Pd Atoms Research Articles

Ambient-condition acetylene hydrogenation to ethylene over WS2-confined atomic Pd sites

Ambient-condition acetylene hydrogenation to ethylene (AC-AHE) is a promising process for ethylene production with minimal additional energy input, yet remains a great challenge due to the difficulty in the coactivation of acetylene and H2 at room temperature. Herein, we report a highly efficient AC-AHE process over robust sulfur-confined atomic Pd species on tungsten sulfide surface. The catalyst exhibits over 99% acetylene conversion with a high ethylene selectivity of 70% at 25 oC, and a record space-time yield of ethylene of 1123 molC2H4 molPd−1 h−1 under ambient conditions, which is nearly four times that of the typical Pd1Ag3/Al2O3 catalyst, and exhibiting superior stability of over 500 h. We demonstrate that the confinement of Pd-S coordination induces positively-charged atomic Pdδ+, which not only facilitates C2H2 hydrogenation but also promotes C2H4 desorption, thereby enabling a high conversion of C2H2 to C2H4 at room temperature while suppressing over-hydrogenation to C2H6.

Anchoring atomic Pd on molybdenum disulfide with state-of-the-art specific activity in the electrochemical dehalogenation of florfenicol

The widespread discharge of halogenated organic pollutants (HOPs) in wastewater brings significant risks to the environment and human health due to potent high toxicity, antibacterial activity, and strong biodegradation resistance. Adsorbed atomic hydrogen (H*ads)-mediated electrocatalytic hydrodehalogenation (EHDH) has been recognized as an efficient strategy for HOPs removal through selectively breaking carbon-halogen bonds. In this work atomic Pd uniformly anchored on molybdenum disulfide (denoted as Pd-MoS2) was synthesized through a facile hydrothermal method and found with state-of-the-art specific activity in florfenicol (FLO) removal via the H*ads-mediated EHDH process. Pd-MoS2 completely dehalogenated (∼100 %) FLO within 30 min at a rate constant of 0.15 min−1, which was 6.0, 6.5 and 33.1 times the value of MoS2, Pd/C and carbon paper samples, respectively. Notably, the toxicity of the wastewater was reduced to 1/6 of its original value after the treatment. Moreover, Pd-MoS2 presented superior catalytic stability in five successive cycles. Furthermore, Pd-MoS2 was also robust in complex water environment with practical applicability for industrial wastewater treatment. A dual-active-center mechanism with enhanced H*ads production capacity and the improved H*ads utilization efficiency was contributed to the increased EHDH activity on Pd-MoS2.

Surface segregation on Ag@MNi (M = Pd, Pt, Rh, and Ru) core–shell nanocrystals for enhancing the oxygen reduction performance

Synthesis of cost-effective electrocatalysts for oxygen reduction reaction (ORR) has received wide attention due to their sluggish kinetics, which limits the development and application of fuel cell technique. In this work, we report a versatile synthetic approach to prepare a series of small-sized Ag@MNi (M = Pd, Pt, Rh, Ru) nanocrystals with core–shell structures by a simple solvothermal method. According to characterization analysis, surface segregation of Pd was proved in the outermost layer with the Pd-rich shell layer, which can regulate the adsorption energy of *OH. Electrochemical results show that the onset potential and half-wave potential of Ag@PdNi nanocrystals (Ag@PdNi NCs) are 1.005 and 0.913 V vs. RHE (reversible hydrogen electrode), respectively, with a Tafel slope of 55.31 mV dec-1 and strong ORR catalytic durability, which is similar to Ag@MNi (M = Pt, Rh, Ru) NCs and slightly higher than that of PdAg alloy nanoparticles (PdAg alloy NPs), PdNi alloy nanoparticles (PdNi alloy NPs), commercial Pd black and even commercial Pt/C, in alkaline medium. Density Functional (DFT) calculations show that the presence of Agcore effectively promotes the segregation of Pd atoms to the outer shell surface, where Ni provides better segregated substitution sites for Pd, which significantly improves the ORR activity and durability due to the electronic synergistic effect between Agcore nuclei and Pdshell can reduce the adsorption strength of OHads.

Water-promoted oxidative coupling of aromatics with subnanometer palladium clusters confined in zeolites

A fundamental understanding of the active sites in working catalysts can guide the rational design of new catalysts with improved performances. In this work, we have followed the evolution of homogeneous and heterogeneous Pd catalysts under the reaction conditions for aerobic oxidative coupling of toluene for the production of 4,4′-bitolyl. We have found that subnanometer Pd clusters made with a few Pd atoms are the working active sites in both homogeneous and heterogeneous catalytic systems. Moreover, water can promote the activity of Pd clusters by nearly one-order magnitude for oxidative coupling reaction by facilitating the activation of O2. These new insights lead to the preparation of a catalyst made with Pd clusters supported on a two-dimensional zeolite, which expands the scope of the oxidative coupling of aromatics to larger substrates.

Embedding Single Pd Atoms on NiGa Intermetallic Surfaces for Efficient and Selective Alkyne Hydrogenation.

Catalytic removal of alkynes is essential in industry for producing polymer-grade alkenes from steam cracking processes. Non-noble Ni-based catalysts hold promise as effective alternatives to industrial Pd-based catalysts but suffer from low activity. Here we report embedding of single-atom Pd onto the NiGa intermetallic surface with replacing Ga atoms via a well-defined synthesis strategy to design Pd1-NiGa catalyst for alkyne semi-hydrogenation. The fabricated Pd1Ni2Ga1 ensemble sites deliver remarkably higher specific mass activity under superb alkene selectivity of >96 % than the state-of-the-art catalysts under industry-relevant conditions. Integrated experimental and computational studies reveal that the single-atom Pd synergizes with the neighbouring Ni sites to facilitate the σ-adsorption of alkyne and dissociation of hydrogen while suppress the alkene adsorption. Such synergistic effects confer the single-atom Pd on the NiGa intermetallic with a Midas touch for alkyne semi-hydrogenation, providing an effective strategy for stimulating low active Ni-based catalysts for other selective hydrogenations in industry.

OH Regulator of Amorphous CrOx on Defect-Rich Ultrafine Pd Nanowires Boosts Electrocatalytic Ethanol Oxidation.

Reasonable construction of high activity and selectivity electrocatalysts is crucial to achieve efficient ethanol oxidation reaction (EOR). However, the oxidation of ethanol tends to produce CO species that poison the active centers of the EOR electrocatalysts. Herein, a unique amorphous CrOx-protected defect-rich ultrafine Pd nanowires (CrOx-Pd NWs) is developed. On the one hand, the CrOx layer can act as a protective layer to maintain the structure of the nanowire. On the other hand, it can play the role of OH regulator to optimize the adsorption energy barrier of intermediate species in Pd nanowire, thereby enhancing the ability of the catalyst to resist CO poisoning. The CrOx-Pd NWs exhibit excellent EOR performance with 3.64 times higher mass activity and 50mV lower CO electro-oxidation potential than commercial Pd black. The results show that the CrOx layer promotes the dissociation of H2O into OHads, while the CrOx transfers electrons to neighboring Pd atoms optimizing the electronic configuration of Pd, thus selectively oxidizing ethanol to acetate and preventing the formation of toxic *CO. This work provides an effective strategy for the synthesis of nanowire materials with oxide/metal interfaces and offers new ideas for the design of catalysts that can efficiently drive EOR.

Efficient selective hydrogenation of phenylacetylene over Pd-based rare earth dual-atomic catalysts

Selective hydrogenation of phenylacetylene to styrene plays a vital role in fine chemical synthesis with palladium (Pd)-based catalysts as the active components and usually suffered from low selectivity due to over-hydrogenation and low stability through polymerization (c.a. green oil generation). In this work, we found that by confining the Pd atom within a Pd-Ln (Ln: rare earth elements, such as Y, Lu, etc. ) diatomic structure [diatomic catalyst (DAC)], the reaction performance of selective hydrogenation of phenylacetylene has been greatly promoted, in which 92% styrene selectivity has been determined at 100% phenylacetylene conversion. This would be attributed to the diatomic structure established, which was achieved by introducing Pd-Ln precursors and confirmed by high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and X-ray adsorption fine structure (XAFS) characterizations and it was demonstrated that slight electron transfer from Ln to the adjacent isolated Pd makes it slightly negatively charged and facilitated the styrene formation. Besides, a Langmuir-Hinshelwood model was established to describe the whole reaction mechanism. After a systematic kinetic investigation, it suggests that the C8H6* + H* elementary step is probably the kinetically relevant for the whole reaction and the surface of the catalyst is mainly covered by C8H6*. The energy relationship of each step along phenylacetylene hydrogenation was quantitatively described by means of parity fitting and gas isothermal adsorption, providing insights into the selective hydrogenation of phenylacetylene over 0.02%Pd-Ln/C (Ln = Y/Lu) catalysts and pave the way of catalytic design at the atomic level.

Trimetallic Alloys as an Electrocatalyst for Fuel Cells: The Case of Methyl Formate on Pt3Pd3Sn2.

The shift toward renewable energy sources plays a central role in the quest for a circular economy. In this context, methyl formate (MF) has garnered attention as a compelling hydrogen carrier and alternative fuel, because of its remarkable characteristics (energy density, ease of storage and transport, and low boiling point). In this study, DFT calculations supported by online electrochemical mass spectroscopy (OE-MS) were performed to investigate the MF electro-oxidation (MFEO) on Pt3Pd3Sn2 (111). The DFT calculations provide insight into the role of Pt, Pd, and Sn atoms in MFEO. Pt and Pd together provide a preferred active site for initiating MFEO through the O-H bond scission, and Sn plays an essential role in the mitigation of CO through oxygenation or water activation. By comparing the reaction energies and activation barriers for all possible reactions in MFEO, the suggested path necessitates a minimum energy of 0.14 eV to initiate the MFEO. This value was supported by the experimental results, showing that the oxidation wave of MF starts at 0.15 V (70 °C). Density functional theory (DFT) results, supported by OE-MS, indicate that the hydrolysis of MF prior to MFEO is not preferred on Pt3Pd3Sn2 (111) surfaces, although the formation of methanol is plausible via a CH3O intermediate. Among the three small organic molecules (SOMs) studied─MF, methanol, and formic acid─MF has the lowest activation energy for the initial bond breaking that starts the whole oxidation process (0.13 eV), compared to formic acid (0.45 eV) and methanol (0.61 eV); thus, MF is the preferred fuel on Pt3Pd3Sn2 (111).

Atomic structure of different surface terminations of polycrystalline ZnPd

The intermetallic compound ZnPd has been found to have desirable characteristics as a catalyst for the steam reforming of methanol. The understanding of the surface structure of ZnPd is important to optimize its catalytic behavior. However, due to the lack of bulk single-crystal samples and the complexity of characterizing surface properties in the available polycrystalline samples using common experimental techniques, all previous surface science studies of this compound have been performed on surface alloy samples formed through thin-film deposition. In this study, we present findings on the chemical and atomic structure of the surfaces of bulk polycrystalline ZnPd studied by a variety of complementary experimental techniques, including scanning tunneling microscopy (STM), x-ray photoelectron spectroscopy (XPS), low energy electron microscopy (LEEM), photoemission electron microscopy (PEEM), and microspot low-energy electron diffraction (μ-LEED). These experimental techniques, combined with density functional theory (DFT)-based thermodynamic calculations of surface free energy and detachment kinetics at the step edges, confirm that surfaces terminated by atomic layers composed of both Zn and Pd atoms are more stable than those terminated by only Zn or Pd layers. DFT calculations also demonstrate that the primary contribution to the tunneling current arises from Pd atoms, in agreement with the STM results. The formation of intermetallics at surfaces may contribute to the superior catalyst properties of ZnPd over Zn or Pd elemental counterparts. Published by the American Physical Society 2024

In Situ Construction of Highly Dispersed Pd on Cobalt Nanoparticle on Hollow Functional Cubic Graphene by Double Framework for ORR.

Developing advanced functional carbon materials is essential for electrocatalysis, caused by their vast merits for boosting many key energy conversion reactions. Herein, the covalent organic frameworks (COFs) is utilized on metal-organic frameworks (MOFs) as the template, under the controllable metal atoms thermal migration process successfully in situ constructs Pd-Co alloy nanoparticles on hollow cubic graphene. The electrocatalytic oxygen reduction reaction (ORR) evaluation showed excellent performances with a half-wave potential of 0.866V, and a limited current density of 4.975mA cm-2, that superior to the commercial Pt/C and Co nanoparticles. The contrast experiments and X-ray absorption spectrum demonstrated the aggregated electrons at highly dispersed Pd atoms on Co nanoparticle that promoted the main activities. This work not only enlightens the novel carbon materials designing strategies but also suggests heterogeneous electrocatalysis.

Alloying effects on the reactivity of Pd are ensemble dominated

In this paper the geometric (“ensemble”) and electronic (“ligand”) effects of alloying on surface reactivity and catalysis are considered. The effect of alloying on the behaviour of Pd, both in single crystal form, and as a nanoparticulate catalyst is discussed. The first case concerns Pd alloyed with Cu, and here the reactivity with formic acid and ethanol is modified by the presence of Cu. However, both Cu and Pd maintain their elemental integrity for the reactions, and it is shown that the main alloying effect is one of dilution of Pd atoms, rather than by global electronic factors such as d-band shifting and filling. Similarly, when Pd is alloyed with Au, then the adsorption characteristics (sticking probability and uptake) for CO, O2, ethene and acetaldehyde are dominated by changes in the surface arrangement of the two atoms. Au mainly acts as an adsorption blocker, but to different degrees depending upon the nature of the adsorbing molecule and its demand for particular ensemble sizes. Finally, nanoparticulate Pd is considered, and the effect of alloying on high pressure methanol synthesis from CO2 and H2 is outlined. Pd on its own is not very selective, instead it mainly produces CO and methane. However, by supporting on oxides such as ZnO, Ga2O3 and In2O3 and by reducing in hydrogen, the Pd forms alloys, which then results in high selectivity to methanol. Again, this is ascribed to the dilution of the Pd ensembles at the surface, which are the cause of methane production.

Pd-Adsorbing CrS2 monolayer as sensing material for detecting CO, C2H2, and C2H4 in dissolved gases: A first-principles study

This study employs density functional theory to initially examine the adsorption characteristics of Pd atom on CrS2 monolayer (termed Pd@CrS2). Subsequently, the adsorption capabilities of Pd@CrS2 monolayer for CO, C2H2, and C2H4 are simulated to assess its prospects for dissolved gas detection. Stable adsorption of Pd atoms onto the CrS2 monolayer atop Cr atoms is observed with a binding energy of −2.69 eV. Pd@CrS2 exhibits chemisorption towards CO, C2H2, and C2H4 with respective adsorption energies of −1.49, −1.13, and −1.22 eV. The band structure and density of states analysis indicate significant alterations in the electronic properties of CrS2 upon Pd adsorption and upon exposure to the gases. The bandgap of Pd@CrS2 is modified by −29.6 %, −24.7 %, and −27.1 % after CO, C2H2, and C2H4 adsorption, corresponding to highly sensitive detection responses of −99.6 %, −98.9 %, and −99.3 %. The research highlights the gas sensing capabilities of Pd@CrS2 monolayers for monitoring the operational status in dissolved gas analysis, showcasing the promising application potential of CrS2.

A DFT study of SF6 decomposition products (H2S, SO2, and CS2) adsorption and detection on Pd-ZnO/SnS2 ternary composites

Real-time and accurate detection of SF6 decomposition products is a crucial approach to diagnosing internal faults of gas-insulated switchgear (GIS). However, the limited sensitivity and selectivity of SnS2 gas sensors have hindered their further development and application. This study employs density functional theory to design the optimal Pd-ZnO/SnS2 monolayer structure and investigate its adsorption behavior toward H2S, SO2, and CS2. The findings indicate that Pd atom doping and ZnO nanoparticle incorporation significantly enhance the conductivity of the SnS2 monolayer, reducing the band gap to 0.54 eV and lowering the work function by 5.019 eV. Regarding gas adsorption and sensing, the Pd-ZnO/SnS2 monolayer outperforms intrinsic SnS2 and ZnO/SnS2, showing the order in which SF6 decomposition products are selected is: CS2 > SO2 > H2S. Additionally, the sensitivity and recovery time of Pd-ZnO/SnS2 as a gas sensor were evaluated, confirming its excellent sensing performance for SO2 and CS2 detection. This study provides theoretical insights to advance the application of gas sensors in online insulation equipment monitoring.

Structure sensitivity in the formic acid-driven catalytic transfer hydrogenation of maleic acid to succinic acid over Pd/C catalysts

A series of carbon-supported palladium catalysts (Pd/C) with average particle size in the range from 3 to 7 nm was prepared by varying the Pd loading. These materials and the influence of their physicochemical properties in the catalytic transfer hydrogenation (CTH) of maleic acid (MAc) to succinic acid (SAc) using formic acid (FAc) as H2 donor were evaluated. The chemical, textural, and surface properties were studied by a number of characterization techniques (ICP-OES, XRD, TEM, and XPS). It was found that the intrinsic rate of SAc formation per surface Pd atom (turn-over frequency, TOF Pdsur) is structure-sensitive. The TOF Pdsur rate increases with the particle size following a volcano-type curve, reaching a maximum for an average particle size of ca. 6 nm. Assuming a cuboctahedral shape with a cubic close-packed structure, an approximation frequently adopted for Pd particles, it was found that, for the series of catalysts, neither the calculated TOF of Pd surface atoms at low coordination sites nor at high coordination are constant. This suggests that no geometric effect is responsible for the structure-sensitivity. Among the different Pd species present in the catalysts (i.e., metallic Pd (Pd0), palladium carbide (PdCx), and oxidized Pd), it was observed that the relative number of surface Pd0 sites also follows a volcano-type curve, which indicates that Pd0 sites are necessarily involved in the most active centers. For particles with an average size larger than 4 nm, the TOF rate of surface Pd0 sites was constant and in the range of 0.12 s−1. For smaller sizes, a more accurate determination of their Pd0 surface concentration is required to obtain reliable surface Pd0 TOF rates.

Enhancing Activity and Stability of Pd-on-TiO2 Single-Atom Catalyst for Low-Temperature CO Oxidation through in Situ Local Environment Tailoring.

The development of efficient Pd single-atom catalysts for CO oxidation, crucial for environmental protection and fundamental studies, has been hindered by their limited reactivity and thermal stability. Here, we report a thermally stable TiO2-supported Pd single-atom catalyst that exhibits enhanced intrinsic CO oxidation activity by tunning the local coordination of Pd atoms via H2 treatment. Our comprehensive characterization reveals that H2-treated Pd single atoms have reduced nearest Pd-O coordination and form short-distanced Pd-Ti coordination, effectively stabilizing Pd as isolated atoms even at high temperatures. During CO oxidation, partial replacement of the Pd-Ti coordination by O or CO occurs. This unique Pd local environment facilitates CO adsorption and promotes the activity of the surrounding oxygen species, leading to superior catalytic performance. Remarkably, the turnover frequency of the H2-treated Pd single-atom catalyst at 120 °C surpasses that of the O2-treated Pd single-atom catalyst and the most effective Pd/Pt single-atom catalysts by an order of magnitude. These findings open up new possibilities for the design of high-performance single-atom catalysts for crucial industrial and environmental applications.

Change of composition and surface plasmon resonance of Pd/Au core/shell nanoparticles triggered by CO adsorption.

Controlling composition and plasmonic response of bimetallic nanoparticles (NPs) is of great relevance to tune their catalytic activity. Herein, we demonstrate reversible composition and plasmonic response transitions from a core/shell to a bimetallic alloyed palladium/gold NP triggered by CO adsorption and sample temperature. The use of self-organized growth on alumina template film allows scrutinizing the impact of core size and shell thickness onto NP geometry and plasmonic response. Topography, molecular adsorption, and plasmonic response are addressed by scanning tunneling microscopy, vibrational sum frequency generation (SFG) spectroscopy, and surface differential reflectance spectroscopy, respectively. Modeling CO dipolar interaction and optical reflectivity corroborate the experimental findings. We demonstrate that probing CO adsorption sites by SFG is a remarkably sensitive and relevant method to investigate shell composition and follow in real-time Pd atom migration between the core and the shell. Pd-Au alloying is limited to the first two monolayers of the shell and no plasmonic response is found, while for a thicker shell, a plasmonic response is observed, concomitant with a lower Pd concentration in the shell. Above 10-4mbar, at room temperature, CO adsorption triggers the shell restructuration, forming a Pd-Au alloy that weakens the plasmonic response via Pd migration from the core to the shell. NP annealing at 550K, after pumping CO, leads to the desorption of remaining CO and gives enough mobility for Pd to migrate back inside the core and recover a pure gold shell with its original plasmonic response. This work demonstrates that surface stoichiometry and plasmonic response can be tuned by using CO adsorption and NP annealing.

Transition-metal atoms embedded MoTe2 single-atom catalyst for efficient electrocatalytic hydrogen evolution reaction

As an attractive catalyst for the electrochemical hydrogen evolution reaction(HER), MoTe2 has attracted great interest. However, scarce catalytic sites and unsatisfactory catalytic activity of pristine MoTe2 basal plane impeded its practical application. The incorporation of single metal atom into 2D-substrate have been demonstrated as an effective strategy to tune HER activity of materials. Herein, we systematically investigated a series of transition-metal atoms(Fe, Co, Ni, Cu, Ru, Rh, Pd and Ag) embedded MoTe2 plane and edge single-atom catalysts(SAC, TM-MoTe2) for HER performance by employing density functional theory calculations. All TM-MoTe2 catalysts exhibit good thermodynamically and electrochemical stability. Compared with pristine MoTe2, HER catalytic activity of TM-MoTe2 are significantly enhanced due to effective modulation of charge transfer on embedded metal, which attribute to synergy interaction between embedded TM and surrounding Mo atoms. Specially, 2 candidate catalysts with Ru-MoTe2 plane and Fe-MoTe2 edge are found to show higher HER catalytic performance with low overpotential of only 10 mV and 60 mV, respectively. Furthermore, we found a key descriptor Δdd′ to well predict HER-activity trend of MoTe2-based material, which is closely correlated with H adsorption energy(ΔEH). This work provides in-depth theoretical insights for understanding active sites and designing high-efficiency MoTe2-based HER catalysts.

Fibrous catalyst based on atomic Pd and N-doped holey graphene functionalized cotton fiber for continuous-flow reaction

Continuous-flow catalysis bridges the gap between bench-scale laboratories and production-scale factories and thus should be a green and promising technology for the manufacture of value-added chemicals. Here, we present the construction of a continuous-flow catalytic system by integrating a tubular reactor with novel catalytic fibers, which are comprised of single-atomic Pd (Pd1) and nitrogen-doped holey graphene (NHG) functionalized cotton fibers (CFs). Due to the loosely packed structure, highly exposed dual-active sites (i.e., single-atomic PdN4 sites and activated C sites in the NHG carbocatalyst) of the CF@(Pd1/NHG) catalytic fibers, the corresponding flowing system exhibites remarkably high catalytic performance (activity and durability) and processing rate in organic reactions, including oxidative hydroxylation of phenylboronic acid and reduction of nitroarenes. Typically, the processing rate of the catalytic system toward 4-nitrophenol (a representative nitroarene) reduction can reach up to 2.46 × 10−3 mmol·mg−1·min−1, significantly higher than that of those packing catalysts reported in recent years.

Heteroatoms‐Stabilized Single Palladium Atoms on Amorphous Zeolites: Breaking the Tradeoff between Catalytic Activity and Selectivity for Alkyne Semihydrogenation

AbstractAs a fundamental industrial catalytic process, the semihydrogenation of alkynes presents a challenge in striking a balance between activity and selectivity due to the issue of over‐hydrogenation. Herein, we develop an efficient catalytic system based on single‐atom Pd catalysts supported on boron‐containing amorphous zeolites (Pd/AZ−B), achieving the tradeoff breaking between the activity and selectivity for the selective hydrogenation of alkynes. Advanced characterizations and theoretical density functional theory calculations confirm that the incorporated B atoms in the Pd/AZ−B can not only alter the geometric and electronic properties of Pd atoms by controlling the electron migration from Pd but also mitigate the interaction between alkene and the catalyst supports. This boosts the exceptional catalytic efficacy in the semihydrogenation of phenylacetylene to styrene under mild conditions (298 K, 2 bar H2), achieving a recorded turnover frequency (TOF) value of 24198 h−1 and demonstrating 95 % selectivity to styrene at full conversion of phenylacetylene. By comparison, the heteroatom‐free amorphous zeolite‐anchored Pd nanoparticles and the commercial Lindlar catalyst have styrene selectivities of 73 % and 15 %, respectively, under identical reaction conditions. This work establishes a solid foundation for developing highly active and selective hydrogenation catalysts by controllably optimizing their electronic and steric properties.

Heteroatoms-Stabilized Single Palladium Atoms on Amorphous Zeolites: Breaking the Tradeoff between Catalytic Activity and Selectivity for Alkyne Semihydrogenation.

As a fundamental industrial catalytic process, the semihydrogenation of alkynes presents a challenge in striking a balance between activity and selectivity due to the issue of over-hydrogenation. Herein, we develop an efficient catalytic system based on single-atom Pd catalysts supported on boron-containing amorphous zeolites (Pd/AZ-B), achieving the tradeoff breaking between the activity and selectivity for the selective hydrogenation of alkynes. Advanced characterizations and theoretical density functional theory calculations confirm that the incorporated B atoms in the Pd/AZ-B can not only alter the geometric and electronic properties of Pd atoms by controlling the electron migration from Pd but also mitigate the interaction between alkene and the catalyst supports. This boosts the exceptional catalytic efficacy in the semihydrogenation of phenylacetylene to styrene under mild conditions (298 K, 2 bar H2), achieving a recorded turnover frequency (TOF) value of 24198 h-1 and demonstrating 95 % selectivity to styrene at full conversion of phenylacetylene. By comparison, the heteroatom-free amorphous zeolite-anchored Pd nanoparticles and the commercial Lindlar catalyst have styrene selectivities of 73 % and 15 %, respectively, under identical reaction conditions. This work establishes a solid foundation for developing highly active and selective hydrogenation catalysts by controllably optimizing their electronic and steric properties.