CO2 Adsorption Research Articles

Mg-Doped Cu Catalyst for Electroreduction of CO2 to Multicarbon Products: Lewis Acid Sites Simultaneously Promote *CO Adsorption and Water Dissociation.

The electroreduction of CO2 to valuable fuels or high-value chemicals by using sustainable electric energy provides a promising strategy for solving environmental problems dominated by the greenhouse effect. Copper-based materials are the only catalysts that can convert CO2 into multicarbon products, but they are plagued by high potential, low selectivity, and poor stability. The key factors to optimize the conversion of CO2 into multicarbon products are to improve the adsorption capacity of intermediates on the catalyst surface, accelerate the hydrogenation step, and improve the C-C coupling efficiency. Herein, we successfully doped Lewis acid Mg into Cu-based materials using a simple liquid-phase chemical method. In situ Raman and FT-IR tracking show that the Mg site enhances the surface coverage of the *CO intermediate, simultaneously promoting water dissociation. Under an industrial current density of 0.7 A cm-2, the FEC2+ reaches 73.9 ± 3.48% with remarkable stability. Density functional theory studies show that doping the Lewis acid Mg site increases the coverage of *CO and accelerates the splitting of water, thus promoting the C-C coupling efficiency, reducing the reaction energy barrier, and greatly improving the selectivity of C2+ products.

Enhanced post-combustion CO2 capture and direct air capture by plasma surface functionalization of graphene adsorbent

Graphene has enormous potential to capture CO2 due to its unique properties and cost-effectiveness. However, graphene-based adsorbents have drawbacks of lower CO2 adsorption capacity and poor selectivity. This work demonstrates a one-step rapid and sustainable N2/H2 plasma treatment process to prepare graphene-based sorbent material with enhanced CO2 adsorption performance. Plasma treatment directly enriches amine species, increases surface area, and improves textural properties. The CO2 adsorption capacity increases from 1.6 to 3.3 mmol/g for capturing flue gas, and from 0.14 to 1.3 mmol/g for direct air capture (DAC). Importantly, the electrothermal property of the plasma-modified aerogels has been significantly improved, resulting in faster heating rates and significantly reducing energy consumption compared to conventional external heating for regeneration of sorbents. Modified aerogels display improved selectivity of 42 and 87 after plasma modification for 5 and 10 min, respectively. The plasma-treated aerogels display minimal loss between 17% and 19% in capacity after 40 adsorption/desorption cycles, rendering excellent stability. The N2/H2 plasma treatment of adsorbent materials would lower energy expenses and prevent negative effects on the global economy caused by climate change.

Rare Earth Er‐Nd Dual Single‐Atomic Catalysts for Efficient Visible‐light Induced CO2 Reduction to CnH2n+1OH (n=1, 2)

Efficient synthesis of CnH2n+1OH (n=1, 2) via photochemical CO2 reduction holds promise for achieving carbon neutrality but remains challenging. Here, we present rare‐earth dual single atoms (SAs) catalysts containing ErN6 and NdN6 moieties, fabricated via an atom‐confinement and coordination method. The dual Er‐Nd SAs catalysts exhibit unprecedented generation rates of 1761.4 μmol g–1 h–1 and 987.7 μmol g–1 h–1 for CH3CH2OH and CH3OH, respectively. Through a combination of theoretical calculation, X‐ray absorption near edge structural analysis, aberration‐corrected transmission electron microscopy, and in‐situ FT‐IR spectroscopy, we demonstrate that the Er SAs facilitate charge transfer, serving as active centers for C−C bond formation, while Nd SAs provide the necessary *CO for C−C coupling in C2H5OH synthesis under visible light. Furthermore, the experiment and density functional theory calculation elucidate that the variety of electronic states induced by 4f orbitals of the Er SAs and the p−f orbital hybridization of Er−N moieties enable the formation of charge‐transfer channel. Therefore, this study sheds light on the pivotal role of *CO adsorption in achieving efficient conversion from CO2 to CnH2n+1OH (n=1, 2) via a novel rare‐earth‐based dual SAs photocatalysis approach.

Rare Earth Er‐Nd Dual Single‐Atomic Catalysts for Efficient Visible‐light Induced CO2 Reduction to CnH2n+1OH (n=1, 2)

Efficient synthesis of CnH2n+1OH (n=1, 2) via photochemical CO2 reduction holds promise for achieving carbon neutrality but remains challenging. Here, we present rare‐earth dual single atoms (SAs) catalysts containing ErN6 and NdN6 moieties, fabricated via an atom‐confinement and coordination method. The dual Er‐Nd SAs catalysts exhibit unprecedented generation rates of 1761.4 μmol g–1 h–1 and 987.7 μmol g–1 h–1 for CH3CH2OH and CH3OH, respectively. Through a combination of theoretical calculation, X‐ray absorption near edge structural analysis, aberration‐corrected transmission electron microscopy, and in‐situ FT‐IR spectroscopy, we demonstrate that the Er SAs facilitate charge transfer, serving as active centers for C−C bond formation, while Nd SAs provide the necessary *CO for C−C coupling in C2H5OH synthesis under visible light. Furthermore, the experiment and density functional theory calculation elucidate that the variety of electronic states induced by 4f orbitals of the Er SAs and the p−f orbital hybridization of Er−N moieties enable the formation of charge‐transfer channel. Therefore, this study sheds light on the pivotal role of *CO adsorption in achieving efficient conversion from CO2 to CnH2n+1OH (n=1, 2) via a novel rare‐earth‐based dual SAs photocatalysis approach.

Performance of CO2 Adsorption on Modified Activated Carbons Derived from Okara Powder Waste: Impacts of Ammonia Impregnation

Performance of CO2 Adsorption on Modified Activated Carbons Derived from Okara Powder Waste: Impacts of Ammonia Impregnation

Oxygen atom activated ZIF-67/carbon cloth in plasma system for CO2 reduction

ZIF-67 was grown in situ on carbon cloth (CC) using a simple one-step method. The prepared ZIF-67/CC electrodes exhibited excellent CO2 reduction reaction (CO2RR) performance in a dielectric barrier discharge plasma reactor. The highest concentrations of produced formic acid and formaldehyde were 9.16 and 0.068 mmol L−1 at a reaction time of 1 h, respectively. The high performance is related to the unique high aspect ratio structure and pad-like cavity of ZIF-67, which results not only in an increase in the specific surface area for CO2 adsorption but also in the hydrophobicity of the electrode. Unexpectedly, the superoxide radical (·O2−) greatly affects the reduction performance of the electrode. In addition, the ZIF-67/CC electrode maintained good CO2RR performance in the presence of different pollutants, and the production of formic acid and formaldehyde increased to 10.81 and 0.11 mmol L−1 at 1 h with the addition of 10 mg L−1 phenol. This research provides new directions in the field of plasma catalysis.

Coupling between the photoactivity and CO2 adsorption on rapidly thermal hydrogenated vs. conventionally annealed copper oxides deposited on TiO2 nanotubes

AbstractHighly ordered spaced titanium dioxide nanotubes were fabricated via electrochemical anodization and modified with titania nanoparticles and copper oxides. Such materials were rapidly annealed in hydrogen atmosphere or conventionally in a tube furnace in air, in which the temperature slowly increases. Applied synthesis procedure can be considered as simple, cost-effective, and environmentally friendly as it allows for reduction in used materials and enhances sustainable engineering. Manipulating the chemical composition of materials by different thermal treatments resulted in various photoelectrochemical activities and density of CO2 adsorption sites. Rapidly annealed nanotubes decorated by copper oxides exhibit excellent electrochemical properties where one electrode combines both: solar to electricity conversion (photocurrent under visible light 30 µA/cm2) and CO2 adsorption systems (18 times higher current after CO2 saturation). Rapidly thermal hydrogenated TiO2 nanotubes with copper oxides had 17 times higher photocurrent and wider absorption band (380–780 nm) than conventionally annealed ones. Furthermore, the crystal planes such as Cu (111), Cu (220), Cu2O (110), CuO (002) and Cu0, Cu+, Cu2+ oxidation states, and oxygen vacancies were recognized for hydrogenated sample. It should be highlighted that thermal annealing conditions significantly affects ability of copper oxide to CO2 adsorption and CO2 reduction reaction for hydrogenated electrode. Graphical abstract

A theoretical simulation of carbon dioxide adsorption capture on amine-functionalized graphene oxides

Amine-functionalized graphene oxides (AFGOs) are potential candidates for CO2 capture applications, as the amine functional groups could act as effective sites, promoting CO2 adsorption strength and selectivity. However, the CO2 adsorption mechanism on AFGO appears to be ambiguous, particularly with no explicit identification of the chemically bonded species. In this work, density functional theory and microkinetic simulations were carried out to investigate the physical and chemical adsorption mechanisms and behavior between AFGO and CO2. Our findings indicate that the van der Waals and hydrogen bonding (HB) interactions constitute physical binding modes between the aminated GO and CO2. The chemical adsorption pathways on AFGO materials have been revealed by the transition state search method, in which the relevant CO2 adsorption species, including carbamic acid and carbamate, and their formation conditions were theoretically identified on AFGOs. The chemisorption mechanisms have been recognized to be the nucleophilic interaction between GO-supported amines and CO2, simultaneously assisted by the cooperative effect of multiple HB interactions. More specifically, the surface hydroxyl groups and water molecules can serve as proton transfer media and offer HB interactions, thus regulating the reaction activity and chemical adsorption species. This theoretical work presents a new insight into CO2-AFGO interaction mechanisms, which is valuable for designing aminated GO adsorbents.

Wannier Function Localization Using Bloch Intrinsic Atomic Orbitals.

We extend the intrinsic atomic orbital (IAO) method for the localization of molecular orbitals to calculate well-localized generalized Wannier functions in crystals in the spirit of the Pipek-Mezey method. We furthermore present a one-shot diabatic Wannierization procedure that aligns the phases of the Bloch functions, providing immediate Wannier localization, which serves as an excellent initial guess for optimization. We test our Wannier localization implementation on a number of solid-state systems, highlighting the effectiveness of the diabatic preparation, especially for localizing core bands. Partial charges of Wannier functions generated using Bloch IAOs align well with chemical intuition, which we demonstrate through the example of the adsorption of CO on a MgO surface.

Constructing functionalized carbon quantum dots on amino-rich graphitic carbon nitride to enhance CO2 photocatalytic reduction: Critical role of functional group modulation

Carbon quantum dots (CQDs) decoration have been widely acknowledged as promising strategy in photocatalysis, yet in-depth understanding of the effect of different functionalized CQDs on CO2 photocatalytic reduction is still lacked. Herein, three kinds of functionalized CQDs, i.e. carboxylic CQDs (CCQDs), amino CQDs (NCQDs) and sulfonated CQDs (SCQDs), were homogeneously anchored on amino-rich g-C3N4 (U1W1-CN) to investigate their CO2 reduction behaviors under simulated solar-light illumination. Structural analysis demonstrated that potential amide covalent bonds formed between U1W1-CN and CCQDs, and noncovalent conjugations might exist between U1W1-CN and SCQDs, while strong electrostatic attraction between U1W1-CN and NCQDs. Performance tests showed CQDs decoration greatly enhanced the CO2 reduction activity, with 7%CCQDs/U1W1-CN exhibiting the optimal CO and CH4 productions of 40.94 μmol g−1 and 2.2 μmol g−1 under 4 h light irradiation, markedly higher than those of 7%SCQDs/U1W1-CN and 7%NCQDs/U1W1-CN. After comprehensive analysis, it was found that CCQDs decoration endowed U1W1-CN with better CO2 adsorption and activation. And due to the potential amide covalent bonds formed between CCQDs and U1W1-CN, 7%CCQDs/U1W1-CN delivered the largest electron density and most abundant COOH– intermediates, contributing much to its superior CO2 reduction activity over 7%NCQDs/U1W1-CN and 7%SCQDs/U1W1-CN. It is expected that the critical role of functional group modulation on CQDs in enhancing CO2 photocatalytic reduction revealed in this work can provide valuable insights into the rational design of more advanced photocatalysts for targeted reactions.

Synergistic integration of zeolite engineering and fixed-bed column design for enhanced biogas upgrading: Adsorbent synthesis, CO2/CH4 separation kinetics, and regeneration assessment

Biogas, a renewable energy vector derived from anaerobic digestion of organic waste, requires CO2 separation to enhance its calorific value for engine fuel. This study integrates CO2/CH4 separation in biogas using a novel approach integrating dual chemically-activated zeolites and fixed-bed column purification. Biogas produced via CSTR/ultrafiltration (69 % CH4, 30 % CO2, 14 ppm H2S) was further upgraded using HCl + NaOH and H2SO4 + NaOH activated zeolites. Optimal absorption capacity of 97.77 ± 0.01 % was achieved at 140 mesh, 60-minute H2SO4 + NaOH activation, 2-hour calcination (400 °C), and 200 mL/min flow rate. Breakthrough was observed at 18.12 min. Langmuir isotherm (R2 = 0.9992) and Elovich kinetics (R2 = 0.9846) best described the adsorption process. XRD analysis showed significant crystal size reduction post-activation (53.31 nm to 16.90 nm). Notably, BET analysis revealed enhanced surface properties surface area of 286.71 m2/g, pore volume of 0.213 cc/g, and pore diameter of 3.532 Å. An innovative dual-column system with non-isothermal TSA protocol optimized CO2 adsorption (30 mins) and desorption (17 mins, 40 °C, 100 mL/min), yielding superior near-pure methane biogas (99.29 % CH4, 0.66 % CO2, trace H2S). A methane loss of 2.75 % during upgrading demonstrated high CO2 selectivity. This synergistic approach presents a promising solution for sustainable biogas purification and engine fuel applications.

A Study Based on the First-Principle Study of the Adsorption and Sensing Properties of Mo-Doped WSe2 for N2O, CO2, and CH4

As industry continues to develop rapidly, the greenhouse effect is becoming increasingly severe. CO2, CH4, and N2O are the three primary greenhouse gases, making their effective monitoring a crucial step in reducing emissions. This paper investigates the gas sensing performance of Mo-doped WSe2 for these three gases, through a theoretical study. First, using first-principles calculations, the doping behavior of Mo in WSe2 is examined. Subsequently, the adsorption properties of Mo-WSe2 for CO2, CH4, and N2O are analyzed by calculating adsorption energy, charge transfer, the electron localization function (ELF), Hirshfeld partition (IGMH), and the density of states (DOSs), culminating in an analysis of its sensing properties. The results indicate that when Mo is positioned above the upper Se atom, the structure is most stable. Therefore, this position is selected as the optimal adsorption site for studying the adsorption of the three gases. The adsorption energies for CO2, CH4, and N2O are 1.349 eV, −1.194 eV, and −0.528 eV, respectively, with corresponding charge transfers of 0.418, 0.450, and 0.115. In the N2O and CO2 adsorption systems, significant adsorption energy and charge transfer are observed, leading to relatively better adsorption compared to the CH4 system. Additionally, considering the adsorption performance, Mo-WSe2 demonstrates good sensor response and desorption times for N2O and CO2 at temperatures above 298 K. The findings of this research provide theoretical guidance for the application of Mo-WSe2 as a gas sensing material for detecting greenhouse gases.

Sulfur-doped Bi2O2CO3 nanosheet for enhanced visible-light-driven photocatalytic CO2 reduction to CO with ultra-high selectivity.

The photocatalytic reduction of carbon dioxide (CO2) has emerged as a compelling strategy for the conversion of renewable energy. However, the expeditious recombination of photogenerated charge carriers and the inadequate light absorption capabilities are currently predominant challenges. Herein, we developed a facile hydrothermal approach to synthesize a sulfur doped Bi2O2CO3 nanosheet with a tunable energy band structure designed to enhance visible light absorption. Our findings indicate that the incorporation of sulfur into the catalytic sites induces an electron sink effect, significantly improving the separation efficiency of photogenerated charge carriers. Consequently, this sulfur-doped Bi2O2CO3 catalyst exhibits a remarkable carbon monoxide (CO) yield of 16.64 μmol gcat-1 h-1 with nearly 100 % selectivity under illumination ranging from 420 to 780 nm. Through in-situ characterization techniques and theoretical calculations, it was revealed that sulfur-coordinated bismuth sites greatly enhance CO2 adsorption and decrease the energy barrier for critical intermediates formation (*COOH), thus selectively driving the reaction towards CO production. This work not only advances our understanding of mechanisms underlying photocatalytic reduction of CO2 on sulfur-doped bismuth-based catalysts but also sets a precedent for developing sophisticated photocatalytic systems for enhanced photoreduction reactions.

Targeted construction of porous biochar with well-developed pore structure for high-performance CO2 adsorption

Targeted construction of porous biochar is vital for the development of carbon capture. In this paper, we use the KOH chemical activation with walnut shell as raw material, to investigate the effects of the preparation process on the targeted construction of CO2 adsorbents. We have revealed the vital factors influencing CO2 adsorption and developed the design strategy for porous biochar under different application conditions. The specific surface area can up to 2115 m2 g−1, and the microporosity can up to 95.5 %. The CO2 adsorption capacities are 6.75 mmol g−1 and 17.59 mmol g−1 at 0°C, 1 bar and 10 bar. Meanwhile, the heat of adsorption ranges from 18 to 30 kJ mol−1. In addition, the sample exhibits outstanding adsorption kinetics, good adsorption selectivity, and its CO2 adsorption capacity fluctuates within 5 % after 10 adsorption-desorption cycles. Therefore, the strategy developed in this paper can be applied to the high-performance adsorption of CO2 under different conditions.

Comparative study of CO adsorption on Au, Cu, MoO2 and MoS2 2D Nanoparticles

This study focuses on a comparative analysis of the electronic properties of triangular, irregular hexagonal, and octagonal 2D nanoparticles containing 10, 12, and 14 motifs, made of Au, Cu, MoO2, and MoS2. The investigation was carried out using density functional theory. The formation energies and vibrational frequencies demonstrate that the 2D nanostructure configurations can exist as stable structures. Edge atoms with lower coordination numbers than central atoms, are the preferred sites for CO adsorption. Using orbital-weighting dual descriptors calculated from Fukui functions enabled the identification of a majority nucleophilic attack sites in Au and Cu nanoparticles, while MoO2 and MoS2-based nanoparticles present almost as many electrophilic sites as nucleophilic sites. The charge transferred between the nanostructures and the CO molecule and the redistribution of the projected density of states were used to assess the strength of interfacial bonds and the nature of the fundamental interaction involved in the bonding.

Operando X-ray and Mass Spectroscopy of Reduced Graphene Oxide ( rGO )-Mediated Cobalt Catalysts for Boosting the Hydrogen Evolution Reaction

Inserting underlying reduced graphene oxide (rGO) into Co aims to regulate the chemical integrity and catalytic ability of the Co upper layer for hydrogen evolution reaction (HER) as a green-hydrogen goal. Principally, an mass spectrometer indicates 3.8 times more considerable hydrogen generation in Co/rGO than in Co. The spectroscopical approaches, combining soft and hard X-ray probing, illustrate the chemical oxidation evolution of electronic Co-3 and Co-4 states differently regarding the underlying rGO contribution. A unique examination is regarded as the phase transition from the initial middle to high oxidation and to deoxidation, related to the intermediate Co0 existence and H2 generation. The chemical adsorption of Co–O(H), Co–Hads, and H2 molecules desorption have been assigned their spectral significances. The rGO mediation indicates two significant metal Co and Co–O(H) blocks in the two-dimensional - domain. Density-functional-theory (DFT) calculation provides the regeneration, sustained stability, and decreasing energy barrier of Co–Hads catalysts due to the rGO incorporation, thereby augmenting the HER enhancement through the alternative Volmer-Heyrovsky process. The experiment, including mass spectrometer, soft, and hard X-ray, provides evidence regarding the catalyst’s HER enhancement. This study offers insights into the chemical composition, electronic structure, and active role of Co bonded with or without the extinct OH and H bonds, advancing our comprehension of electrocatalytic reactions, thus taking our knowledge of composite materials to stepwise electrocatalytic reactions forward. This cutting-edge experiment under environment and DFT studies gives critical information regarding the catalytic mechanism and chemical stability of the Co and rGO materials. Published by the American Physical Society 2024

Investigation into geometric configurations and electronic properties of CeO2-supported gold clusters

A detailed understanding of the geometric structure and electronic properties of gold nanoparticles on the ceria surface is crucial for comprehending their unique catalytic activity. Using the first-principles method based on density functional theory, the adsorption of Aux (x = 1–4) clusters on the CeO2(111) surface was studied. It was discovered that the standing configurations of Au2 and Au3, as well as the tetrahedral structure of Au4, are the most stable adsorption structures. The stability of these configurations is jointly determined by the number and strength of Au-Au bonds, the Au-O bonding energy, and the interaction dynamics between the clusters and the substrate. The analysis of Bader charge, difference charge density and density of states suggested that lattice relaxation and electronic localization occur in the reduced Ce3+. The reduced amount and location of Ce3+ are significantly influenced by the position and charge transfer amount of Aux cluster. The adsorption of CO on Au4/CeO2(111) indicated that stronger Au-C bonding energy due to the hybridization of Au-5d and C-2p, thereby enhancing the catalytic activity for CO oxidation reactions.

A Study on the Mechanisms of Coal Fly Ash to Improve the CO2 Capture Efficiency of Calcium-Based Adsorbents

Utilizing calcium-based adsorbents for CO2 adsorption through cyclic calcination/carbonization is one of the most cost-effective methods for carbon emission reduction. In order to improve the cycle stability of the adsorbents and the capture efficiency of CO2, this study used industrial solid waste coal fly ash for the hydration treatment of calcium-based adsorbent to explore the variations in the cyclic adsorption performance of the adsorbent under different doping ratios and hydration conditions. By means of various characterization techniques, the microscopic mechanism for improving the performance of the modified adsorbent was analyzed from the perspectives of chemical composition, physical structure, and surface functional groups of the adsorbents. The results demonstrated that the modification of coal fly ash could significantly enhance the carbonation performance and cycle stability of the adsorbent in multiple CO2 capture processes. The modified material doped with 5% coal fly ash had the highest total CO2 adsorption capacity, which increased by 13.7% compared to before modification. Additionally, the modified material doped with 10% coal fly ash exhibited the strongest cyclic adsorption capacity, which was 14.0% higher than that before modification, and the adsorption attenuation rate decreased by 32.2%. The characterization results showed that the reaction between calcium oxide and coal fly ash formed CaSiO3 and Ca12Al14O33 during the modification process, which was the primary reason for the improvement in the CO2 capture performance of the modified materials. This study provided a new perspective on the resource utilization of solid waste fly ash and efficient CO2 capture.

Selectivity Modulation of Multistep Reduction Reactions by Gold Nanoclusters

The selective synthesis of valuable azo‐ and azoxyaromatic chemicals via transfer coupling of nitroaromatic compounds has been achieved by fine‐tuning the catalyst structure. Here, a direct method to modulate nitrobenzene reduction and selectively alter the product from azobenzene to azoxybenzene by employing the size effect of Au is reported. Au nanoclusters (NCs) with smaller sizes embedded in ZIF‐8 controllably converted nitrobenzene into azoxybenzene, while supported Au nanoparticles (NPs) catalyzed nitrobenzene reduction to azobenzene. X‐ray photoelectron spectroscopy (XPS) and Diffuse reflectance infrared Fourier transform spectroscopy on CO adsorption (CO‐DRIFTS) of Au NC/ZIF‐8 revealed a higher valence state and a lower electron density of Au than that of Au NP/ZIF‐8, combined with the desorption of azoxybenzene from the Au NC and Au NP surface, suggesting that the Au NCs with lower electron density exhibit stronger adsorption. Density functional theory (DFT) calculations and charge density difference maps indicated that azoxybenzene bonded to Au NC/ZIF‐8 with greater adsorption energy, resulting in more electron transfer between azoxybenzene and the generated Au sites, which inhibited further reduction of azoxybenzene and resulted in high azoxybenzene selectivity. The application of the size effect of Au particles to regulate nitrobenzene transfer coupling provided new insights into the structure‐selectivity relationships.

Selectivity Modulation of Multistep Reduction Reactions by Gold Nanoclusters.

The selective synthesis of valuable azo- and azoxyaromatic chemicals via transfer coupling of nitroaromatic compounds has been achieved by fine-tuning the catalyst structure. Here, a direct method to modulate nitrobenzene reduction and selectively alter the product from azobenzene to azoxybenzene by employing the size effect of Au is reported. Au nanoclusters (NCs) with smaller sizes embedded in ZIF-8 controllably converted nitrobenzene into azoxybenzene, while supported Au nanoparticles (NPs)catalyzed nitrobenzene reduction to azobenzene. X-ray photoelectron spectroscopy (XPS) and Diffuse reflectance infrared Fourier transform spectroscopy on CO adsorption (CO-DRIFTS) of Au NC/ZIF-8 revealed a higher valence state and a lower electron density of Au than that of Au NP/ZIF-8, combined with the desorption of azoxybenzene from the Au NC and Au NP surface, suggesting that the Au NCs with lower electron density exhibit stronger adsorption. Density functional theory (DFT) calculations and charge density difference maps indicated that azoxybenzene bonded to Au NC/ZIF-8 with greater adsorption energy, resulting in more electron transfer between azoxybenzene and the generated Au sites, which inhibited further reduction of azoxybenzene and resulted in high azoxybenzene selectivity. The application of the size effect of Au particles to regulate nitrobenzene transfer coupling provided new insights into the structure-selectivity relationships.