and induced reactive oxygen species generation and mitochondrial oxidative stress. As a result, cytochrome c release increased with the opening of the mitochondrial permeability transition pore, which finally activated the caspase-dependent cell apoptosis pathway. Therefore, our designed HMON@Mn-PEI@FTCD could induce apoptosis by activating the mitochondria-mediated apoptosis signalling pathway, and finally significantly suppressed the proliferation of HCC both in vitro and in vivo, which provides an effective strategy for the treatment of HCC.
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Carcinoma Hepatocelular , Neoplasias Hepáticas , Apoptosis , Carcinoma Hepatocelular/diagnóstico por imagen , Carcinoma Hepatocelular/tratamiento farmacológico , Línea Celular Tumoral , Humanos , Neoplasias Hepáticas/diagnóstico por imagen , Neoplasias Hepáticas/tratamiento farmacológico , Imagen por Resonancia Magnética , Plásmidos , Tetrahidrofolatos , Nanomedicina TeranósticaRESUMEN
The intrinsic factors affecting the bulk structures of nanocrystallites are not well explored during crystallization. In this study, it is demonstrated that the chemical potential of growth units plays decisive role in governing the final structure of nanocrystals. It is found that the types of reaction vessels are able to vary the chemical potential of growth units, and make the Pt and Pd nanocrystals (NCs) unexpectedly evolve from the cyclic penta-twinned to the single-crystal nanostructures. In turn, it is concluded that the crystal growth units with lower chemical potential favor the formation of crystal nuclei with lower chemical potential during the nucleation. This new approach in tuning the bulk structures of NCs enriches the understanding of the crystallization process under supersaturated (nonequilibrium) condition, and would provide a general guidance for controlling nanocrystals with various thermodynamic forms.
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Renewable energy-based electrocatalytic hydrogenation of acetylene to ethylene (E-HAE) under mild conditions is an attractive substitution to the conventional energy-intensive industrial process, but is challenging due to its low Faradaic efficiency caused by competitive hydrogen evolution reaction. Herein, we report a highly efficient and selective E-HAE process at room temperature and ambient pressure over the Cu catalyst. A high Faradaic efficiency of 83.2% for ethylene with a current density of 29 mA cm-2 is reached at -0.6 V vs. the reversible hydrogen electrode. In-situ spectroscopic characterizations combined with first-principles calculations reveal that electron transfer from the Cu surface to adsorbed acetylene induces preferential adsorption and hydrogenation of the acetylene over hydrogen formation, thus enabling a highly selective E-HAE process through the electron-coupled proton transfer mechanism. This work presents a feasible route for high-efficiency ethylene production from E-HAE.