Pd Atoms Research Articles

Atom-Pd catalysts supported by hollow N-doped carbon nanospheres for ultra-efficient nitrogen reduction reaction

Electrochemical N2 reduction reaction (eNRR) presents a promising alternative to the Haber-Bosch process, owing to its mild preparation conditions, absence of costly reagents, and high energy conversion efficiency. However, the process poses significant challenges due to its poor selectivity and low yield. Here, single atom Pd is successfully anchored on N-doped hollow carbon nanospheres via a simple wet impregnation method under relatively mild loading temperature, anhydrous and anaerobic environments. Our experiment demonstrates that SA-Pd/N@C exhibits outstanding catalytic performance in comparison to Pd nanoparticles which is consistent with the results of the DFT calculations, achieving an NH3 yield rate of 132.8 μg·h − 1·mgcat−1 and a corresponding FE of 6 % at -0.2 V versus RHE in HCl electrolyte (pH=1), as well as superior stability with only 5 % decrease after 10 consecutive cycles of electrochemical testing at room temperature, positioning it as one of the most effective catalyst materials reported for eNRR. The exceptional eNRR activity and stability can be attributed to the abundant active sites resulting from the relatively mild loading temperature, as well as electronic effects and structural engineering, which further diminish *H adsorption and efficiently suppress hydrogen evolution reaction. This work will provide a novel approach to enhance the eNRR performance through the effective design of Pd single-atom catalyst

Ab initio morphology prediction of Pd, Ag, Au, and Pt nanoparticles on (0001) sapphire substrates

We energetically predict the morphology of Pd, Ag, Au, and Pt nanoparticles on (0001) sapphire substrates, using density functional theory (DFT) simulations and the well-known Young–Dupre equation. In all cases, the contact angles exceed 90°, indicating that the nanoparticles are spherical. Notably, Au nanoparticles exhibit a higher contact angle than those of their counterparts. The validity of the proposed abinitio nanoparticle morphology prediction approach based on DFT simulations was assessed in comparison with our previous experimental findings pertaining to the time variation of the full width at half maximum (FWHM) of the resonant peak. Furthermore, the diffusivities of single Pd, Ag, Au, and Pt atoms on the substrate were evaluated by calculating the activation energy, offering insights into the underlying physics governing the timing of FWHM peaks. The analysis confirms a higher diffusivity of Au and Ag compared with Pd and Pt. According to the comparison between DFT and experiment results, although no clear relation is observed between the contact angles and timing of FWHM peaks, the diffusivity of sputtered atoms may influence the timing of FWHM peaks. Thus, timing can help to clarify the nanoparticle size, rather than shape.

Local In-O-Pd Lewis acid-base pair boosting CO2 selective hydrogenation to methanol

CO2 hydrogenation into valuable chemicals is industrially essential but very challenging since CO2 is chemically inert and the selectivity is difficult to control. Here, we design and construct In2O3 supported Pd single atoms (Pd1/In2O3 SAC) to boost the methanol yield (254.8 gmethanol·gPd−1·h−1) and selectivity (99.4 %) via the Lewis acid-base pair, which activates the CO2 and forms the intermediate species of formate (HCOO*). The comprehensive experimental and theoretical results confirm that the local Lewis acid-base pair is composed of the isolated Pd atom coupling with the adjacent O and In atoms. The space–time yield (STY) of methanol over Pd1/In2O3 SAC is around 1.7 times higher than the best reported catalysts under comparable conditions. The strategy of constructing local Lewis acid-base pairs with single-atom site and metal oxides reported in this work opens new avenues to develop highly selective catalysts for CO2 utilization.

Light‐Driven C−C Coupling for Targeted Synthesis of CH3COOH with Nearly 100 % Selectivity from CO2

AbstractTargeted synthesis of acetic acid (CH3COOH) from CO2 photoreduction under mild conditions mainly limits by the kinetic challenge of the C−C coupling. Herein, we utilized doping engineering to build charge‐asymmetrical metal pair sites for boosted C−C coupling, enhancing the activity and selectivity of CO2 photoreduction towards CH3COOH. As a prototype, the Pd doped Co3O4 atomic layers are synthesized, where the established charge‐asymmetrical cobalt pair sites are verified by X‐ray photoelectron spectroscopy and X‐ray absorption near edge spectroscopy spectra. Theoretical calculations not only reveal the charge‐asymmetrical cobalt pair sites caused by Pd atom doping, but also manifest the promoted C−C coupling of double *COOH intermediates through shortening of the coupled C−C bond distance from 1.54 to 1.52 Å and lowering their formation energy barrier from 0.77 to 0.33 eV. Importantly, the decreased reaction energy barrier from the protonation of two*COOH into *CO intermediates for the Pd‐Co3O4 atomic layer slab is 0.49 eV, higher than that of the Co3O4 atomic layer slab (0.41 eV). Therefore, the Pd‐Co3O4 atomic layers exhibit the CH3COOH evolution rate of ca. 13.8 μmol g−1 h−1 with near 100% selectivity, both of which outperform all previously reported single photocatalysts for CO2 photoreduction towards CH3COOH under similar conditions.

Light-Driven C-C Coupling for Targeted Synthesis of CH3 COOH with Nearly 100 % Selectivity from CO2.

Targeted synthesis of acetic acid (CH3 COOH) from CO2 photoreduction under mild conditions mainly limits by the kinetic challenge of the C-C coupling. Herein, we utilized doping engineering to build charge-asymmetrical metal pair sites for boosted C-C coupling, enhancing the activity and selectivity of CO2 photoreduction towards CH3 COOH. As a prototype, the Pd doped Co3 O4 atomic layers are synthesized, where the established charge-asymmetrical cobalt pair sites are verified by X-ray photoelectron spectroscopy and X-ray absorption near edge spectroscopy spectra. Theoretical calculations not only reveal the charge-asymmetrical cobalt pair sites caused by Pd atom doping, but also manifest the promoted C-C coupling of double *COOH intermediates through shortening of the coupled C-C bond distance from 1.54 to 1.52 Å and lowering their formation energy barrier from 0.77 to 0.33 eV. Importantly, the decreased reaction energy barrier from the protonation of two*COOH into *CO intermediates for the Pd-Co3 O4 atomic layer slab is 0.49 eV, higher than that of the Co3 O4 atomic layer slab (0.41 eV). Therefore, the Pd-Co3 O4 atomic layers exhibit the CH3 COOH evolution rate of ca. 13.8 μmol g-1 h-1 with near 100% selectivity, both of which outperform all previously reported single photocatalysts for CO2 photoreduction towards CH3 COOH under similar conditions.

Sustainable conversion of alkaline nitrate to ammonia at activities greater than 2 A cm−2

Nitrate (NO3‒) pollution poses significant threats to water quality and global nitrogen cycles. Alkaline electrocatalytic NO3‒ reduction reaction (NO3RR) emerges as an attractive route for enabling NO3‒ removal and sustainable ammonia (NH3) synthesis. However, it suffers from insufficient proton (H+) supply in high pH conditions, restricting NO3‒-to-NH3 activity. Herein, we propose a halogen-mediated H+ feeding strategy to enhance the alkaline NO3RR performance. Our platform achieves near-100% NH3 Faradaic efficiency (pH = 14) with a current density of 2 A cm–2 and enables an over 99% NO3–-to-NH3 conversion efficiency. We also convert NO3‒ to high-purity NH4Cl with near-unity efficiency, suggesting a practical approach to valorizing pollutants into valuable ammonia products. Theoretical simulations and in situ experiments reveal that Cl-coordination endows a shifted d-band center of Pd atoms to construct local H+-abundant environments, through arousing dangling O-H water dissociation and fast *H desorption, for *NO intermediate hydrogenation and finally effective NO3‒-to-NH3 conversion.

Generating active metal/oxide reverse interfaces through coordinated migration of single atoms

Identification of active sites in catalytic materials is important and helps establish approaches to the precise design of catalysts for achieving high reactivity. Generally, active sites of conventional heterogeneous catalysts can be single atom, nanoparticle or a metal/oxide interface. Herein, we report that metal/oxide reverse interfaces can also be active sites which are created from the coordinated migration of metal and oxide atoms. As an example, a Pd1/CeO2 single-atom catalyst prepared via atom trapping, which is otherwise inactive at 30 °C, is able to completely oxidize formaldehyde after steam treatment. The enhanced reactivity is due to the formation of a Ce2O3-Pd nanoparticle domain interface, which is generated by the migration of both Ce and Pd atoms on the atom-trapped Pd1/CeO2 catalyst during steam treatment. We show that the generation of metal oxide-metal interfaces can be achieved in other heterogeneous catalysts due to the coordinated mobility of metal and oxide atoms, demonstrating the formation of a new active interface when using metal single-atom material as catalyst precursor.

The interaction between Pd/CeO2 crystal surface and electric field: Application to complete oxidation of methane

Pd/CeO2 with different crystal faces can significantly affect the methane oxidation process, but the catalytic behavior in electric field is not clear yet. The supported Pd/CeO2 with rod, octahedral and cubic morphologies were synthesized by hydrothermal method, and their methane oxidation efficiency in electric field was measured. The structure of Pd/CeO2 and reaction mechanism in electric field were investigated by XRD, BET, XPS, H2-TPR, TEM and in situ DRIFTs. Studies show that the synergistic effect between electric field and (111) crystal plane in octahedral CeO2 is the strongest and (110) in rod CeO2 is the main active restraint crystal plane. The Pd atoms on the surface of Pd/CeO2-oct are exposed to the most amount of Pd atoms and the main Pd nanoparticles are present. Pd species on CeO2-cube and CeO2-rod surface with relatively low activity exist mainly in the form of Pd2+ and Pd4+, whereas Pd0 and Pd2+ on the Pd/CeO2-oct surface are more favorable for CH4 oxidation in the catalytic cycle. Pd4+ is inactive for CH4 oxidation. In addition, H migration from Pd active site to the support induced by hydrogen spillover can enhance the oxidation activity of CH4 in electric field. The conversion of carbonate/hydrogencarbonate to formate is an advantageous step in the methane oxidation process, with the active sequence being octahedral (111) > cubic (100) > rod (110) faces in/without electric field.

Effects of Pd atom vibration in the Sr–Te octahedral interstitial space in Zintl compound SrPdTe on lattice anharmonicity and thermoelectric properties

Based on first-principles calculations, the current study deeply explores the thermoelectric properties of the Zintl compound SrPdTe. We found that the anharmonic vibration of Pd atoms plays an important role in the quartic anharmonic effect and the temperature dependence of the thermal conductivity. In the crystalline structure, Sr atoms form octahedra with eight surrounding Te atoms, while Pd atoms are located in the gaps between the octahedra. This structure makes the strong atomic mean square displacement of Pd atoms the main factor leading to the ultralow thermal conductivity. The study also reveals the effects of phonon frequency renormalization and four-phonon scattering on heat transfer performance. Even considering the spin–orbit coupling effect, multiple secondary valence band tops maintain the power factor of the material at high temperatures, providing a potential opportunity for achieving excellent thermoelectric performance.

Decreasing the O2‐to‐H2O2 Kinetic Energy Barrier on Dilute Binary Alloy Surfaces with Controlled Configurations of Isolated Active Atoms

AbstractShifting from the typical 4e– pathway to H2O in electrochemical oxygen reduction to the 2e– pathway to H2O2 is increasingly recognized as an environmentally friendly approach for producing H2O2. However, the competitive 4e− pathway is a significant obstacle to the production of H2O2 since H2O is the thermodynamically favored product. Here, a series of Pt, Pd, and Rh active atoms diluted within inert‐Au matrices with precisely controlled atomic arrangements and coordination environments are synthesized via facet engineering for O2‐to‐H2O2 production. Surprisingly, individually dispersed Pt atoms within the Au surface enclosed by the square atomic arrangements exhibit superior H2O2 selectivity and achieve a maximum selectivity of 90% at 0.36 V versus the reversible hydrogen electrode. Operando synchrotron ambient pressure X‐ray photoelectron spectroscopy identifies the presence of *OOH key intermediates on these isolated Pt active sites. Grand canonical density‐functional theory also reveals that the kinetic energy barrier for the 2e− pathway (0.08 eV; OOH* + H+ + e− → H2O2) on the isolated Pt sites is significantly lower than the 4e− pathway (0.29 eV; OOH* + H+ + e− → O* + H2O). This work enables atomic‐scale control in dilute binary alloy surfaces with specific configurations of isolated active atoms and provides essential guidance for catalyst design to boost O2‐to‐H2O2 production.

Catechol Sensing Performance of Pd-Functionalized Two-Dimensional Polyaramid: A DFT Investigation.

Catechol (Cc) molecule adsorption on a pristine and transition metal (TMs = Sc, Pd, and Cu)-functionalized two-dimensional polyaramid (2DPA) monolayer is systematically studied by the first-principles density functional theory method. The weak physisorption (-0.29 eV) and charge transfer of the Cc molecule with p-2DPA result in a very quick recovery time (150 μs), hindering the Cc sensing capability of p-2DPA. Although TM functionalization greatly improved the adsorption ability, the Pd-functionalized 2DPA was shown to be the best choice for Cc adsorption due to the reasonable adsorption energy of -1.39 eV and expedited charge transfer between the Cc and Pd atom. The change of band gap and, hence, the conductivity of the Pd-2DPA system in response to the adsorption of the Cc molecule demonstrate its higher sensitivity than that of p-2DPA. The work function sensitivity of Pd-2DPA upon the Cc adsorption is also investigated. In addition to the change in the electronic properties, the change in the optical properties of Pd-2DPA after Cc adsorption is also analyzed. The structural stability of Pd-2DPA is validated by performing ab initio molecular dynamics simulations at 300 K. The complete desorption of the Cc molecule from Pd-2DPA is attained by annealing the material at 550 K under visible light (τ = 5.4 s) and at 450 K under UV light (τ = 3.7 s). Moreover, the higher diffusion energy barrier of +1.35 eV confirmed that the functionalized Pd atoms did not diffuse through the crystal to form clusters. This study could lay a theoretical foundation for developing possibly new-generation sensors for detecting Cc molecules.

Transition metal doped 2D SiC (TM=Ag, Pd and Rh) as a potential candidate for NOx (x = 1,2) and NH3 sensing

To control the nitrogen oxide emissions in large power plants, accurate monitoring NOx and NH3 gases at the outlet of the selective catalytic reduction system is vital to determine the degree of NOx reaction and adjust the amount of injected NH3. In this study, transition-metal (TM) atoms (Ag, Pd and Rh) doped 2D graphene-like SiC monolayers have been designed based on first-principles calculations. The adsorption and detection characteristics of TM-doped 2D SiC monolayers for NOx (x = 1, 2) and NH3 were systematically investigated. It is found that TM-doped 2D SiC monolayers exhibit strong potential in developing chemical sensors capable of detecting NO, NO2 and NH3. With the decoration of TM atoms in SiC monolayers, the adsorption ability of NO, NO2 and NH3 could be enhanced ascribed to the increased adsorption energy and electrical conductivity. In addition, the TM-SiC monolayers exhibit desirable thermostability at 298 K, 498 K and 798 K. By comparing the variations in atom-to-atom distances, plane-averaged charge density differences, charge transfers, density of states, energy gap variation and the recovery times of TM-doped SiC before and after adsorbed NOx and NH3, we found that Pd-SiC, Ag-SiC and Rh-SiC are optimal for the detection and recovery of NO, NO2 and NH3 gases with adsorption energies − 1.82 eV, − 2.17 eV, − 1.10 eV, respectively.

Feeble Single-Atom Pd Catalysts for H2 Production from Formic Acid.

Single-atom catalysts are thought to be the pinnacle of catalysis. However, for many reactions, their suitability has yet to be unequivocally proven. Here, we demonstrate why single Pd atoms (PdSA) are not catalytically ideal for generating H2 from formic acid as a H2 carrier. We loaded PdSA on three silica substrates, mesoporous silicas functionalized with thiol, amine, and dithiocarbamate functional groups. The Pd catalytic activity on amino-functionalized silica (SiO2-NH2/PdSA) was far higher than that of the thiol-based catalysts (SiO2-S-PdSA and SiO2-NHCS2-PdSA), while the single-atom stability of SiO2-NH2/PdSA against aggregation after the first catalytic cycle was the weakest. In this case, Pd aggregation boosted the reaction yield. Our experiments and calculations demonstrate that PdSA in SiO2-NH2/PdSA loosely binds with amine groups. This leads to a limited charge transfer from Pd to the amine groups and causes high aggregability and catalytic activity. According to the density functional calculations, the loose binding between Pd and N causes most of Pd's 4d electrons in amino-functionalized SiO2 to remain close to the Fermi level and labile for catalysis. However, PdSA chemically binds to the thiol group, resulting in strong hybridization between Pd and S, pulling Pd's 4d states deeper into the conduction band and away from the Fermi level. Consequently, fewer 4d electrons were available for catalysis.

Pd 4d Orbital Overlapping Modulation on Au@Pd Nanowires for Efficient H2O2 Production.

Isolating Pd atoms has been shown to be crucial for the design of a Pd-based electrocatalyst toward 2e- oxygen reduction reaction (ORR). However, there are limited studies focusing on the systematic compositional design that leads to an optimal balance between activity and selectivity. Herein, we design a series of Au@Pd core@shell structures to investigate the influence of the Pd 4d orbital overlapping degree on 2e- ORR performance. Density functional theory (DFT) calculations indicate that enhanced H2O2 selectivity and activity are achieved at Pdn clusters with n ≤ 3, and Pd clusters larger than Pd3 should be active for 4e- ORR. However, experimental results show that Au@Pd nanowires (NWs) with Pd4 as the primary structure exhibit the optimal H2O2 performance in an acidic electrolyte with a high mass activity (7.05 A mg-1 at 0.4 V) and H2O2 selectivity (nearly 95%). Thus, we report that Pd4, instead of Pd3, is the upper threshold of Pd cluster size for an ideal 2e- ORR. It results from the oxygen coverage on the catalyst surface during the ORR process, and such an oxygen coverage phenomenon causes electron redistribution and weakened *OOH binding strength on active sites, leading to enhanced activity of Pd4 with only 0.06 V overpotential in acidic media.

Synergistically enhancing nitrate reduction into N2 in water by N-doped Pd–Cu biochar bimetallic single-atom electrocatalysis

Noble metal materials have been identified as high efficiency catalysts for electrocatalytic reduction of nitrate, and the synthesis and manufacture of high catalytic activity and environmentally friendly catalysts of activating hydrogen for water purification applications is extremely attractive. In this work, the Pd–Cu single-atom catalysts (Pd–Cu-N-BC) were first prepared by direct growth of Pd–Cu single-atom on bamboo biochar by regulating the concentration of precursors and doping method, and then enhanced electrocatalytic reduction nitrate performance and N2 generation. The results showed that Pd–Cu-N-BC displayed excellent catalytic activity and reusability in electrocatalytic reduction nitrate with a low potential of 0.47 V vs. RHE (@10 mA cm−2). The maximum nitrate removal efficiency and N2 generation could reach about 100% and 72.32% within 180 min, respectively. The density functional theory (DFT) calculations confirmed that Cu atoms could catalyze the electrochemical reduction of nitrate to nitrite, and Pd atoms anchored in the nitrogen-doped biochar (N-BC) lattice could catalyze electrochemical reduction of nitrite to N2 involving the formation of hydrogen radical (H*). The characterization results of XANES showed that electronic synergistic effect between Pd and Cu single atoms significantly promotes the N2 production through hydrogenation while inhibiting the generation of byproducts, leading to significantly enhanced electrocatalytic reduction of nitrate to N2. Finally, Pd–Cu-N-BC was designed as a 3D particle electrode for enhanced electrocatalytic reduction of nitrate, exhibiting excellent stability and reusability, which could be considered as a suitable candidate for applications in the remediation of nitrate contamination.Graphical

Nanocatalytic and antimicrobial potency of CQD@Pd nanoparticles: Experimental and theoretical approach

A single-pot approach has been developed for the fabrication of novel heterogeneous nanocatalyst of carbon quantum dots doped palladium (CQD@Pd-NPs) nanoparticles. Herein, Aegle marmelos fruit extract was utilized as a reducing and capping agent for the fabrication of CQD@Pd-NPs. Synthesis of metallic nanoparticles through green chemistry route is environment beneficial technology owing to its low cost and ecological compatibility. The formation of CQD-NPs and CQD@Pd-NPs was confirmed with high-end sophisticated techniques and theoretical studies. The computational analysis revealed a discernible decrease in the band gap value (Egap = ELUMO - EHOMO) from 0.08 eV to 0.03 eV upon the introduction of Pd atoms into carbon quantum dots (CQDs). Therefore, computational data also authenticates the stability of the CQD@Pd-NPs nanocatalyst which was predominantly supported by electrostatic interaction between Pd and CQDs. The developed nanocatalyst has vouched for an effective candidature in the Suzuki-Miyaura and Mizoroki-Heck coupling reactions with a superior selectivity for product formation. The excellent antibacterial properties against E. coli and S. aureus were further supported by visualizing bacterial growth, inhibition zone, FESEM results and molecular docking studies. Moreover, the nanocatalyst displayed facile separation from the reaction system and showcased efficient recyclability with minimal activity loss. This further supports an effective potential over existing commercial catalysts and holds immense future prospective in industrial applications.

Research of the caged dynamics of clusters center atoms in the Pd82Si18 amorphous alloy

Abstract To date, there is still a lack of a comprehensive explanation for caged dynamics which is regarded as one of the intricate dynamic behaviors in amorphous alloys. This study focuses on Pd82Si18 as the research object to further elucidate the underlying mechanism of caged dynamics from multiple perspectives, including the cage’s lifetime, atomic local environment, and atomic potential energy. The results reveal that Si atoms exhibit a pronounced cage effect due to the hindrance of Pd atoms, resulting in an anomalous peak in the non-Gaussian parameters. An in-depth investigation was conducted on the caged dynamics differences between fast and slow Si atoms. In comparison to fast Si atoms, slow Si atoms were surrounded by more Pd atoms and occupied lower potential energy states, resulting in smaller diffusion displacements for the slow Si atoms. Concurrently, slow Si atoms tend to be in the centers of smaller clusters with coordination numbers of 9 and 10. During the isothermal relaxation process, clusters with coordination numbers 9 and 10 have longer lifetimes, suggesting that the escape of slow Si atoms from their cages is more challenging. The findings mentioned above hold significant implications for understanding the caged dynamics.

Reversible hydrogenation and dehydrogenation of benzene for hydrogen storage on highly dispersed Pd/γ-Al2O3 catalyst

The research and development of efficient catalyst is the key to achieving high-capacity hydrogen storage in liquid organic hydrogen carriers (LOHCs). The highly dispersed Pd/γ-Al2O3 catalysts with few-atom Pd were prepared by impregnation method using HNO3 as promoter. The hydrogen storage capacity of the benzene/cyclohexane hydrogen carriers was further investigated by vapor phase benzene hydrogenation and cyclohexane dehydrogenation reactions over the studied Pd/γ-Al2O3 catalysts. The results showed that the metal Pd was the active centers for the benzene hydrogenation/cyclohexane dehydrogenation reactions. The addition of HNO3 can effectively promote the metal Pd to be highly dispersed, thus improving the Pd atoms utilization and reducing the Pd dosage. Meanwhile, the strongly electronic effects between the highly dispersed Pd species and the Al2O3 support promoted the electron-deficient Pdδ+ sites to be formed, which enhanced the adsorption and activation ability for the reactants molecules. The benzene conversion on the Pd/γ-Al2O3 catalyst with a metallic Pd loading of 1.0 wt% reached 97.51 % at 200 °C. While the cyclohexane conversion reached 90.94 % at 400 °C with the actual hydrogen storage capacity of 6.54 wt%, which provided an effective idea for large-scale storage and transportation of H2 based on LOHCs.

Atomic intimacy in Pd1Ni/SiO2 single-atom alloy prepared by galvanic replacement for enhanced semi-hydrogenation of acetylene

Metal single-atom alloys (SAAs) are important catalysts in many catalytic reactions, while the preparation of metal SAA catalysts is a major challenge because the metal species can inevitably deposit on both support and the host metal when using conventional preparation methods, leading to decreased catalytic performances. In this work, we report the preparation of metal SAA by the galvanic replacement (GR) to selectively deposit metal species on the host nanocrystals (NCs) prior to loading on a support. It includes the first synthesis of Ni NCs by colloidal method and the following deposition of Pd atoms onto Ni NCs via GR. After that, the Pd1Ni nanocrystal alloys were deposited onto SiO2 and the atomic intimacy of Pd with Ni was confirmed by multiple characterization techniques. The Pd1Ni/SiO2 SAA prepared by GR presented improved catalytic reactivity in semi-hydrogenation of acetylene, as compared to the reference PdNi/SiO2 catalyst prepared by impregnation. Moreover, the Pd1Ni/SiO2-GR catalyst showed higher C2H4 selectivity in a wide range of temperatures (30–180 °C), which was better than Pd1Ni/SiO2-I SAA, Pd/NiO-I and Pd/SiO2-I catalysts prepared by impregnation. The DFT explains the enhanced selectivity, which is due to the electron transfer from Ni nanocrystal to Pd single atoms. The electron transfer was resulted from the improved intimacy of Pd atoms and Ni nanocrystals.

Linkage Isomers of Triangular Pd Metallacycles and Catalysis in Aqueous Suzuki Coupling Reaction.

The water-soluble trinuclear Pd metallacycles [Pd(tmeda)(4-Spy)]3(X)3 (tmeda = tetramethylethylenediamine, X = OTf, 2; NO3, 3) were synthesized from the ambidentate ligand 4-pyridylthiolate (Spy-) and [Pd(tmeda)X2] in 80 and 70% yield, respectively. Two possible linkage isomers are found in solution (slow interconversion found in the NMR) and in the solid state. Density functional calculations showed that the energy of the isomer with a D3-symmetric arrangement of the SPy ligand and all Pd atoms having N∧NPdSN coordination is only 7 kcal/mol lower. When reacting [Pd(tmeda)(NO3)2] with 4,4'-biphenyldithiolate (S2bph2-), the tetranuclear [{Pd(tmeda)}4(μ-S2bph)2](NO3)4 (1) was formed. A new type of undecanuclear Pd cluster was separated as a minor product from an acetone solution of 2 in air. The new complexes represent the first examples of water-soluble Pd metallacycles constructed from a pyridine-thiolate ligand. They show catalytic activity with turnover numbers ranging from 9 to 420 in aqueous Suzuki cross-coupling reactions using phenyl boronic acid and a number of aryl halides. An optimized system gave a TON of 6,900,000 and a TOF of 492,857 h-1. The catalyst could be reused eight times, and the activity has been attributed to the formation of PdNPs.