Pd Nanocrystals Research Articles

Palladium nanocrystals immobilized on boron and nitrogen codoped mesoporous carbon spheres as efficient methanol oxidation electrocatalysts

The development of cost-effective and high-performance electrocatalysts is crucial for the widespread application of direct methanol fuel cell. Herein, a convenient and robust method is developed to the controllable fabrication of Pd nanocrystals in situ immobilized on boron and nitrogen codoped mesoporous carbon spheres (Pd/BNMCS) as anode catalysts for the methanol oxidation reaction. The as-derived Pd/BNMCS hybrids are equipped with a series of useful structural features, such as large specific surface area, abundant mesoporous channels, presence of plentiful B and N atoms, well-dispersive Pd nanoparticles, and good electrical conductivity. As a consequence, the optimized Pd/BNMCS catalyst demonstrates superior electrocatalytic methanol oxidation properties in terms of a large electrochemically active surface area, high mass/specific activities, and reliable long-term stability, which are significantly better than those of traditional carbon black and undoped mesoporous carbon sphere supported Pd catalysts. This study highlights the potential of heteroatom codoped mesoporous carbon matrixes in the construction of advanced noble metal electrocatalysts for practical fuel cell applications.

In situ Raman investigation to electrochemical synthesis of ammonia on Pd nanocrystals.

Nitrate and nitrite are widely present in industrial wastewater and domestic sewage, so electrocatalytic reduction of both nitrate and nitrite to ammonia synthesis is considered to be a sustainable development approach. Pd nanostructures have attracted much attention because of their high activity in catalyzing the nitrate electrochemical reduction reaction. Here we prepare Pd nanocube and octahedron for the electrochemical reduction of nitrate and nitrite. It is found that Pd octahedron shows slightly higher activity toward nitrate reduction than Pd nanocube, while for nitrite reduction, Pd octahedron shows much higher activity than Pd nanocube. The ammonia yield rate is more potential-dependent. In situ Raman characterization further confirms the existence of adsorbed ammonia on the surface of nanocube and octahedron, indicating similar reduction pathways on (111)-facet octahedron and (100)-facet nanocube.

Triple junction excess energy in polycrystalline metals

The energetics of triple lines are often negligible in polycrystalline systems, but may play a significant role in the finest nanocrystals, and in fact lower the excess defect energies of those polycrystals. This paper develops a methodology to assess polycrystalline average grain boundary and triple junction excess energies for pure fcc metals Ni, Cu, Al, Pd, Pt, Ag and Au using embedded atom method potentials. It is found that there are correlations between the triple line energy and physical quantities such as grain boundary and dislocation line energy, but with a negative sign indicating that triple junctions reduce intergranular excess energy per area on average. The relationship with grain boundary energy is of order ∼−4.5 × 10−10 m, and the triple junction energy is about −1/12 of the dislocation line energy. Despite their low energy, triple junctions can significantly affect total system energy due to their high density in the finest nanocrystals; for example, 6-nm Pd nanocrystals have an effective intergranular energy of ∼0.83 J/m2 (compared with the large grain size limit of 0.93 J/m2), translating to a measurable bulk excess enthalpy of ∼6 kJ/mol. Such excess enthalpy is experimentally assessable, and the present framework can be used to measure triple junction energies. For instance, re-analyzing data of Lu and Sun (Phil. Mag., 1997) we obtain grain boundary and triple junction energies of 0.33 J/m2 and −3.0 × 10−10 J/m respectively for Selenium nanocrystals, which can be compared with modeled values of 0.76 J/m2 and −1.02 × 10−10 J/m by using our method with a published bond-order potential for Se.

Temperature Dependent Growth Kinetics of Pd Nanocrystals: Insights from Liquid Cell Transmission Electron Microscopy.

Quantifying the role of experimental parameters on the growth of metal nanocrystals is crucial when designing synthesis protocols that yield specific structures. Here, the effect of temperature on the growth kinetics of radiolytically-formed branched palladium (Pd) nanocrystals is investigated by tracking their evolution using liquid cell transmission electron microscopy (TEM) and applying a temperature-dependent radiolysis model. At early times, kinetics consistent with growth limited is measured by the surface reaction rate, and it is found that the growth rate increases with temperature. After a transition time, kinetics consistent with growth limited by Pd atom supply is measured, which depends on the diffusion rate of Pd ions and atoms and the formation rate of Pd atoms by reduction of Pd ions by hydrated electrons. Growth in this regime is not strongly temperature-dependent, which is attributed to a balance between changes in the reducing agent concentration and the Pd ion diffusion rate. The observations suggest that branched rough surfaces, generally attributed to diffusion-limited growth, can form under surface reaction-limited kinetics. It is further shown that the combination of liquid cell TEM and radiolysis calculations can help identify the processes that determine crystal growth, with prospects for strategies for control during the synthesis of complex nanocrystals.

Surfactant-free CuPd nano-alloy for N2H4 oxidation-assisted H2 evolution and H2O2 detection

The utilization of hydrazine oxidation reaction (HzOR) with a lower thermodynamic oxidation potential has been regarded as an efficient strategy for H2 generation through electrolysis. However, a highly efficient and stable bifunctional electrocatalyst for overall hydrazine (N2H4) splitting was scarce. This work verified promising CuPd nano-alloy as a bifunctional electrocatalys for energy-efficient electrolytic hydrogen production, with hydrazine assistance. It is demonstrated that the CuPd nano-alloy exhibited enhanced electrocatalytic activity for both cathodic and anodic reactions compared to pure Cu and Pd nanocrystals, benefiting from its favorable electronic structure. Under 1.0 M KOH electrolyte with 0.1 M N2H4, the surfactant-free CuPd nano-alloy only required a potential of 0.648 V to achieve the N2H4 splitting (OHzS). The surfactant-free surface maximized exposed active sites, which facilitated the adsorption and desorption of reactants, resulting in enhanced electrocatalytic activity. And working potential for HzOR by surfactant-free CuPd was only 50.4 % compared to the CuPd nano-alloy with surfactant. This work provided an efficient electrocatalyst for OHzS. The enhanced electro-catalytic performances resulting from the electronic structure of alloy and the surfactant-free interface effect have been thoroughly discussed and verified, which would be invaluable for the design of efficient electrocatalysts for H2 production.

Systematic combination of palladium facets and monolayer metal hydroxide nanosheets for promotion of ethanol oxidation reaction

The design of catalyst surfaces that exhibit high activities for ethanol oxidation reaction (EOR) is essential to achieving practical application of direct ethanol fuel cells. Composite catalysts of Pd nanoparticles and metal hydroxide are promising candidates for EOR; however, a guide of catalyst design, including appropriate valence states and interfacial structures between component materials, has not been identified. Herein, we synthesize composite electrocatalysts of cubic and octahedral Pd nanocrystals with well-defined facets and monolayer metal hydroxide nanosheets with an identical structure and different composition containing Ni, Fe and Mn, and systematically elucidate highly active interfacial sites between Pd and metal hydroxides for EOR. Promotion of OH− adsorption by the hydroxide nanosheets enhances the catalytic activities of the Pd nanocrystals and the nanosheet having higher affinity to OH− result in higher EOR performances of the composite catalysts. The improved activities are greater for (111) facet than for (100) facet of the Pd whereas the (100) facet is superior for EOR to the (111) facet for the bare Pd nanocrystals. Our study suggests that combination of the Pd (111) facet and metal hydroxides is favorable for developing highly active electrocatalysts for EOR.

Wet-Chemical Synthesis of Concave Hexoctahedral Pd and Pd@Pt Nanocrystals for Methanol Electrooxidation.

Nanocrystals (NCs) exposed with high-index facets usually show enhanced electrocatalytic performances. However, it is a great challenge to persevere with high-index facets against their high surface energy during the synthesis. Herein, we successfully synthesize concave hexoctahedral (c-HOH) Pd NCs exposed with 48 high-index {741} facets using a facile one-pot wet-chemical protocol. Control experiments illustrate that l-ascorbic acid plays a critical role in the formation of the c-HOH morphology, acting as both reducing and capping agents. Moreover, we can extend the synthesis for fabricating c-HOH Pd@Pt core-shell NCs by simply introducing a Pt precursor into the reaction solution, attaining remarkably boosted electrocatalysis for methanol electrooxidation reaction (MOR). Integrating the merits of {741} facets, concave structure, and ligand and strain effect of the core-shell structure, c-HOH Pd4@Pt1 core-shell NCs showed an excellent MOR mass activity of 1.18 A mgPGM-1 or 3.60 A mgPt-1, which is 3.80 or 11.61 times higher than that of commercial Pt/C, respectively.

Epitaxial growth of Pd clusters on N-doped Ag nanowires for oxygen reduction reaction

Efficient and stable Pt-free electrocatalysts for oxygen reduction reaction (ORR) are indispensable for future fuel cells. Herein, we describe a heterostructure of Pd nanocrystals (PdNCs) on N-doped Ag nanowires (NWs) synthesized using a direct epitaxial growth strategy with a Pd loading of only 9.5 wt.%. The PdAg bimetallic heterostructure showed the highest mass activity among reported PdAg-based ORR electrocatalysts and exhibited excellent stability, with only a 1.5 mV decay in the half-wave potential even after 20000 cycles of continuous testing. The remarkably enhanced activity and durability can be attributed to the distinct advantages of the ultrasmall PdNCs, cocatalysts of N-doped AgNWs, and their heterointerfaces. This work reveals that the epitaxial growth of a heterostructure on a stable support is a promising strategy for promoting catalytic performance.

Size, shape, and dimension effects on the melting temperature of metallic nanocrystals

Melting is the most common phenomenon in nature and one of the most important properties of metallic materials. Exploring the size D, shape α, and dimension d effects on the melting temperature T m of nanocrystals is of great significance for the design, fabrication, and application of quantum devices. In this work, by redefining the critical diameter D 0 and introducing shape factor α, a unified model without any adjustable parameters has been developed to describe the T m(D, α, d) function. The model is compared with the available experimental and simulation data of Cu, Pd, In, Pb, Au, Ag, and Ni nanocrystals and other theoretical works, and a consistent agreement is obtained, which verifies the accuracy of the prediction. This model is also compared with other theoretical works, and we find that it agrees well with Lu’s model, while the BOLS method underestimates the melting point. This work not only gives a new perspective on the relationship between size, shape, dimension, and melting temperature but also provides theoretical guidance for the design and optimization of low-dimensional quantum devices.

Freestanding Penta-Twinned Palladium Nanosheets.

Control over the morphology of nanomaterials to have a 2D structure and manipulating the surface strain of nanostructures through defect control have proved to be promising for developing efficient catalysts for sustainable chemical and energy conversion. Here a one-pot aqueous synthesis route of freestanding Pd nanosheets with a penta-twinned structure (PdPT NSs) is presented. The generation of the penta-twinned nanosheet structure can be succeeded by directing the anisotropic growth of Pd under the controlled reduction kinetics of Pd precursors. Experimental and computational investigations showed that the surface atoms of the PdPT NSs are effectively under a compressive environment due to the strain imposed by their twin boundary defects. Due to the twin boundary-induced surface strain as well as the 2D structure of the PdPT NSs, they exhibited highly enhanced electrocatalytic activity for oxygen reduction reaction compared to Pd nanosheets without a twin boundary, 3D Pd nanocrystals, and commercial Pd/C and Pt/C catalysts.

What Elements Really Intercalate into Pd Lattice When Heated in Dimethylformamide?

Palladium hydrides (PdHx) are pivotal in both fundamental research and practical applications across a wide spectrum. PdHx nanocrystals, synthesized by heating in dimethylformamide (DMF), exhibit remarkable stability, granting them widespread applications in the field of electrocatalysis. However, this stability appears inconsistent with their metastable nature. The substantial challenges in characterizing nanoscale structures contribute to the limited understanding of this anomalous phenomenon. Here, through a series of well-conceived experimental designs and advanced characterization techniques, including aberration-corrected scanning transmission electron microscopy (AC-STEM), in situ X-ray diffraction (XRD), and time-of-flight secondary ion mass spectrometry (TOF-SIMS), we have uncovered evidence that indicates the presence of C and N within the lattice of Pd (PdCxNy), rather than H (PdHx). By combining theoretical calculations, we have thoroughly studied the potential configurations and thermodynamic stability of PdCxNy, demonstrating a 2.5:1 ratio of C to N infiltration into the Pd lattice. Furthermore, we successfully modulated the electronic structure of Pd nanocrystals through C and N doping, enhancing their catalytic activity in methanol oxidation reactions. This breakthrough provides a new perspective on the structure and composition of Pd-based nanocrystals infused with light elements, paving the way for the development of advanced catalytic materials in the future.

Palladium‐Boride Nanoflowers with Controllable Boron Content for Formic Acid Electrooxidation

AbstractThe rational design of the electronic structure and elemental compositions of anode electrocatalysts for formic acid electrooxidation reaction (FAOR) is paramount for realizing high‐performance direct formic acid fuel cells. Herein, palladium‐boride nanoflowers (Pd‐B NFs) with controllable boron content are rationally designed via a simple wet chemical reduction method, utilizing PdII‐dimethylglyoxime as precursor and NaBH4 as both reductant and boron source. The boron content of Pd‐B NFs can be regulated through manipulation of reaction time, accompanying with the crystal phase transition from face‐centered cubic to hexagonal close‐packed within the parent Pd lattice. The obtained Pd‐B NFs exhibit increased FAOR mass and specific activity with increasing boron content, showcasing remarkable inherent stability and anti‐poisoning capability compare to commercial Pd and platinum (Pt) nanocrystals. Notably, the sample reacted for 12 h reveals high FAOR specific activity (31.5 A m−2), which is approximately two times higher than the commercial Pd nanocrystals. Density functional theory calculations disclose that the d‐sp orbital hybridization between Pd and B modifies surface d‐band properties of Pd, thereby optimizing the adsorption of key intermediates and facilitating FAOR kinetics on the Pd surface. This study paves the way toward the utilization of metal boride‐based materials with simple synthesis methods for various electrocatalysis applications.

Ultrasmall Pd nanocrystals confined into Co-based metal organic framework-decorated MXene nanoarchitectures for efficient methanol electrooxidation

The natural scarcity and insufficient utilization of noble metal-based catalysts bring a heavy block in the way of the widespread applications of direct methanol fuel cells. Herein, we propose a feasible bottom-up approach to the construction of ultrasmall Pd nanocrystals confined into Co-based metal organic framework-decorated Ti3C2Tx MXene (Pd/MOF-MX) nanoarchitectures via a controllable solvothermal process. The ultrathin MXene nanolamellas and porous Co-based MOFs constitute an ideal hybrid carrier with high electron conductivity and large accessible surface areas, which not only facilitates the size restriction and uniform dispersion of Pd nanocrystals, but also ameliorates their intrinsic catalytic activity through the direct electronic interactions. By virtue of the pronounced synergistic coupling effects, the newly-developed Pd/MOF-MX nanoarchitectures exhibit markedly enhanced electrocatalytic properties towards the methanol oxidation reaction, including a large electrochemically active surface area of 116.7 m2 g−1, a high mass activity of 1700.4 mA mg−1 as well as a satisfactory long-term durability, which are superior to those of traditional Pd electrocatalysts anchored on carbon blacks, carbon nanotubes, graphene, and undecorated MXene matrixes.

Feasible preparation of preferentially oriented (111) Pd nanocrystals supported on cyano-COFs for ultrahigh activity in C-C cross-couplings

It is much challenging to synthesize highly dispersed noble metal nanocrystals (MNCs) and prevent their aggregation during the catalytic cycles. Choosing suitable solid supports to mediate the growth of MNCs can provide stable yet ultra-highly active heterogenous catalysts. However, very few studies have provided the controllable preparation of ultrafine MNCs. Herein, cyano-functionalized covalent organic frameworks (cyano-COFs)-mediated ultrafine preferentially oriented (111) PdNCs with particle diameter of 2.88 ± 0.60 nm were easily prepared in MeOH without any other external reducing agent. The obtained Pd/cyano-COFs presented ultrahigh activity in Suzuki-Miyaura couplings, with TOF of 2578 h−1 and chemo-selectivity of > 99 % for the cross-coupling between p-iodotoluene and phenylboronic acid at room temperature in the air. Furthermore, outstanding catalytic performance of Pd/cyano-COFs was found in Heck couplings as well. This study provides a new idea for the controllable preparation of metallic nanomaterials with high performance, which could facilitate the research on the regulation of catalytic performance by the chemical composition of supports.

Catalytic hydrodechlorination of chlorophenols over facet-specific Pd nanocrystals

Clarifying the reaction mechanism of catalytic hydrodechlorination (HDC) and designing Pd surface structures with high catalytic activity are crucial for maximizing its ability to remove chlorophenol pollutants. In this study, single-crystalline Pd nanocrystals enclosed by {110}, {100} or {111} facets with average particle diameters ∼ 6.5 nm were prepared and then originally evaluated their activities for catalytic HDC of chlorophenols. The experimental results indicate that dodecahedral Pd nanocrystals enclosed with {110} facets show the highest catalytic activity for HDC of chlorophenols with a turnover frequency up to 19.1 min−1, which is ∼ 3.1 times as high as that of cubic Pd nanocrystals and 12.7 times higher than that of octahedral Pd nanocrystals. Theoretic calculations reveal that Pd (110) facets have the strongest activation ability for chlorophenol and the lower energy barrier in dechlorination and hydrogenation steps. Moreover, dodecahedral Pd nanocrystals exhibit high HDC activity for various chlorophenolic derivatives and structural stability. We believe that the study could provide insights into the understanding and design of highly efficient Pd systems for various HDC reactions.

Interfacial Electronic Interactions within the Pd-CeO2/Carbon Onions Define the Efficient Electrocatalytic Ethanol Oxidation Reaction in Alkaline Electrolytes.

Porous Pd-based electrocatalysts are promising materials for alkaline direct ethanol fuel cells (ADEFCs) and ethanol sensors in the development of renewable energy and point-of-contact ethanol sensor test kits for drunk drivers. However, experimental and theoretical investigations of the interfacial interaction among Pd nanocrystals on supports (i.e., carbon black (CB), onion-like carbon (OLC), and CeO2/OLC) toward ADEFC and ethanol sensors are not yet reported. This is based on the preparation of Pd-CeO2/OLC nanocrystals by the sol-gel and impregnation methods. Evidently, the porous Pd-CeO2/OLC significantly increased membrane-free micro-3D-printed ADEFC performance with a high peak power density (Pmax = 27.15 mW cm-2) that is 1.38- and 7.58-times those of Pd/OLC (19.72 mW cm-2) and Pd/CB (3.59 mW cm-2), besides its excellent stability for 48 h. This is due to the excellent interfacial interaction among Pd, CeO2, and OLC, evidenced by density functional theory (DFT) simulations that showed a modulated Pd d-band center and facile active oxygenated species formation by the CeO2 needed for ethanol fuel cells. Similarly, Pd-CeO2/OLC gives excellent sensitivity (0.00024 mA mM-1) and limit of detection (LoD = 8.7 mM) for ethanol sensing and satisfactory recoveries (89-108%) in commercial alcoholic beverages (i.e., human serum, Amstel beer, and Nederberg Wine). This study shows the excellent possibility of utilizing Pd-CeO2/OLC for future applications in fuel cells and alcohol sensors.

Cellulose/GO monolith covered with Pd–Pt bimetallic nanocrystals for continuous-flow catalytic reduction of hexavalent chromium

Cellulose monolith materials have interconnected open porous structures with very high porosity, making them attractive structures for use as support materials in heterogeneous catalysis applications. In this study, we developed a highly efficient and reusable continuous-flow reactor for Cr(VI) remediation by combining the advantageous features of cellulose monoliths with suitable reinforcement techniques. We fabricated a porous monolithic cellulose/graphene oxide (GO) composite with a continuous three-dimensional skeletal framework using the thermally induced phase separation technique. Pd nanocrystals were synthesized in situ on the surface of the composite monolith, and then converted to porous Pd–Pt bimetallic nanocrystals through a galvanic replacement reaction. This approach eliminated the need for additional reductants and stabilizers, making the process simpler and more environmentally friendly. Under carefully optimized conditions, the cellulose/GO/Pd–Pt nanocomposite monolith exhibited outstanding performance in continuous-flow reactions for Cr(VI) reduction, achieving a maximum conversion rate of 98 %. Moreover, the nanocomposite monolith-based heterogeneous catalyst exhibited remarkable long-term stability, maintaining its catalytic activity even after extended periods of storage in the dried state. These findings highlight the potential of cellulose-based composite monoliths as versatile and robust support materials for heterogeneous catalysis.

Site-targeted decoration of palladium nanocrystals for catalytic CH4 removal in lean-burn exhaust.

Site-targeted decoration of catalytic nanocrystals is essential for maximizing performance with minimal materials use. Here, we demonstrate successful, site-targeted decoration of palladium (Pd) nanocrystals with nickel (Ni) exclusively along crystal facet edges through the thermal decomposition of nickel carbonyl (Ni(CO)4) vapor. Strong interactions between carbon monoxide and Pd facet for passivation or between Ni(CO)4 and crystal facet edges resulted in selective Ni decoration at the nanocrystal edges. The Ni-decorated Pd nanocrystals exhibit superior catalytic performance for methane (CH4) removal in an oxygen-rich lean-burn exhaust atmosphere, requiring 10 times less Ni decoration than conventional Pd-Ni composite catalysts prepared by the wet impregnation method. The site-targeted decoration of nanocrystals introduced in this work offers an efficient and resource-minimizing strategy for enhanced catalytic applications.

Crucial size effect on dicarbonylation of acetylene over Pd/CsHPMo heterogeneous catalysts

Structure-sensitive activity of Pd catalyst in carbonylation reaction is an urgent problem to be explored. Herein, Pd nanocrystals with uniform particle size (2.3 nm, 3.4 nm, 5.0 nm and 6.7...

Photochemical engineering unsaturated Pt islands on supported Pd nanocrystals for a robust pH-universal hydrogen evolution reaction.

The rational design of heterostructured nanocrystals (HNCs) is of great significance for developing highly efficient hydrogen evolution reaction (HER) electrocatalysts. However, a significant challenge still lies in realizing the controllable synthesis of desired HNCs directly onto a support and exploring their structure-activity-dependent HER performance. Herein, we reported various controllable Pd7@Ptx core-shell HNCs with optimal hybrid structures via a photochemical deposition strategy. The growth patterns of a Pt shell can be finely controlled by adjusting the growth kinetics, resulting in a varying deposition rate. In particular, the as-prepared Pd7@Pt3 HNCs with a Pt shell in the Stranski-Krastanov mode showed the best performances over a wide pH range media, delivering low overpotentials of 33, 18 and 49 mV, resulting in a catalytic current density of 10 mA cm-2 at a low effective catalyst loading of 0.021 mg cm-2. The resulting Tafel slopes were 23.1, 52.6 and 42.7 mV dec-1 in 0.5 M H2SO4, 1.0 M phosphate-buffered saline (PBS) and 1.0 M KOH electrolyte, respectively. It was found that the increased fraction of unsaturated coordination of Pt islands in the resultant material is the key to the enhanced and robust HER activity, which has been confirmed through density functional theory (DFT) calculations. This strategy could be extended to the rational design and synthesis of other heterostructured catalysts for energy conversion and storage.