Cooperative Communication Between the Active Sites and Surrounding Environments in a Supported Ag ₄ Pt ₂ (SR) ₈ Cluster on Carbon Black

Open AccessCCS ChemistryRESEARCH ARTICLES27 Jun 2024Cooperative Communication Between the Active Sites and Surrounding Environments in a Supported Ag4Pt2(SR)8 Cluster on Carbon Black Tongxin Song†, Bingqing Ge†, Chao Juan, Shuangshuang Huang, Dan Li, Qingxi Zhai, Xiao Cai, Xu Liu, Weiping Ding and Yan Zhu Tongxin Song† Key Lab of Mesoscopic Chemistry of MOE and Jiangsu Key Lab of Vehicle Emissions Control, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093 , Bingqing Ge† Key Lab of Mesoscopic Chemistry of MOE and Jiangsu Key Lab of Vehicle Emissions Control, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093 , Chao Juan Key Laboratory of Green Chemistry and Technology, College of Chemistry, Sichuan University, Chengdu 610064 , Shuangshuang Huang School of Physics and Technology, Center for Electron Microscopy, MOE Key Laboratory of Artificial Micro- and Nano-structures, Wuhan University, Wuhan 430072 , Dan Li *Corresponding authors: E-mail Address: [email protected] E-mail Address: [email protected] Key Laboratory of Green Chemistry and Technology, College of Chemistry, Sichuan University, Chengdu 610064 , Qingxi Zhai Key Lab of Mesoscopic Chemistry of MOE and Jiangsu Key Lab of Vehicle Emissions Control, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093 , Xiao Cai Key Lab of Mesoscopic Chemistry of MOE and Jiangsu Key Lab of Vehicle Emissions Control, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093 , Xu Liu Key Lab of Mesoscopic Chemistry of MOE and Jiangsu Key Lab of Vehicle Emissions Control, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093 , Weiping Ding Key Lab of Mesoscopic Chemistry of MOE and Jiangsu Key Lab of Vehicle Emissions Control, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093 and Yan Zhu *Corresponding authors: E-mail Address: [email protected] E-mail Address: [email protected] Key Lab of Mesoscopic Chemistry of MOE and Jiangsu Key Lab of Vehicle Emissions Control, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093 Citation: CCS Chemistry. 2024;0:1–9https://doi.org/10.31635/ccschem.024.202404169 SectionsSupplemental MaterialAboutAbstractPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail Identifying catalytically active sites and understanding the role of the environment surrounding the active sites on heterogeneous catalysis remains a challenge. Here we show the cooperative, multisite reactivity within an atomically precise nanocluster Ag4Pt2(SR)8 (SR = 2,4-dimethylbenzenethiol) for electrochemical hydrogen evolution reaction. Our spectroscopic analysis coupled with the computational modeling indicate that the hydrogen production proceeds via a stepwise mechanism, with the hydrogen intermediate initially presenting on the apical sites of the S atoms sequentially to bind at the pyramidally shaped location containing Ag-Pt-Ag linkages. The adsorption of hydrogen species on surrounding ligands is found to perturb the electronic structure of catalytic sites and further regulate the affinity of hydrogen species with the metal center. More notably, the subtle interplay between the catalytic function and the surrounding environment indeed facilitates the hydrogen evolution on the Ag4Pt2(SR)8 catalyst with an overpotential of only 23.3 mV at a current density of 10 mA·cm−2, which not only overperforms most metal nanoclusters reported but is also comparable to a typical Pt/C catalyst under identical conditions. Download figure Download PowerPoint Introduction Identifying the active sites and revealing the structure of active sites are of utmost significance to understanding catalytic mechanisms and designing high-performance catalysts.1,2 Unlike homogeneous catalysis using molecules or complexes as well-defined catalysts, heterogeneous catalysis involves almost exclusively nanoscale particle catalysts that can catalyze many chemical processes occurring on their surface or interface,3–6 which are usually complicated by the active sites, interaction of active sites and substrates, and the surrounding environment controlling access to the active sites.7,8 To approach the local structure of catalytic sites in heterogeneous catalysts, solution phase syntheses of nanoparticles are currently available that can allow excellent control over size and shape with the help of the surface stabilizers.9,10 Unfortunately, another complication is the surface residues, such as ligands or surfactants, on the nanoparticle surface, which are invisible but add to the ambiguity in pinpointing the active sites. In addition, to stabilize the reaction sites, nanoparticles are often dispersed on the supports. The catalyst surface/interfaces can also be structurally and electronically coupled with the supports at the nanoscale. Therefore, to decouple the size, structure, stabilizer, and support effect, the ideal catalysts should be crystallographically characterized,11 just like nature's most efficient nanoscale catalysts-enzyme, in which the active sites and the surrounding environment that can control access to the active sites have been established.12,13 Atomically precise metal nanoclusters can act as ideal model catalysts, since their total structures can be solved by single-crystal X-ray crystallography.14,15 Such nanocluster-based catalysts hold promise in heterogeneous catalysis including the identification of the active sites,16–18 the relationship of structure and properties,19 the contribution of metal core to the overall performance,20 and control of catalytic selectivity by surface ligands surrounding the metal core.21,22 Specifically, a striking example of the specificity of such nanoclusters is reported to combine advantages of homogeneous and heterogeneous catalysts, with a clarified mechanism and high performance being integrated into a catalytic system.23,24 These metal nanoclusters provide opportunities to explore the intricate cooperative interaction between the active sites and the nanoscale environment including surface ligands and supports surrounding the active sites.25,26 Here we report an atomically precise Ag4Pt2(SR)8 nanocluster supported on highly conductive XC-72R carbon black as a catalyst that exhibits high catalytic efficiency in the electrochemical hydrogen evolution reaction (HER). Our observation shows that this nanocluster is robust and its total structure (metal core plus surface ligand) is intact even if it is dispersed on the carbon support for the HER reaction. Our studies suggest the preferential chemisorption of hydrogen species on the S sites in the ligand, thereby further promoting the adsorption of hydrogen species on the active sites containing Ag-Pt-Ag triangle plane. This previously missing link between the active sites and the collaborative environment of carbon support and surface ligand is represented to afford hydrogen production on the Ag4Pt2(SR)8/C catalyst. Experimental Methods Clusters synthesis Synthesis of Ag4Pt2(SR)8 (SR = 2,4-dimethylbenzenethiol, DMBT) and Ag4Pd2(SR)8 clusters were based on previously reported methods.27 For the synthesis of Ag4Pt2(SR)8, 40 mg of H2PtCl6·6H2O and 40 mg of AgNO3 were dissolved thoroughly in 3 mL of CH3OH by ultrasound. The solutions were poured into 15 mL of CH2Cl2. After vigorously stirring for 10 min, 84 μL of DMBT was added. After 30 min, 3 mL freshly prepared ice solution of 45 mg NaBH4 was added into the above solution quickly. The mixture was allowed to stir overnight. After the reaction, the crude product was washed with CH3OH several times and extracted with CH2Cl2. The crude product was purified by preparative thin-layer chromatography to obtain Ag4Pt2(DMBT)8. When 40 mg of H2PtCl6·6H2O was replaced with 40 mg of Na2PdCl4, and other conditions remained unchanged, Ag4Pd2(SR)8 clusters were obtained. Catalytic reaction All of the electrochemical measurements of HER were evaluated on a Shanghai Chenhua CHI660E electrochemical workstation (CH Instruments, Inc., Shanghai, China) by using a three-electrode H-type electrolytic cell, for which the anode and cathode compartments were separated by a Nafion 117 membrane (Suzhou Sinero Technology Co., Ltd, Suzhou, China). The three-electrode setup was assembled with a Pt wire counter electrode, an Ag/AgCl reference electrode, and a carbon paper loaded catalyst as the working electrode. Clusters were loaded onto XC-72R carbon black to prepare the cluster electrocatalyst with a mass fraction of 20%. The mass of cluster loading was 40 μg·cm−2. Further experimental details can be found in the Supporting Information. Results and Discussion The total structure of Ag4Pt2(SR)8 can be viewed as an ortho-octahedron with a tetragonal plane composed of four Ag atoms, two Pt atoms located above and below the plane, and each metal atom binding to one thiol ligand (Figure 1a).27 The valence states of Pt and Ag in the pristine Ag4Pt2(SR)8 cluster were first characterized by X-ray photoelectron spectroscopy (XPS) as shown in Supporting Information Figure S1. Pt and Ag exited as Pt2+ and Ag+ species, respectively. To explore the metal charge state of the nanocluster supported on carbon, X-ray absorption near-edge structure spectroscopy (XANES) was performed. As can be seen from Figure 1b, the Pt valence states of Ag4Pt2(SR)8 and Ag4Pt2(SR)8/C were slightly higher than that of Pt foil, and the valence state of Pt had no significant difference between Ag4Pt2(SR)8 and Ag4Pt2(SR)8/C. As such, the Ag exhibited the same positive monovalent valence in the cluster before and after loading on carbon (Figure 1c). The local coordination environments in Ag4Pt2(SR)8 and Ag4Pt2(SR)8/C were monitored by extended X-ray absorption fine structure (EXAFS) experiments. As shown in Figure 1d and Supporting Information Table S1, the peak located at 1.96 Å was attributed to the Pt–S bond in Ag4Pt2(SR)8, and no Pt–Pt bond was observed after loading onto carbon. Likewise, the Ag–S bond hardly underwent any change after loading (Figure 1h and Supporting Information Table S2). From the wavelet transform analysis (Figure 1e–g,i–k), the Pt–S, Pt–Pt, Ag–S, and Ag–Ag bonds were located at 1.96, 2.61, 1.90, and 2.64 Å, respectively, which further suggested that no agglomeration occurred after loading of the clusters, thereby implying no significant interaction between cluster and support. To unveil the surrounding environment around active sites of clusters, we analyzed the C 1s XPS profile of the carrier carbon from Ag4Pt2(SR)8/C and found a large number of oxygenated species such as hydroxyl and aldehyde groups on the carbon surface (Figure 1l).28 Transmission electron microscopy (TEM) and scanning transmission electron microscopy energy-dispersive spectrometry (STEM-EDS) analyses indicated that these clusters were uniformly distributed on the carbon black and no aggregation occurred (Figure 1m,n and Supporting Information Figure S2). We also compared the fingerprint signals of Ag4Pt2(SR)8 and Ag4Pt2(SR)8/C by Raman spectroscopy ( Supporting Information Figure S3), in which the characteristic peaks of the clusters were identical except for the D and G band signals belonging to carbon, revealing that the total structure of the cluster was intact. We unambiguously proposed the weak interaction between hydrogen of cluster and oxygen species of carbon, as shown in Figure 1o, and thereby the total structure of the cluster was maintained and the effect of carbon black in the active sites might be negligible. Figure 1 | (a) The crystal structure of Ag4Pt2(SR)8 cluster. (b) Pt L3-edge and (c) Ag K-edge XANES data of Ag4Pt2(SR)8, Ag4Pt2(SR)8/C, Pt foil, and Ag foil. (d) Fourier transform EXAFS profiles of Pt L3-edge for Ag4Pt2(SR)8, Ag4Pt2(SR)8/C, and Pt foil. (e–g) Wavelet transform contour spectra for k3-weighted Pt L3-edge EXAFS of the Ag4Pt2(SR)8, Ag4Pt2(SR)8/C, and Pt foil. (h) Fourier transform EXAFS profiles of Ag K-edge for Ag4Pt2(SR)8, Ag4Pt2(SR)8/C, and Ag foil. (i–k) Wavelet transform contour spectra for k3-weighted Ag K-edge EXAFS of the Ag4Pt2(SR)8, Ag4Pt2(SR)8/C, and Ag foil. All data were not phase corrected in EXAFS. (l) C 1s XPS spectrum for Ag4Pt2(SR)8/C. (m) TEM image of Ag4Pt2(SR)8 loaded on carbon. (n) Corresponding STEM-EDS element mapping of Ag4Pt2(SR)8/C. (o) Schematic illustration of supported Ag4Pt2(SR)8 clusters on carbon as an electrocatalyst. Download figure Download PowerPoint We next turned our attention to the catalytic performance of the Ag4Pt2(SR)8/C on HER to investigate the synergy between metal sites and surface ligand. The Ag4Pd2(SR)8 cluster with an identical structure as Ag4Pt2(SR)8 as well as commercial 20 wt % Pt/C were chosen as references. The linear scanning voltammetry curves were first measured in 0.5 M H2SO4 solution with a scanning rate of 5 mV·s−1 with 90% iR compensation. As shown in Figure 2a, Ag4Pt2(SR)8/C showed the smallest overpotential of 23.3 mV versus reversible hydrogen electrode at a current density of 10 mA·cm−2, which was slightly better than commercial Pt/C (25.2 mV). Ag4Pt2(SR)8/C exhibited a remarkably lower overpotential than Ag4Pd2(SR)8/C (55.5 mV). Moreover, the mass activity of Ag4Pt2(SR)8/C also outperformed Ag4Pd2(SR)8/C and Pt/C ( Supporting Information Figure S4). Figure 2b showed that the Tafel slope of Ag4Pt2(SR)8/C was 45 mV·dec−1, which was much smaller than those of commercial Pt/C and Ag4Pd2(SR)8/C. A smaller Tafel slope indicates the faster hydrogen production kinetics of Ag4Pt2(SR)8/C. By extending the Tafel plots outward to an overpotential of 0 mV, the exchange current densities of the three catalysts were obtained ( Supporting Information Figure S5).29 Ag4Pt2(SR)8/C showed the highest exchange current of 3.6 mA·cm−2, demonstrating its favorable intrinsic electrochemical activity. The charge transfer capability was investigated by electrochemical impedance spectroscopy, as shown in Figure 2c, and Ag4Pt2(SR)8/C displayed a charge transfer impedance (32.4 Ω) similar to commercial Pt/C (27.2 Ω), indicating rapid electron transfer between the catalyst interface and the electrolyte. Furthermore, the radar plots showed the comprehensive performance of the three catalysts (Figure 2d), including the mass activity at the overpotential of 50 mV, the turnover frequency (TOF) of platinum sites at 30 mV, the overpotential at a current density of 10 mA·cm−2, Tafel slope, and the active electrochemically surface area (ECSA). Overall, the Ag4Pt2(SR)8/C seemed the most satisfactory for HER performance among the three catalysts. Figure 2 | HER activity and stability of Ag4Pt2(SR)8/C, Ag4Pd2(SR)8/C, and commercial Pt/C. (a) Linear sweep voltammetry curves in the solution of 0.5 M H2SO4 with 90% iR correction. (b) Tafel plots obtained from the corresponding polarization curves. (c) Electrochemical impedance spectra at the potential of 25 mV. (d) Comparison of mass activity, TOF, overpotential, Tafel slope, exchange current density, and ECSA of the three electrocatalysts. (e) Accelerated durability test before and after 500 cycles in 0.5 M H2SO4 solution. (f) Long-term stability at the overpotential in 0.5 M H2SO4 electrolyte. (g) Comparison of the overpotentials of Ag4Pt2(SR)8/C at the current density of 10 mA·cm−2 with the other reported HER cluster catalysts. (h) Comparison of overpotentials obtained under identical conditions for other clusters tested in this work. Download figure Download PowerPoint In addition, the Ag4Pt2(SR)8/C catalyst showed long-term stability during the HER. It can be seen from Figure 2e that Ag4Pt2(SR)8/C exhibited a negligible change in the polarization curve after 500 cycles of cyclic voltammetry, while commercial Pt/C showed a marked degradation. From the current-time curves (Figure 2f), the current density of Pt/C decayed by 53% when the reaction had been performed for only 45 h. The current density of Ag4Pd2(SR)8/C decreased by 30% when the reaction was carried out for 80 h, whereas the current of Ag4Pt2(SR)8/C was maintained at 88% after 120 h of reaction. Supporting Information Figure S6 depicts the variation of potential with time at the current density of 10 mA·cm−2 in 0.5 M H2SO4, which also demonstrates the excellent catalytic stability of Ag4Pt2(SR)8/C. Especially, the clusters were dissolved from the loaded catalysts with dichloromethane solvent and it was found that the geometric structure of the Ag4Pt2(SR)8 and Ag4Pd2(SR)8 remained unchanged after long-term stability tests ( Supporting Information Figure S7). TEM images of the used Ag4Pt2(SR)8/C catalyst, as shown in Supporting Information Figure S8, indicate no aggregation of the clusters during the reaction. Notably, compared to the HER clusters reported (detailed test conditions are listed in Supporting Information Table S3), Ag4Pt2(SR)8/C exhibited optimal catalytic performance for HER (Figure 2g).30–36 As such, we also tested the HER performance of other clusters under identical conditions, as shown in Figure 2h. Ag4Pt2(SR)8/C showed the smallest overpotential among the tested cluster catalysts. Although some platinum-free clusters such as Au50Ag2(SR)36, Au19Ag4(SR)15, and Ag17Cu12(SR)15(PPh3)4 showed excellent catalytic activity, the UV characteristic absorption of the used catalysts disappeared, indicating that their precise structure was no longer maintained. Considering the excellent HER performance of Ag4Pt2(SR)8, we coupled it with commercial RuO2 into a two-electrode couple to drive the overall water splitting reaction under acidic conditions. As can been seen from Supporting Information Figure S9a, the Ag4Pt2(SR)8 ‖ RuO2 electrode couple can provide a current density of 20 mA·cm−2 at a potential of only 1.59 V, whereas the Pt/C ‖ RuO2 couple required a potential of 1.62 V to achieve a current density of 20 mA·cm−2. The stability of the Ag4Pt2(SR)8 ‖ RuO2 couple was evaluated by the chronopotentiometry test ( Supporting Information Figure S9b), indicating that a current density of 20 mA·cm−2 can be kept for more than 60 h at a consistent cell voltage. With the catalytic performances in hand, we next sought to initiate mechanistic studies to determine if the ligand could mediate access of reactant or intermediate species to the active sites involving experimental measurement and computational modeling. The elucidation of ligand effect on electrocatalysis was previously elusive, due to the heave relying on theory as opposed to direct experimental observation. Here the fresh and used catalysts were characterized by 1H nuclear magnetic resonance (NMR). In Figure 3a, the thiol ligand (2,4-dimethylbenzenethiol short for DMBT) had a characteristic peak at 3.21 ppm assigned to S–H, and the peaks at 2.31 and 2.28 ppm attributed to –CH3. We also tested the hydrogen signal of m-xylene (m-Me2Ph) that might be generated if the S–C bond was broken with a distinct –CH3 peak at 2.37 ppm. Compared to a fresh Ag4Pt2(SR)8/C sample, a used Ag4Pt2(SR)8/C sample exhibited identical hydrogen signals and no fingerprints of DMBT or m-Me2Ph were observed, implying that no ligand detachment and breakage occurred during the HER process. Figure 3 | (a) 1H NMR spectra of fresh and used Ag4Pt2(SR)8 catalysts. (b) Potential-dependent Raman testing of Ag4Pt2(SR)8 cluster without carbon support in 0.5 M H2SO4 electrolyte. (c) In situ Raman spectra of Ag4Pt2(SR)8/C in 0.5 M H2SO4 electrolyte. (d) In situ Raman spectra of Ag4Pt2(SR)8 without carbon support in 0.5 M H2SO4 in D2O. Download figure Download PowerPoint Moreover, potential-dependent Raman spectroscopy was carried out to explore the cluster change. With the increase of applied potential, the fingerprint signals on the cluster remained unchanged and the signal intensity did not diminish in 0.5 M H2SO4 electrolyte, as shown in Figure 3b, which indicated that the cluster was robust in the electrolytic environment. In situ electrochemical Raman spectroscopy was employed to monitor H2 evolution process in 0.5 M H2SO4 electrolyte over the Ag4Pt2(SR)8/C catalyst. As shown in Figure 3c, the peaks at 1348.88 and 1605.38 cm−1 were attributed to the D and G bands of carbon materials and the peaks at 889.63 and 980.25 cm−1 were caused by the adsorption of SO42− on carbon in solution. The peak at 1053.98 cm−1 is responsible for either H species in the solution or cluster signals. During the increase in potential from 20 to 200 mV, weak Raman signals can also be observed near 2129.13 and 2559.19 cm−1, whose intensity gradually increased with the applied potential. The band at 2129.13 cm−1 was attributed to the Pt–H stretching vibration, and the band at 2559.19 cm−1 was assigned to the stretching vibration of the S–H bond, suggesting that the H species were directly bonded to the Pt and S atoms in the HER process.37,38 The ν(S–H) peak at 2559.19 cm−1 can be further confirmed by deuterium isotope substitution experiments. As shown in Figure 3d and Supporting Information Figure S10, the S–H signal can still be observed in the 0.5 M H2SO4 electrolyte of D2O, while the S–H signal disappeared in the 0.5 M D2SO4 solution of D2O. Unfortunately, the S–D signal was too weak to be observed. Therefore, it can be concluded that both metal and S atoms in Ag4Pt2(SR)8 can contribute to the HER reaction and the carbon black adsorbed SO42− from the solution. On the basis of the intact structure of the Ag4Pt2(SR)8 cluster remained, density functional theory (DFT) calculations were performed to further reveal the structure and nature of the active sites. Figure 4a shows the optimized conformations of H* species binding to Ag, Pt, S, Ag-Ag bridge and Pt–S bridge sites, respectively. The Gibbs free energies of H* (ΔGH*) at the different cases were calculated. The results of adsorption free energy in Figure 4b showed that the S-related sites (such as S site and Pt-S site) on the original Ag4Pt2(SR)8 cluster presented a lower adsorption free energy for H*, indicating that H* preferentially adsorbed near the S site in H2SO4 electrolyte. A similar conclusion can be obtained for the Ag4Pd2(SR)8 cluster in Supporting Information Figure S11. However, the ΔGH* on the S-related site of Ag4Pt2(SR)8 cluster could not be matched with its extremely small overpotential. Considering that the S sites were more accessible for adsorption of hydrogen atoms, we constructed H-saturated Ag4Pt2(SR)8 and Ag4Pd2(SR)8 clusters by blocking all the S sites with H atoms ( Supporting Information Figure S12). In this way, H* could be stably adsorbed at the cavity sites of Ag-Pt-Ag or Ag-Pd-Ag (Figure 4c and Supporting Information Figure S13). The ΔGH* for H* adsorption on H-saturated Ag4Pt2(SR)8 and H-saturated Ag4Pd2(SR)8 were 0.25 and 0.40 eV (Figure 4d), respectively, demonstrating better catalytic performance of Ag4Pt2(SR)8 than that of Ag4Pd2(SR)8. In addition, we constructed Pt(111) to simulate commercial Pt/C, which showed a free energy of H* adsorption of −0.29 eV, accounting for comparable catalytic performance of Ag4Pt2(SR)8 and Pt/C. To gain in-depth insight into the interaction between the metal core and the ligand, we simulated the differential charge density of H-saturated Ag4Pt2(SR)8 and H-saturated Ag4Pd2(SR)8 and a remarkable transfer of electrons from the ligand to the metal core can be observed ( Supporting Information Figure S14). The accumulated electrons of metal core was 0.26 |e| for Ag4Pt2(SR)8 and 0.10 |e| for Ag4Pd2(SR)8, respectively, which suggested that the former was more favorable for H* adsorption than the latter, and hence Ag4Pt2(SR)8 showed higher catalytic activity than Ag4Pd2(SR)8. Figure 4 | DFT simulation results. (a) The optimized configurations of intermediate H* adsorption on the different site of Ag4Pt2(SR)8. (b) The calculated free energy diagram of H* adsorption on the different site of Ag4Pt2(SR)8. (c) The optimized configurations of intermediate H* adsorption on the Ag4Pt2(SR)8 clusters with the S sites saturated by H. (d) The calculated free energy diagram of H* adsorption on Ag4Pt2(SR)8 and Ag4Pd2(SR)8 with the S sites saturated by H as well as Pt(111). Download figure Download PowerPoint Conclusions In summary, through the combination of experimental measurement and calculation analysis, we established the identity of a tricoordinate active site in an atomically precise Ag4Pt2(SR)8 catalyst loaded on carbon black for the HER. This work provided the first definitive evidence for the involvement of the carbon support and surface ligand that can approach the active sites. We demonstrated that the S sites in the ligand rather than the carbon were able to control the intermediate hydrogen species access to the active sites, which regulated the affinity of the substrates with reaction sites and further impacted catalytic performance. This study has enabled a previously elusive elucidation of cooperative interaction between the active sites and nanoscale environment around the active sites. Extensions of this study can be envisioned to tailor the active site structure by tuning surface stabilizers and to unravel the fundamental insights into the metal-support interaction that is currently not available in impregnation-made catalysts. Supporting Information Supporting Information is available and includes detailed experimental section, Figures S1–S14, and Tables S1–S3. Conflict of Interest There is no conflict of interest to report. Funding Information We acknowledge financial support from the National Natural Science Foundation of China (grant nos. 22125202, 21932004, and 22302091), Natural Science Foundation of Jiangsu Province (grant no. BK20220033), Programs for high-level entrepreneurial and innovative talents introduction of Jiangsu Province, and China Postdoctoral Science Foundation (grant no. 2022M721551). References 1. Seong H.; Efremov V.; Park G.; Kim H.; Yoo J. 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