Bimetallic Au–Pd alloy nanoparticles supported on MIL-101(Cr) as highly efficient catalysts for selective hydrogenation of 1,3-butadiene

Gold–palladium (Au–Pd) bimetallic nanoparticle (NP) catalysts supported on MIL-101(Cr) with Au : Pd mole ratios ranging from 1 : 3 to 3 : 1 were prepared through coimpregnation and H₂ reduction. Au–Pd NPs were homogeneously distributed on the MIL-101(Cr) with mean particle sizes of 5.6 nm. EDS and XPS analyses showed that bimetallic Au–Pd alloys were formed in the Au(2)Pd(1)/MIL-101(Cr). The catalytic performance of the catalysts was explored in the selective 1,3-butadiene hydrogenation at 30–80 °C on a continuous fixed bed flow quartz reactor. The bimetallic Au–Pd alloy particles stabilized by MIL-101(Cr) presented improved catalytic performance. The as-synthesized bimetallic Au(2)Pd(1)/MIL-101(Cr) with 2 : 1 Au : Pd mole ratio showed the best balance between the activity and butene selectivity in the selective 1,3-butadiene hydrogenation. The Au–Pd bimetallic-supported catalysts can be reused in at least three runs. The work affords a reference on the utilization of a MOF and alloy nanoparticles to develop high-efficiency catalysts.

Bimetallic Au–Pd alloy particles stabilized by MIL-101(Cr) showed high activity and butene selectivity for 1,3-butadiene hydrogenation reaction.     

Au–Ag and Pt–Ag bimetallic nanoparticles@halloysite nanotubes: morphological modulation,improvement of thermal stability and catalytic performance

In this study, Au–Ag and Pt–Ag bimetallic nanocages were loaded on natural halloysite nanotubes (HNTs) via galvanic exchange based on Ag@HNT. By changing the ratio of Au to Ag or Pt to Ag in exchange processes, Au–Ag@HNT and Pt–Ag@HNT with different nanostructures were generated. Both Au–Ag@HNT and Pt–Ag@HNT systems showed significantly improved efficiency as peroxidase-like catalysts in the oxidation of o-phenylenediamine compared with monometallic Au@HNT and Pt@HNT, although inert Ag is dominant in the composition of both Au–Ag and Pt–Ag nanocages. On the other hand, loading on HNTs enhanced the thermal stability for every system, whether monometallic Ag nanoparticles, bimetallic Au–Ag or Pt–Ag nanocages. Ag@HNT sustained thermal treatment at 400 °C in nitrogen with improved catalytic performance, while Au–Ag@HNT and Pt–Ag@HNT maintained or even had slightly enhanced catalytic efficiency after thermal treatment at 200 °C in nitrogen. This study demonstrated that natural halloysite nanotubes are a good support for various metallic nanoparticles, improving their catalytic efficiency and thermal stability.

Bimetallic Au–Ag@HNT and Pt–Ag@HNT nanocages showed significantly improved efficiency in the oxidation of o-phenylenediamine as peroxidase-like catalyst compared with corresponding monometallic nanoparticles.     

Pt–Nix alloy nanoparticles: a new strategy for cocatalyst design on a CdS surface for photo-catalytic hydrogen generation

Solar photocatalytic water splitting for the production of hydrogen has been a core aspect for decades. A highly active and durable photocatalyst is crucial for the success of the renewable hydrogen economy. To date, the development of highly effective photocatalysts has been seen by the contemporary research community as a grand challenge. Thus, herein we put forward a sincere attempt to use a Pt–Ni_x alloy nanoparticle (NP) cocatalyst loaded CdS photocatalyst ((Pt–Ni_x)/CdS) for photocatalytic hydrogen production under visible light. The Pt–Ni_x alloy NP cocatalyst was synthesized using a one-pot solvothermal method. The cocatalyst nanoparticles were deposited onto the surface of CdS, forming a Pt–Ni_x/CdS photocatalyst. Photocatalytic hydrogen production was carried out using a 300 W Xe light equipped with a 420 nm cut-off filter. The H₂ evolution rate of the Pt–Ni₃/CdS photocatalyst can reach a value as high as 48.96 mmol h⁻¹ g⁻¹ catalyst, with a quantum efficiency of 44.0% at 420 nm. The experimental results indicate that this Pt–Ni₃/CdS photocatalyst is a prospective candidate for solar hydrogen generation from water-splitting.

In this report, PtNi_x alloy NPs coupled with a CdS photocatalyst for photocatalytic hydrogen generation under visible light have been explored.     

Palladium nanoparticles loaded on nitrogen and boron dual-doped single-wall carbon nanohorns with high electrocatalytic activity in the oxygen reduction reaction

Palladium nanoparticles with a diameter of 2–4 nm supported on nitrogen and boron dual-doped single-wall carbon nanohorns (Pd-NBCNHs) are synthesized via a one-step method and their electrocatalytic activities are investigated for the oxygen reduction reaction (ORR) in alkaline media. The electrochemical results demonstrate that the oxygen reduction peak potential of Pd-NBCNHs is similar to that of commercial 20% Pt–C. Furthermore, Pd-NBCNHs show a more positive half-wave potential than 20% Pt–C and display better long-term stability and resistance to methanol than 20% Pt–C, which is attributed to the synergetic effect of the Pd nanoparticles and NBCNHs. As NBCNHs have abundant pyrrolic nitrogen, charged sites and defective structures, they not only act as a carrier, but also provide the active sites for oxygen adsorption during the oxygen reduction reaction process. The outstanding electrochemical performance makes Pd-NBCNHs promising to be applied in fuel cells.

Palladium nanoparticles with a diameter of 2–4 nm loaded on nitrogen and boron dual-doped single-wall carbon nanohorns (Pd-NBCNHs) are prepared via one-step method and their electrocatalytic activities are studied for the oxygen reduction reaction.     

Physical process-aided fabrication of periodic Au–M (M = Ag,Cu, Ag–Cu) alloyed nanoparticle arrays with tunable localized surface plasmon resonance and diffraction peaks

Periodic alloyed (Au–Ag, Au–Cu, Au–Ag–Cu) nanoparticle (NP) arrays with uniform size, controllable composition and center-to-center spacing were fabricated by a novel and facile strategy based on physical vapor deposition on a monolayer colloidal crystal template and further heat treatment. The composition and center-to-center spacing were manipulated by adjusting the sputtering target in the deposition process and the size of colloidal spheres of the template, respectively. The shadow effect and a dewetting model were employed to analyze the whole process of evolution from a metallic thin film to spherical nanoparticles with uniform size. The localized surface plasmon resonance (LSPR) and diffraction peaks of these alloyed arrays were systematically measured. The dielectric constant has an important influence on LSPR peaks and diffraction peaks. Both the LSPR and diffraction peaks of Au–Ag alloyed NPs arrays exhibit a blue shift due to their lower dielectric constant than that of pure Au NPs. However, compared with Au, Cu possesses a higher dielectric constant, leading to a red shift of the LSPR and diffraction peaks of Au–Cu alloyed NPs arrays. With the increase of NP size, the diffraction peaks of both binary alloyed NPs exhibit a slight red shift. Moreover, the LSPR absorption peaks were more sensitive to the composition of the NPs than the diffraction peaks. This work would open up a novel strategy in the production of alloyed NP arrays with tunable LSPR peaks and diffraction peaks, which would be very helpful to improve their practical applications in various fields.

An interesting and facile physical route is proposed to fabricate multi-elemental alloyed nanoparticle arrays with controllable size, composition and periodicity.     

Biosynthesis of Ag–Pd bimetallic alloy nanoparticles through hydrolysis of cellulose triggered by silver sulfate

We report a simple but efficient biological route based on the hydrolysis of cellulose to synthesize Ag–Pd alloy nanoparticles (NPs) under hydrothermal conditions. X-ray powder diffraction, ultraviolet-visible spectroscopy and scanning transmission electron microscopy-energy dispersive X-ray analyses were used to study and demonstrate the alloy nature. The microscopy results showed that well-defined Ag–Pd alloy NPs of about 59.7 nm in size can be biosynthesized at 200 °C for 10 h. Fourier transform infrared spectroscopy indicated that, triggered by silver sulfate, cellulose was hydrolyzed into saccharides or aldehydes, which served as both reductants and stabilizers, and accounted for the formation of the well-defined Ag–Pd NPs. Moreover, the as-synthesized Ag–Pd nanoalloy showed high activity in the catalytic reduction of 4-nitrophenol by NaBH₄.

We report a simple but efficient biological route based on the hydrolysis of cellulose to synthesize Ag–Pd alloy nanoparticles (NPs) under hydrothermal conditions.     

Catalysis with magnetically retrievable and recyclable nanoparticles layered with Pd(0) for C–C/C–O coupling in water

Nanoparticles layered with palladium(0) were prepared from nano-sized magnetic Fe₃O₄ by coating it with silica and then reacting sequentially with phenylselenyl chloride under an N₂ atmosphere and palladium(ii) chloride in water. The resulting Fe₃O₄@SiO₂@SePh@Pd(0) NPs are magnetically retrievable and the first example of NPs in which the outermost layer of Pd(0) is mainly held by selenium. The weight percentage of Pd in the NPs was found to be 1.96 by ICP-AES. The NPs were authenticated via TEM, SEM-EDX, XPS, and powder XRD and found to be efficient as catalysts for the C–O and C–C (Suzuki–Miyaura) coupling reactions of ArBr/Cl in water. The oxidation state of Pd in the NPs having size distribution from ∼12 to 18 nm was inferred as zero by XPS. They can be recycled more than seven times. The main features of the proposed protocols are their mild reaction conditions, simplicity, and efficiency as the catalyst can be separated easily from the reaction mixture by an external magnet and reused for a new reaction cycle. The optimum loading (in mol% of Pd) was found to be 0.1–1.0 and 0.01–1.0 for O-arylation and Suzuki–Miyaura coupling, respectively. For ArCl, the required amount of NPs was more as compared to that needed for ArBr. The nature of catalysis is largely heterogeneous.

Fe₃O₄@SiO₂@SePh@Pd(0) (Pd, 1.96%) as the first example of NPs having a Pd(0) layer held by selenium can execute C–C/C–O coupling in 2–6 h (80 °C).     

Ultra-small palladium nano-particles synthesized using bulky S/Se and N donor ligands as a stabilizer: application as catalysts for Suzuki–Miyaura coupling

Two chalcogenated ligands L1 and L2 containing anthracene core and amine functionality have been synthesized. Both the ligands have been characterized using ¹H and ¹³C{¹H} NMR techniques. The structure of L1 has also been corroborated by single crystal X-ray diffraction. Application of L1 and L2 as stabilizers for palladium nano-particles (NPs) has been explored and six different types of NPs 1–6 have been prepared by varying the quantity of stabilizer. The nano-particles have been characterized by PXRD, EDX, and HRTEM techniques. The size of NPs has been found to be in the range of ∼1–2 nm, 2–3 nm, 4–6 nm, 1–2 nm, 1–2 nm and 3–5 nm for 1–6 respectively. The catalytic activities of 1–6 have been explored for Suzuki–Miyaura coupling of phenyl boronic acid with various aryl halides. These NPs showed good catalytic activity for various aryl chlorides/bromides at low catalyst loading (5 mg). Among 1–6, the highest activity has been observed for NPs 1, probably due to their relatively small size and high uniformity in the dispersion. The recyclability of the NPs upto 5 catalytic cycles is a distinct advantage.

Monodispersed ultrasmall Pd nanoparticles synthesized utilizing bulky organochalcogen secondary amines as stabilizers and application in Suzuki coupling of aryl chlorides at low catalyst loading.     

Polymer microgels for the stabilization of gold nanoparticles and their application in the catalytic reduction of nitroarenes in aqueous media

Polymer microgels containing a polystyrene core and poly(N-isopropylmethacrylamide) shell were synthesized in aqueous media following a free radical precipitation polymerization. Au nanoparticles were fabricated into the shell region of the core–shell microgels denoted as P(STY@NIPM) by the in situ reduction of chloroauric acid with sodium borohydride. Various characterization techniques such as transmission electron microscopy (TEM), ultraviolet–visible spectroscopy (UV-visible) and Fourier transform infrared spectroscopy (FTIR) were used for the characterization of Au–P(STY@NIPM). The catalytic potential of Au–P(STY@NIPM) toward the reductive reaction of 4-nitrophenol (4NP) under various reaction conditions was evaluated. The Arrhenius and Eyring parameters for the catalytic reduction of 4NP were determined to explore the process of catalysis. A variety of nitroarenes were converted successfully into their corresponding aminoarenes with good to excellent yields in the presence of the Au–P(STY@NIPM) system using NaBH₄ as a reductant. The Au–P(STY@NIPM) system was found to be an efficient and recyclable catalyst with no significant loss in its catalytic efficiency.

A core–shell microgel system was synthesized and used as a micro-reactor for the synthesis of gold nanoparticles. The resulting hybrid system has the ability to catalyze the reduction of various nitroarenes in aqueous media.     

Au-based bimetallic catalysts: how the synergy between two metals affects their catalytic activity

Supported bimetallic nanoparticles are particularly attractive catalysts due to increased activity and stability compared to their monometallic counterparts. In this work, gold-based catalysts have been studied as catalysts for the selective base-free oxidation of glucose. TiO₂-supported Au–Pd and Au–Cu series prepared by the sol-immobilization and precipitation-reduction methods, respectively, showed a significant synergistic effect, particularly when the theoretical weight ratio of the two metals was close to 1 : 1 (with an actual experimental bulk Au/Pd molar ratio of ca. 0.8 and ca. 0.4 for Au/Cu) in both cases. XPS analysis showed that the presence of Au^δ+, Pd²⁺ and CuOH species played an important role in the base-free glucose oxidation.

Supported bimetallic nanoparticles are particularly attractive catalysts due to increased activity and stability compared to their monometallic counterparts.     

Ultrafine Pd nanoparticles loaded benzothiazole-linked covalent organic framework for efficient photocatalytic C–C cross-coupling reactions

We proposed a strategy that a benzothiazole-linked covalent organic framework (TTT-COF) was used as a substrate to prepare metal composite photocatalyst Pd NPs@TTT-COF. Firstly, benzothiazole linked TTT-COF exhibited superior chemical stability and photoresponse. Moreover, a finer particle size (2.01 nm) and more uniform distribution of Pd NPs were observed in Pd NPs@TTT-COF owing to the binding interaction between Pd NPs and S in benzothiazole groups. Pd NPs@TTT-COF exhibited superior efficiency and reusability in photocatalytic C–C cross-coupling reactions. Mechanism study suggested that photogenerated electrons and holes on TTT-COF played important roles in these reactions.

Benzothiazole-linked covalent organic framework with characteristic properties loaded Pd nanoparticles for photocatalytic C–C cross-coupling reactions.     

Size effect studies in catalysis: a simple surfactant-free synthesis of sub 3 nm Pd nanocatalysts supported on carbon

Supported Pd nanoparticles are prepared under ambient conditions via a surfactant-free synthesis. Pd(NO₃)₂ is reduced in the presence of a carbon support in alkaline methanol to obtain sub 3 nm nanoparticles. The preparation method is relevant to the study of size effects in catalytic reactions like ethanol electro-oxidation.

A simple surfactant-free synthesis of sub 3 nm carbon-supported Pd nanocatalysts is introduced to study size effects in catalysis.

A key achievement in the design of catalytic materials is to optimise the use of resources. This can be done by designing nanomaterials with high surface area due to their nanometre scale. A second achievement is to control and improve catalytic activity, stability and selectivity. These properties are also strongly influenced by size.^1–3 To investigate ‘size effects’ it is then important to develop synthesis routes that ensure well-defined particle size distribution, especially towards smaller sizes (1–10 nm).Metal nanoparticles are widely studied catalysts. In several wet chemical syntheses, NP size can be controlled using surfactants. These additives are, however, undesirable for many applications^4,5 since they can block active sites and impair the catalytic activity. They need to be removed in ‘activation’ steps which can negatively alter the physical and catalytic properties of the as-produced NPs. Surfactant-free syntheses are well suited to design catalysts with optimal catalytic activity⁶ but their widespread use is limited by a challenging size control.³Palladium (Pd) NPs are important catalysts for a range of chemical transformations like selective hydrogenation reactions and energy applications.^7–9 It is however challenging to obtain sub 3 nm Pd NPs, in particular without using surfactants.² Surfactant-free syntheses are nevertheless attracting a growing interest due to the need for catalysts with higher performances.^10–14Promising surfactant-free syntheses of Pd NPs were recently reported.^8,15 The NPs obtained in these approaches are in the size range of 1–2 nm and show enhanced activity for acetylene hydrogenation⁸ and dehydrogenation of formic acid.¹⁵ Enhanced properties are attributed to the absence of capping agents leading to readily active Pd NPs. The reported syntheses consist in mixing palladium acetate, Pd(OAc)₂, in methanol and the reduction of the metal complex to NPs occurs at room temperature. The synthesis is better controlled in anhydrous conditions to achieve a fast reaction in ca. 1 hour. Another drawback is that the synthesis must be stopped to avoid overgrowth of the particles. Therefore, a support material needs to be added after the synthesis has been initiated and no simple control over the NP size is achieved.^8,15In this communication a more straightforward surfactant-free synthesis leading to sub 3 nm carbon-supported Pd NPs in alkaline methanol at ambient conditions is presented. A solution of Pd(OAc)₂ in methanol undergoes a colour change from orange to dark, indicative of a reduction to metallic Pd, after ca. a day. However, only ca. 1 hour is needed with Pd(NO₃)₂, Fig. 1 and UV-vis data in Fig. S1.^† The fast reduction of the Pd(NO₃)₂ complex in non-anhydrous conditions is a first benefit of the synthesis presented as compared to previous approaches.Open in a separate windowFig. 1Pictures of 4 mM Pd metal complexes in methanol without or with a base (as indicated).For particle suspensions prepared with Pd(OAc)₂ or Pd(NO₃)₂ the NPs agglomerate and quickly sediment leading to large ‘flake-like’ materials. When the reduction of Pd(NO₃)₂ in methanol is performed in presence of a carbon support and after reduction the solution is centrifuged and washed in methanol, a clear supernatant is observed indicating that no significant amount of NPs are left in methanol. Transmission electron microscope (TEM) analysis confirms that NPs are formed and well-dispersed on the carbon support surface and no unsupported NPs are observed, Fig. 2a. Likely, the reduction of the NPs proceeds directly on the carbon support. However, the size of the NPs is in the range 5–25 nm, which is still a relatively large particle size and broad size distribution.Open in a separate windowFig. 2TEM micrographs of Pd NPs obtained by stirring 4 mM Pd(NO₃)₂ in methanol and a carbon support for 3 hours, (a) without NaOH and (b) with 20 mM NaOH. Size distribution histograms are reported in Fig. S4.^† The same samples after electrochemical treatments are characterised in (c) and (d) respectively. Size distribution histograms are reported in Fig. S7.^†Assuming a ‘nucleation and growth’ mechanism, the NPs should become larger over time.¹⁶ But the reaction is so fast that by stopping the reaction before completion, size control is not achieved and unreacted precious metal is observed, Fig. S2.^† To achieve a finer size control and more efficient use of the Pd resources, a base was added to the reaction mixture, e.g. NaOH.³ In alkaline media, the formation of Pd NPs is slower; it takes ca. 60 minutes to observe a dark colour for a 5 mM Pd(NO₃)₂ solution with a base/Pd molar ratio of 10 in absence of a support, Fig. 1.Also in alkaline methanol, the NPs agglomerate over time in absence of a support material. However, if the alkaline solution of Pd(NO₃)₂ is left to stir in presence of a carbon support the desired result is achieved, i.e. Pd NPs with a significantly smaller size and size distribution of ca. 2.5 ± 1.0 nm, Fig. 2b. The NPs homogeneously cover the carbon support and no unsupported NPs are observed by TEM suggesting that the NPs nucleate directly on the carbon surface. Furthermore, the supernatant after centrifugation is clear, indicating an efficient conversion of the Pd(NO₃)₂ complex to NPs, Fig. S3.^† Furthermore, there is no need for an extra reducing agent as in other approaches, for instance in alkaline aqueous solutions.⁹The benefits of surfactant-free syntheses of Pd NPs for achieving improved catalytic activity have been demonstrated for heterogeneous catalysis.^8,15 Surfactant-free syntheses are also well suited for electrochemical applications where fully accessible surfaces are required for fast and efficient electron transfer. Several reactions for energy conversion benefit from Pd NPs. An example is the electro-oxidation of alcohols,⁷ in particular ethanol¹⁷ (see also Table S1^†).Previous studies optimised the activity of Pd electrocatalysts by alloying,^18–20 by using different supports^17,21–23 or crystal structures.^24,25 Investigating NPs with a diameter less than 3 nm was challenging.^2,26,27 The surfactant-free synthesis method presented here allows to further study the size effect on Pd NPs supported on carbon (Pd/C) for electrocatalytic reactions.In Fig. 3, results for ethanol electro-oxidation in 1 M ethanol solution mixed with 1 M KOH aqueous electrolyte are reported based on cyclic voltammetry (CV) and chronoamperometry (CA) with Pd/C catalysts exhibiting 2 significantly different size distributions. The electrode preparation, the measurement procedure and the sequence of electrochemical treatments are detailed in the ESI.^† In order to highlight size effects, we compare geometric and Pd mass normalized currents (Fig. 3a and c) as well as the oxidation currents normalized to the Pd surface area (Fig. 3b).Open in a separate windowFig. 3Electrochemical characterisation of carbon supported Pd NPs with 5–25 nm (grey) and 2.5 nm (dark) size in 1 M KOH + 1 M ethanol aqueous electrolyte. (a) 2^nd CV before chronoamperometry (CA), (b) current normalised by the electrochemically active surface area of Pd, (c) CA recorded at 0.71 V vs. RHE after 50 cycles between 0.27 and 1.27 V.It is clearly seen that based on the geometric current density, the smaller Pd NPs exhibit significantly higher currents for ethanol oxidation than the larger NPs. To differentiate if this observation is a sole consequence of the different surface area, the electrochemically active surface area (ECSA) has been estimated based on “blank” CVs (without ethanol) recorded between 0.27 and 1.27 V vs. RHE in pure 1 M KOH aqueous electrolyte and integrating the area of the reduction peak at ca. 0.68 V, Fig. S5.^† As conversion factor, 424 μC cm⁻² was used.²⁸Using this method, the smaller NPs with a size around 2.5 nm exhibit an ECSA of 92 m² g⁻¹ whereas the larger NPs with a size in the range 5–25 nm exhibit an ECSA of 47 m² g⁻¹, consistent with a larger size. Normalising the ethanol electro-oxidation to these ECSA values instead of the geometric surface area, Fig. 3b, still indicates a size effect. It is clearly seen that the smaller Pd NPs exhibit higher surface specific ethanol oxidation currents, in particular at low electrode potentials. Furthermore, a clear difference in the peak ratios in the CVs is observed. The ratio in current density of the forward anodic peak (j_f, around 0.9 V) and the backward cathodic peak (j_b, around 0.7 V vs. SCE) is around one for the smaller NPs, whereas it is about 0.5 for the larger NPs. The forward scan corresponds to the oxidation of chemisorbed species from ethanol adsorption. The backward scan is related to the removal of carbonaceous species not fully oxidised in the forward scan. The higher j_f/j_b ratio therefore confirms that the smaller NPs are more active for ethanol electro-oxidation and less prone to poisoning, e.g. by formation of carbonaceous species that accumulate on the catalyst surface.^29,30 This observation is further supported by a chronoamperometry (CA) experiment, Fig. 3c, at 0.71 V performed after continuous cycling (50 cycles between 0.27 and 1.27 V at a scan rate of 50 mV s⁻¹). In the CA testing of the thus aged catalysts at 0.71 V, the ethanol oxidation current on the two catalysts starts at around the same values, however, its decay rate is significantly different. The Pd mass related oxidation currents for the smaller NPs are after 30 minutes almost twice as high (ca. 200 A g_Pd⁻¹) as for the larger ones (ca. 130 A g_Pd⁻¹), confirming that the small Pd NPs are less prone to poisoning. In particular a factor up to 4 in the Pd mass related ethanol oxidation currents after 1800 s of continuous operation is achieved compared to a recently characterised commercial Pd catalyst on carbon,²⁰ Table S1.^† Despite different testing procedure reported in the literature, it can be concluded from these investigations that the surfactant-free synthesis presented shows promising properties for electrocatalytic ethanol oxidation even after extended cycling.The extended cycling, however, has different consequences for the two catalysts. For the small (2.5 nm) NPs of the Pd/C catalyst, a massive particle loss, but only moderate particle growth is observed as highlighted in Fig. 2 (see also Fig. S6^†). TEM micrographs of the two Pd/C samples recorded before and after the complete testing (CVs and CAs, for details see Fig. S7^†) show that the catalyst with small Pd NPs exhibits a pronounced particle loss as well as a particle growth to ca. 6 nm probably due to sintering. By comparison, for the Pd/C catalyst with the large Pd NPs, no significant influence of the testing on particle size or particle density is apparent.     

Green synthesis of palladium nanoparticles using lentinan for catalytic activity and biological applications

The green synthesis of palladium nanoparticles (Pd NPs) for catalysis and biological applications has been gaining great interest. To replace complex plant extracts, lentinan (LNT) may be a good reducing and stabilizing agent. In this work, a simple and green method using LNT to reduce and stabilize palladium Pd NPs was verified. The resulting LNT stabilized palladium nanoparticles (Pd_n-LNT NPs) were characterized by UV-Vis spectroscopy, DLS, TEM, and XPS. The results indicated that Pd NPs inside of Pd_n-LNT NPs had a small size (2.35–3.32 nm). Pd_n-LNT NPs were stable in solution for 7 days. In addition, Pd_n-LNT NPs had higher catalytic activity towards the reduction of 4-nitrophenol than other catalysts. More importantly, Pd_n-LNT NPs had negligible cytotoxicity towards cells and showed good antioxidant activity. Taken together, the prepared Pd_n-LNT NPs have great potential bio-related applications.

Lentinan stabilized palladium nanoparticles had high catalytic activity, negligible cytotoxicity and good antioxidant activity.     

Peptide-directed Pd-decorated Au and PdAu nanocatalysts for degradation of nitrite in water

In this work, a palladium binding peptide, Pd4, has been used for the synthesis of catalytically active palladium-decorated gold (Pd-on-Au) nanoparticles (NPs) and palladium–gold (Pd_xAu_100−x) alloy NPs exhibiting high nitrite degradation efficiency. Pd-on-Au NPs with 20% to 300% surface coverage (sc%) of Au showed catalytic activity commensurate with sc%. Additionally, the catalytic activity of Pd_xAu_100−x alloy NPs varied based on palladium composition (x = 6–59). The maximum nitrite removal efficiency of Pd-on-Au and Pd_xAu_100−x alloy NPs was obtained at sc 100% and x = 59, respectively. The synthesized peptide-directed Pd-on-Au catalysts showed an increase in nitrite reduction three and a half times better than monometallic Pd and two and a half times better than Pd_xAu_100−x NPs under comparable conditions. Furthermore, peptide-directed NPs showed high activity after five reuse cycles. Pd-on-Au NPs with more available activated palladium atoms showed high selectivity (98%) toward nitrogen gas production over ammonia.

In this work, a palladium binding peptide, Pd4, has been used for the synthesis of catalytically active palladium-decorated gold (Pd-on-Au) nanoparticles (NPs) and palladium–gold (Pd_xAu_100−x) alloy NPs exhibiting high nitrite degradation efficiency.     

Novel Au nanorod/Cu2O composite nanoparticles for a high-performance supercapacitor

Metal–oxide nanomaterials have attracted great interest in recent years due to their novel characteristics such as surface effect and quantum confinement. A fascinating Au nanorod (NR)/cuprous oxide core–shell composite (AuNR/Cu₂O) was directly synthesized using a moderate one-pot facile green redox method and further utilized for energy storage applications in a supercapacitor. The synthesis mechanism is based on the use of reducing agents to form the core shell. The resultant composite was deposited on the surface of nickel foam as a result of redox reactions between Au and Cu via a hydrothermal method. AuNR/Cu₂O composite nanoparticles (NPs) were characterized using various spectroscopic and microscopic techniques, including UV-vis and X-ray photoelectron spectroscopies, Brunauer–Emmett–Teller surface area analysis, X-ray diffractometry, and transmission electron microscopy. The AuNR/Cu₂O composite NPs grow via the depositing of a 20–50 nm Cu₂O shell on an AuNR core with dimensions of 5–20 nm in width and 40–70 nm in length. The as-synthesized AuNR/Cu₂O composite NPs were effectively used as electrode materials in a supercapacitor, and their electrochemical performance was determined by cyclic voltammetry, galvanostatic charge–discharge measurements, and electrochemical impedance spectroscopy in 2 M KOH aqueous solution as an electrolyte. The composite NPs showed excellent average specific capacitance of 235 F g⁻¹ at a current density of 2 A g⁻¹ and durable cycling stability (96% even after 10 000 cycles). The higher efficiency of the AuNR/Cu₂O composite NPs can be attributed to the presence of AuNR in the core. The AuNR/Cu₂O composite NPs exhibit a high surface area and high electrical conductivity, which consequently result in their excellent specific capacitance and outstanding rate as an all-solid-state supercapacitor electrode.

Synthesis of an Au/Cu₂O composite and its supercapacitor behavior.     

Facile ZnO-based nanomaterial and its fabrication as a supercapacitor electrode: synthesis,characterization and electrochemical studies

In recent times, tremendous efforts have been devoted to the efficient and cost-effective advancements of electrochemically active metal oxide nanomaterials. Here, we have synthesized a facile nanomaterial of ZnO@PdO/Pd by employing extracted fuel from E. cognata leaves following a hydrothermal route. The phyto-fueled ZnO@PdO/Pd nanomaterial was fabricated into a supercapacitor electrode and was scrutinized by galvanostatic charge–discharge, electrochemical impedance spectroscopy and cyclic voltammetry to evaluate its energy storage potential, and transport of electrons and conductivity. Substantial specific capacitance i.e., 178 F g⁻¹ was obtained in the current study in aKOH electrolyte solution. A specific energy density of 3.7 W h Kg⁻¹ was measured using the charge–discharge data. A high power density of 3718 W Kg⁻¹ was observed for the ZnO@PdO/Pd electrode. Furthermore, the observed low internal resistance of 0.4 Ω suggested effective electron- and ion diffusion. Thus, the superb electrochemical behavior of the ZnO@PdO/Pd nanocomposite was exposed, as verified by the significant redox behavior shown by cyclic voltammetry and galvanostatic charge–discharge.

In recent times, tremendous efforts have been devoted to the efficient and cost-effective advancements of electrochemically active metal oxide nanomaterials.     

Surface functionality density regulated in situ reduction of nanosilver on hierarchial wrinkled mesoporous silica nanoparticles and their antibacterial activity

Hierarchical wrinkled mesoporous silica nanoparticles (WMS NPs) bedecked with diverse functionality density of amino groups (WMSs-N2, WMSs-NN and WMSs-NNN) were first synthesized via typical Sol–Gel method, and then utilized for the in situ reduction of nanosilver with sodium borohydride. Elegantly distributed Ag NPs (ca. 7–10 nm, 3–5 nm) on WMSs-N2 and WMSs-NN without any agglomeration were obtained respectively, while Ag NPs (ca. 50 nm) dispersed on WMSs-NNN were obviously larger and slightly agglomerated. Compared to pure Ag NPs, all the obtained Ag@WMSs composites were durable and displayed much better antibacterial performance, with a minimal inhibitory concentration of 12–80 mg L⁻¹ and a minimal bactericidal concentration of 24–108 mg L⁻¹, respectively. Moreover, it was found that the functionality density of amino groups and the specific surface area of WMSs played a crucial role for the antibacterial performance of the obtained nanocomposites. Because WMSs-NN had higher specific surface area and surface amino density than WMSs-N2, the size and dispersion of Ag NPs on WMSs-NN were smaller and superior to those of Ag NPs on WMSs-N2, respectively. Accordingly, Ag@WMSs-NN displayed a better antibacterial capacity than Ag@WMSs-N2. As for Ag@WMSs-NNN, owing to the high loading content of Ag NPs, they exhibited the best antibacterial and bactericidal properties.

Nanosilver with diverse particle size was attached onto hierarchical WMS, and the resulted samples showed excellent antibacterial properties.     

Room-temperature coalescence of Pd nanoparticles with sacrificial templates and sintering agents,and their catalytic activities in the Suzuki coupling reaction

Porous metal structures are very useful for heterogeneous catalysts in organic syntheses. This study reports a novel method to fabricate porous Pd structures by room-temperature (RT) coalescence of Pd nanoparticles (Pd NPs). First, oleylamine-capped Pd NPs were synthesized, and then Pd NP pastes were fabricated by mixing with tri-n-octylphosphine oxide as a sacrificial template. Finally, the Pd NP paste was dipped into methanol containing a sintering agent. When KOH was used as the sintering agent, porous Pd structures could be successfully obtained at RT. The catalytic activities of porous Pd structures were investigated in the Suzuki coupling reaction and they increased with the increase of the KOH concentration in the sintering process. These results indicate that pre-activation of porous Pd structures by KOH increased the catalytic activities.

Porous Pd structures with high catalytic performance were prepared by dipping a tri-n-octylphosphine oxide (TOPO) paste of Pd nanoparticles (Pd NPs) on a glass substrate into a KOH methanol solution at room-temperature.      

N,N-Dimethylformamide-stabilized palladium nanoclusters as a catalyst for Larock indole synthesis

We show that N,N-dimethylformamide-stabilized Pd nanoclusters (NCs) have high catalytic activity in the reaction of substituted 2-iodoanilines with alkynes to give 2,3-disubstituted indoles. This indole synthesis does not require phosphine ligands and proceeds with low Pd catalyst loadings. The Pd NCs were separated from the mixture after the reaction, and recycled at least three times. Transmission electron microscopy images showed that the Pd particle size before the reaction was 1.5–2.5 nm. The particle size after the reaction was 2–3 nm. X-ray photoelectron spectroscopy showed that the binding energy of the Pd NCs before the reaction was 335.0 eV.

Pd NCs serve recyclable and highly active catalyst to indole synthesis.     

Ecofriendly densitometric RP-HPTLC method for determination of rivaroxaban in nanoparticle formulations using green solvents

A literature survey revealed no suitable “reversed phase-high performance thin layer chromatography (RP-HPTLC)” method for the analysis of rivaroxaban in nanoparticle (NP) formulations. Therefore, a novel rapid, simple, economical and environment friendly RP-HPTLC method has been established for the quantification of rivaroxaban in NP formulations and commercial tablets. RP-HPTLC analysis of rivaroxaban was performed using “RP-18 silica gel 60 F254S HPTLC plates”. The binary mixture of green solvents ethanol : water (7 : 3 v/v) was utilized as the mobile phase. The quantification of rivaroxaban was carried out in densitometric mode at λ_max = 253 nm. Rivaroxaban peaks from NP formulations was confirmed by comparing its single spot at R_f = 0.71 ± 0.02 with that of the standard. The proposed RP-HPTLC method was found to be linear in the range of 50–600 ng per band with R² = 0.9994. The equation for linear regression analysis was obtained as Y = 13.28x + 1189.4. The proposed RP-HPTLC technique was validated for “precision, accuracy, robustness and sensitivity”. The accuracy of the method was obtained as 97.97–99.67%. The % RSD in repeatability and intermediate precision was recorded as 0.46–0.64 and 0.48–0.86%, respectively. The LOD and LOQ for rivaroxaban were obtained as 18.45 and 55.35 ng per spot, respectively. The % content of rivaroxaban in marketed tablets and NPs was recorded as 99.20 and 98.08%, respectively. The proposed RP-HPTLC technique could be successfully applied for the pharmaceutical assay of rivaroxaban in NPs, marketed tablets and related formulations.

A literature survey revealed no suitable “reversed phase-high performance thin layer chromatography (RP-HPTLC)” method for the analysis of rivaroxaban in nanoparticle (NP) formulations.