Pd Sites Research Articles

Atomically Dispersed CrOX on Pd Metallene for CO-Resistant Methanol Oxidation.

The effective design and construction of high-performance methanol oxidation reaction (MOR) electrocatalysts are significant for the development of direct methanol fuel cells. But the active sites of the MOR electrocatalysts are susceptible to being poisoned by CO, resulting in poor durability. Herein, we report an atomically dispersed CrOX species anchored on Pd metallene through bridging O atoms. This catalyst shows an outstanding MOR performance with 7 times higher mass activity and 100 mV lower CO electrooxidation potential than commercial Pd/C. The results of operando electrochemical Fourier transform infrared spectroscopy demonstrate the rapid removal of CO* on CrOX-Pd metallene. Theoretical calculations reveal that atomically dispersed CrOX can lower the adsorption energy of CO* on Pd sites and enhance that of OH* through the formation of a hydrogen bond, decreasing the formation energy of COOH*. This work provides a new strategy for improving MOR performance via atomically engineering oxide/metal interfaces.

Patterns of Failure, Volume of Disease Progression, and Subsequent Ablative Management in Locally Advanced Non-Small Cell Lung Cancer (LA-NSCLC) Treated with Definitive Chemoradiation and Consolidation Immune Checkpoint Inhibitors (ICI)

For patients (pts) with LA-NSCLC treated with chemoradiation and consolidation ICI (CRT+ICI), the patterns of failure (POF) and volume of disease progression (PD) are not well characterized. The primary objective of this study was to classify POFs, the frequency of low volume relapse (LVR), and identify pts eligible for further ablative therapy. We retrospectively identified pts with unresectable stage III NSCLC treated with CRT+ICI between October 2017 and December 2021 at a single institution. Site of first failure was classified as locoregional (LRF), distant (DF), or synchronous LRF + DF. Any LRF was subclassified as in field (IFF; PD within 90% isodose line), marginal (MF; within 50% isodose line) or out of field (OOF; outside of 50% isodose line). LVR was defined as < 3 discrete sites of PD in any number or location of organs. Pts with distant LVR were considered to have oligometastatic relapse. Ablative candidates were defined as pts with < 3 discrete sites of PD amenable to further RT or surgery. Cumulative incidence of PD was calculated with death as a competing risk. Progression free survival (PFS) and overall survival (OS) were calculated from the end of RT and assessed via Kaplan Meier. Multivariable Cox modeling was used to assess correlation of pt characteristics and time-to-event outcomes. Logistic regression was used to predict variables associated with LVR. A total of 229 pts received CRT+ICI. Median follow up was 39 months and 119 pts experienced PD. Median PFS and OS were 18.4 and 34.5 months, respectively. Of pts with PD, 71 (60%) had DF, 28 (24%) had LRF+DF, and 20 (17%) had LRF. Of pts with any LRF, 28 (57%) had IFF, 10 (21%) had MF, and 10 (21%) had OOF. Estimated 1-year cumulative incidence of LRF, DF, and LRF+DF were 9.3% (95% CI 4.5-16), 39% (95% CI 31-48), and 19% (95% CI 12-27), respectively. A total of 63 (53%) pts had LVR. In pts with LVR, 19 (30%) had isolated thoracic relapse and 44 (69%) had oligometastatic relapse. Most oligometastatic disease was intracranial (22 metastases, 44%). Pts with LVR had a longer median OS vs pts with high volume relapse (37.4 vs 15.2 months, p<0.001). At time of PD, 56 (47%) pts were candidates for further ablative therapies. Subsequent anticancer therapies were local therapy alone (35%), local and systemic therapy (16%), systemic therapy alone (36%), or no therapy (13%). On multivariable analysis, LVR (HR 0.39; 95% CI 0.21-0.73, p = 0.003) and longer receipt of ICI (HR 0.96; 95% CI 0.95-0.98; p<0.001) were associated with improved survival while squamous histology (HR 2.26; 95% CI 1.18-4.32; p = 0.039) was associated with worse survival. Longer receipt of ICI was the only variable predictive for the development of LVR (OR 1.03; 95% CI 1.01-1.05; p = 0.004). This is the largest real-world series reporting POF after CRT+ICI for stage III NSCLC. Approximately half of pts experience LVR and are candidates for further ablative therapy. Further data are needed to define optimal treatment strategies for pts with LVR after CRT+ICI.

Patterns of Failure in Metastatic NSCLC Treated With First Line Pembrolizumab and Use of Local Therapy in Patients With Oligoprogression

IntroductionThe patterns of failure (POF) for metastatic non–small-cell lung cancer (mNSCLC) treated with immunotherapy are not well established. MethodsWe conducted a retrospective cohort study of mNSCLC that received first-line pembrolizumab with or without chemotherapy at a single academic center from 2015 to 2021. We defined POF with 2 classifications: 1) local, regional, or distant failure, or 2) failure in existing lesions, new lesions, or a combination. Oligoprogression was defined as disease progression (PD) in ≤3 sites of failure. Overall survival (OS) was measured via Kaplan-Meier and modelled with Cox regression. ResultsOf 298 patients identified, 198 had PD. Using POF classification 1, most failures were distant (43.9%) or a combination of locoregional and distant (34.4%). For POF classification 2, failures occurred in a combination of new and existing lesions (45.0%), existing lesions alone (33.3%), or in new lesions only (21.7%). Oligoprogression occurred in 39.9% (n = 79) cases. Median OS was higher in the following: PD in existing lesions vs. new or new + existing lesions (28.7 vs. 20.2 vs. 13.9 months, P < .001) and oligoprogression vs. polyprogression (35.1 vs. 12.2 months, P < .001). In oligoprogression, median OS was better for those who received radiation to all sites of PD (62.2 months) than for those who changed systemic therapy (22.9 months, P = .007). On multivariable analysis, radiation for oligoprogression (HR 0.35, 95% CI: 0.20-0.62, P < .001) was associated with improved OS. ConclusionsIn mNSCLC treated with pembrolizumab, oligoprogression is relatively common. Randomized data are needed to define the benefits of radiation in oligoprogressive mNSCLC.

Atomically dispersed Pd on defective BN nanosheets for nitrite electroreduction to ammonia

Electrocatalytic NO2− reduction to NH3 (NO2RR) offers a prospective strategy to concurrently achieve polluted NO2− removal and effective NH3 electrosynthesis. In this work, we report atomically dispersed Pd on defective BN nanosheets (Pd1/BN) as an efficient catalyst for the NO2RR, achieving the highest NH3-Faradaic efficiency of 91.7% with an NH3 yield rate of 347.1 μmol h−1 cm−2 at −0.6 V vs. RHE, superior to those of most previously reported electrocatalysts. Theoretical computations reveal the isolated Pd sites as catalytic centers to selectively adsorb NO2− and accelerate NO2−-to-NH3 hydrogenation process with a minimized reaction barrier, eventually contributing to the considerably enhanced NO2RR selectivity and activity of Pd1/BN.

Partial hydrogenation of anisole to cyclohexanone in water medium catalyzed by atomically dispersed Pd anchored in the micropores of zeolite

Cyclohexanone is an important raw material for manufacturing nylon and other chemicals. The sustainable conversion of biomass derived molecules to cyclohexanone is desired but still challenging. Herein, a palladium single atom catalyst anchored in the micropores of zeolite (namely Pd1/ZSM-5) is designed and exhibits remarkable catalytic activity in transforming anisole to cyclohexanone in water medium (H2O), without using of organic solvent or halogen promoter. The selectivity to cyclohexanone is 91.2% and the turnover rate (TOR) is 400.8 h−1 at 453 K. The Pd sites, acid sites, and microporous confinement environment of zeolite cooperate to promote the partial hydrogenation to cyclohexanone, and inhibit further hydrogenation as the side reaction. H2O not only acts as the solvent, but also participates significantly in the partial hydrogenation. Moreover, as revealed by isotope labelled experiments (D2O and H218O), the water participated hydrogenolysis and the consequent partial hydrogenation mechanism is proposed.

Atomic Layers of B2 CuPd on Cu Nanocubes as Catalysts for Selective Hydrogenation.

The search for highly active and selective catalysts with high precious metal atom utilization efficiency has attracted increasing interest in both the fundamental synthesis of materials and important industrial reactions. Here, we report the synthesis of Pd-Cu nanocubes with a Cu core and an ordered B2 intermetallic CuPd shell with controllable atomic layers on the surface (denoted as Cu/B2 CuPd), which can efficiently and robustly catalyze the selective hydrogenation of acetylene (C2H2) to ethylene (C2H4) under mild conditions. The optimized Cu/B2 CuPd with a Pd loading of 9.5 at. % exhibited outstanding performance in the C2H2 semi-hydrogenation with 100% C2H2 conversion and 95.2% C2H4 selectivity at 90 °C. We attributed this outstanding performance to the core/shell structure with a high surface density of active Pd sites isolated by Cu in the B2 intermetallic matrix, representing a structural motif of single-atom alloys (SAAs) on the surface. The combined experimental and computational studies further revealed that the electronic states of Pd and Cu are modulated by SAAs from the synergistic effect between Pd and Cu, leading to enhanced performance compared with pristine Pd and Cu catalysts. This study provides a new synthetic methodology for making single-atom catalysts with high precious metal atom utilization efficiency, enabling simultaneous tuning of both geometric and electronic structures of Pd active sites for enhanced catalysis.

(Invited) Recent Development of Electrochemical Nitrate Reduction

Understanding the complexities of nitrogen cycle is critical because when the cycle is not in balance, excess reduced and oxidized nitrogen compounds could result in harmful impacts to life. Electrocatalytic conversion of waste nitrate (NO3 -) to benign dinitrogen (N2) and ammonia (NH3) fuel is an appealing strategy that may easily integrate with renewable energy. The process does not require chemical addition and thus requires operating costs lower than thermal routes. Nearly all nitrogen-based fertilizers rely on ammonia as a feedstock, and thus the demand for this chemical is heavily dependent on the global population and food demand. Over the next three decades, the global population will continue to dictate the market size and value for ammonia, which consequently will have a significant impact on our energy infrastructure. While electrochemical nitrogen reduction reaction (NRR) requires multiple proton and electron transfer process, ammonia production from nitrate reduction (NO3RR) is catalytic easier than NRR because the adsorbed/activated ion reactants (nitrate and nitrite) have an advantage of a lower dissociation energy for the N−O and N=O bonds (204 and 607 kJ mol-1) than that of N≡N bond (941 kJ mol-1). The synergistic effect between Cu and Pd has shown a high nitrate conversion yield and nitrogen selectivity. Engineering the Pd and Cu sites is critical but examination of the use of secondary metals in shape-controlled nanoparticle and atomic reconstruction are rare.Here, we controlled Cu surface coverage on Pd nanocube nanoparticle to steer the selectivity between nitrogen and ammonia. In addition, the engineered the atomic structure of Pd and Cu nanoparticles showed high nitrate conversion yield, excellent dinitrogen selectivity, and outstanding cyclic stability. This study provides insights into the rational design of NO3RR electrocatalyst for efficiently transforming nitrate into nitrogen and ammonia.

Selectivity of Diphenylacetylene Semi-Hydrogenation on Pt1Pd99/C Using PEM Electrolyzer

Introduction For carbon neutralization, organic synthesis should be electrified with renewable electricity besides energy synthesis. The Lindlar catalyst has been a common means for stereoselective Z-alkene synthesis from alkynes, which need hydrogen as a reactant and lead as an additive on the catalyst and has substrate limitation. By contrast, a proton exchange membrane (PEM) reactor is one of the alternative ways of Z-alkene formation, enabling the synthesis under mild conditions without lead use and substrate restriction, using renewable electricity and water instead of hydrogen.The previous research figured Pt1Pd99/C (at%) catalyst had the highest selectivity among various compositions of Pt-Pd catalysts for semi-hydrogenation of diphenylacetylene (DPA) to cis-stilbene. Pd sites selectively adsorb the DPA, while even a small amount of Pt sites quickly reduces protons to Had, which hydrogenate the DPA. The Pt1Pd99 catalyst indicated the best synergy effect of Pt and Pd.1,2) For an optimal PEM electrolyzer on a larger scale, its flow field structure and dimension must be decided with the selected electrocatalyst property. Therefore, a better understanding of the electrocatalyst activity is essential.In this study, we have investigated the relationship among catalyst loading, reactant flow rate, overall current density, and selectivity to understand the nature of the Pt1Pd99 catalyst. Experimental DSE® (De Nora Permelec Ltd) was used for the oxygen evolution as the anode and Nafion® 117 (DuPont) as the PEM, respectively. Carbon paper (39BB, SGL Carbon), loaded with 0.2–1.6 mg cm-2-precious metal of Pt1Pd99 (ISHIFUKU Metal Industry Co., Ltd.) and cut into 3.3 cm × 3.5 cm, was employed as the cathode. The cathode was hot-pressed on the PEM at 120 ℃, 3 MPa, for 3 min to make a membrane cathode assembly. In the anode compartments, 1 M (= mol dm-3) sulfuric acid circulated, and 1 M cyclohexane solution of DPA in the cathode compartments.As electrochemical measurements, electrochemical impedance spectroscopy at 100 kHz–0.1 Hz with an amplitude of 10 mV, chronoamperometry at 1.3–2.0 V for catalyst loading dependency experiments, chronopotentiometry at 9–36 mA cm-2 for flow rate dependency were conducted. The concentrations of cis-Stilbene and dibenzyl in electrolytes were quantified with high-performance liquid chromatography (HPLC) after collection during the last 2 min out of 5 min of electrolysis at 60 ℃. Each partial current was derived by the multiplications of each concentration, the stoichiometric coefficient of electrons (2 for cis-stilbene and 4 for dibenzyl), the Faraday constant, and the flow rate. Results and Discussion Figure 1 shows anode and cathode potentials as functions of current density. The anode potential was stable around 1.6 V vs. RHE, while the cathode potential appeared to get higher with more catalyst loading, considering the variation of the anode potential.Figures 2 and 3 show the current efficiencies of cis-stilbene and dibenzyl as functions of cathode potential. The current efficiency of cis-stilbene decreased with the cathode potential increase, while that of dibenzyl increased and peaked at approximately -0.2 V vs. RHE, where cis-stilbene current efficiency steeply dropped.Figures 4 and 5 show both current efficiencies at various cathode potentials as functions of the catalyst loading. The current efficiency of cis-stilbene decreased with the catalyst loading increase, while that of dibenzyl increased. Both absolute values of the slopes of Figs. 4 and 5 are the highest at -0.2 V vs. RHE, where over-hydrogenation to dibenzyl overwhelmed cis-stilbene formation. Since at a more negative potential, reducing current was almost consumed by hydrogen evolution, the effect of the catalyst layer thickness on the selectivity was maximum here.The current efficiencies of cis-stilbene and dibenzyl and the selectivity at various flow rates are shown in Figure 6. As the flow rate rose, the current efficiency and selectivity of cis-stilbene increased.With a thin catalyst layer, the substrate quickly moved away from the reaction field, and the same happened at a high flow rate. Therefore, produced cis-stilbene is less over-hydrogenated, and the selectivity increased.According to these results, since the reaction of cis-stilbene formation is quick, speedy product elimination would be the key to further selectivity improvement. Acknowledgment This work was financially supported by CREST (JST Grant 18070940). The authors are grateful to ISHIFUKU Metal Industry Co., Ltd. for providing the cathode catalysts. References 1) S, Nogami, K. Nagasawa, A. Fukazawa, K. Tanaka, S. Mitsushima, M. Atobe, J. Electrochem. Soc., 167, 155506 (2020).2) S. Nogami, N. Shida, S. Iguchi, K. Nagasawa, H. Inoue, I. Yamanaka, S. Mitsushima, M. Atobe, ACS Catal., 12, 5430 (2022). Figure 1

Dioxin-Linked Covalent Organic Framework-Supported Palladium Complex for Rapid Room-Temperature Suzuki–Miyaura Coupling Reaction

Covalent organic framework (COF)-supported palladium catalysts have garnered enormous attention for cross-coupling reactions. However, the limited linkage types in COF hosts and their suboptimal catalytic performance have hindered their widespread implementation. Herein, we present the first study immobilizing palladium acetate onto a dioxin-linked COF (Pd/COF-318) through a facile solution impregnation approach. By virtue of its permanent porosity, accessible Pd sites arranged in periodic skeletons, and framework robustness, the resultant Pd/COF-318 exhibits exceptionally high activity and broad substrate scope for the Suzuki–Miyaura coupling reaction between aryl bromides and arylboronic acids at room temperature within an hour, rendering it among the most effective Pd/COF catalysts for Suzuki–Miyaura coupling reactions to date. Moreover, Pd/COF-318 demonstrates excellent recyclability, retaining high activity over five cycles without significant deactivation. The leaching test confirms the heterogeneity of the catalyst. This work uncovers the vast potential of dioxin-linked COFs as catalyst supports for highly active, selective, and durable organometallic catalysis.

Tensile-Strained Holey Pd Metallene toward Efficient and Stable Electrocatalysis.

Noble metal-based metallenes are attracting intensive attention in energy catalysis, but it is still very challenging to precisely control the surface structures of metallenes for higher catalytic properties on account of their intrinsic thermodynamic instability. Herein, the synthesis of tensile-strained holey Pd metallene by oxidative etching is reported using hydrogen peroxide, which exhibits highly enhanced catalytic activity and stability in comparison with normal Pd metallene toward both oxygen reduction reaction and formic acid oxidation. The pre-prepared Pd metallene functions as a catalyst to decompose hydrogen peroxide, and the Pd atoms in amorphous regions of Pd metallene are preferentially removed by the introduced hydrogen peroxide during the etching process. The greatly enhanced ORR activity is mainly determined by the strong electrostatic repulsion between intermediate O* and the dopant O, which balances the adsorption strength of O* on Pd sites, ultimately endowing a weakened adsorption energy of O* on TH-Pd metallene. This work creates a facile and economical strategy to precisely shape metallene-based nanoarchitectures with broad applications for energy systems and sensing devices.

Mild Methane Electrochemical Oxidation Boosted via Plasma Pre-Activation.

Obtaining partial methane oxidation reaction (MOR) with various oxygenates via a mild electrochemical method is practically difficult because of activation of stable C─H bond and consequent reaction pathway regulation. Here, a real-time tandem MOR with cascaded plasma and electrocatalysis to activate and convert the methane (CH4 ) synergistically is reported for the first time. Boosted CH4 conversion is demonstrated toward value-added products including, alcohols, carboxylates, and ketone via use of commercial Pd-based electrocatalysts. Compared with hash industrial processes, a mild condition, that is, anode potential < 1.0V versus RHE (reversible hydrogen electrode) is used that mitigates overoxidation of oxygenates and obviates competing reaction(s). One evidence that Pd(II) sites and surface adsorbed hydroxyls are important in facilitating activated-CH4 species conversion, and establish a reaction mechanism for conversion(s) that involves coupling reactions between adsorbed hydroxyls, carbon monoxide and C1 /C2 alkyls. One conclude that pre-activation is important in boosting electrochemical partial MOR under mild conditions and will be of benefit in the development of sustainable CH4 conversion technology.

Metal-Acid Interface Engineering in Pd-WOx Bifunctional Catalysts for the Hydroalkylation Tandem Reaction of Benzene.

The hydroalkylation tandem reaction of benzene to cyclohexylbenzene (CHB) provides an atom economy route for conversion and utilization of benzene; yet, it presents significant challenges in activity and selectivity control. In this work, we report a metal-support synergistic catalyst prepared via calcination of W-precursor-containing montmorillonite (MMT) followed by Pd loading (denoted as Pd-mWOx/MMT, m = 5, 15, and 25 wt %), which shows excellent catalytic performance for hydroalkylation of benzene. A combination study (X-ray diffraction (XRD), hydrogen-temperature programmed reduction (H2-TPR), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), UV-vis, Raman, and density functional theory (DFT) calculations) confirms the formation of interfacial sites Pd-(WOx)-H, whose concentration is dependent on the interaction between Pd and WOx. The optimized catalyst (Pd-15WOx/MMT) exhibits a CHB yield of up to 45.1% under a relatively low hydrogen pressure, which stands at the highest level among state-of-the-art catalysts. Investigations on the structure-property correlation based on in situ FT-IR and control experiments further verify that the Pd-(WOx)-H structure serves as the dual-active site: the interfacial Pd site accelerates benzene hydrogenation to cyclohexene (CHE), while the interfacial Bronsted (B) acid site in Pd-(WOx)-H boosts the alkylation of benzene and CHE to CHB. This study offers a new strategy for the design and preparation of metal-acid bifunctional catalysts, which shows potential application in the hydroalkylation reaction of benzene.

Insight into the Effects of Pd Single-atom Particles in the Activation of the Carbon-Chloride Bond

Palladium (Pd) shows high activity in a variety of catalysis reactions that refer to the activation of the carbon-halogenation bond, and single-atom Pd catalysts have received significant attention as new technology. Nevertheless, there is a huge knowledge gap regarding which Pd sites could form highly reactive centers. It is unclear whether single-atom Pd sites are active in this process or not. In this study, we synthesized Pd/TiO2 nanosheets with Pd loadings of 1%, 5%, and 10% and designed single atom Pd sites and Pd nanoparticles on similar substrates. A scanning transmission electron microscope was used to characterize the synthesized Pd catalysts. As a catalyst, Pd/TiO2 featuring Pd NPs showed high activity in activating the carbon-halogen bond in the activation of carbon-chloride bond, whereas Pd/TiO2 with single Pd atoms showed very low activity in this pros. Accordingly, our results demonstrate that the activation of carbon-halogen bonds cannot be catalyzed by the single-atom Pd sites and emphasize the significance of the ensemble effect in determining the activity of Pd sites.

Electrochemical NO3- Reduction Catalyzed by Atomically Precise Ag30Pd4 Bimetallic Nanocluster: Synergistic Catalysis or Tandem Catalysis?

Electrochemically converting NO3- compounds into ammonia represents a sustainable route to remove industrial pollutants in wastewater and produce valuable chemicals. Bimetallic nanomaterials usually exhibit better catalytic performance than the monometallic counterparts, yet unveiling the reaction mechanism is extremely challenging. Herein, we report an atomically precise [Ag30Pd4 (C6H9)26](BPh4)2 (Ag30Pd4) nanocluster as a model catalyst toward the electrochemical NO3- reduction reaction (eNO3-RR) to elucidate the different role of the Ag and Pd site and unveil the comprehensive catalytic mechanism. Ag30Pd4 is the homoleptic alkynyl-protected superatom with 2 free electrons, and it has a Ag30Pd4 metal core where 4 Pd atoms are located at the subcenter of the metal core. Furthermore, Ag30Pd4 exhibits excellent performance toward eNO3-RR and robust stability for prolonged operation, and it can achieve the highest Faradaic efficiency of NH3 over 90%. In situ Fourier-transform infrared study revealed that a Ag site plays a more critical role in converting NO3- into NO2-, while the Pd site makes a major contribution to catalyze NO2- into NH3. The bimetallic nanocluster adopts a tandem catalytic mechanism rather than a synergistic catalytic effect in eNO3-RR. Such finding was further confirmed by density functional theory calculations, as they disclosed that Ag is the most preferable binding site for NO3-, which then binds a water molecule to release NO2-. Subsequently, NO2- can transfer to the vicinal exposed Pd site to promote NH3 formation.

SERS for Probing Highly Reactive Pd Sites with Elongated Pd–Pd Bonds on the Au Surface

SERS for Probing Highly Reactive Pd Sites with Elongated Pd–Pd Bonds on the Au Surface

Pd‐Enriched‐Core/Pt‐Enriched‐Shell High‐Entropy Alloy with Face‐Centred Cubic Structure for C1 and C2 Alcohol Oxidation

AbstractHigh‐entropy alloy nanoparticles (HEA NPs) have aroused great interest globally with their unique electrochemical, catalytic, and mechanical properties, as well as diverse activity and multielement tunability for multi‐step reactions. Herein, a facile low‐temperature synthesis method at atmospheric pressure is employed to synthesize Pd‐enriched‐HEA‐core and Pt‐enriched‐HEA‐shell NPs with a single phase of face‐centred cubic structure. Interestingly, the lattice of both Pd‐enriched‐HEA‐core and Pt‐enriched‐HEA‐shell enlarge during the formation process of HEA, with tensile strains included in the core and shell of HEA. The as‐obtained PdAgSn/PtBi HEA NPs show excellent electrocatalytic activity and durability for methanol oxidation reaction (MOR) and ethanol oxidation reaction (EOR). The specific (mass) activity of PdAgSn/PtBi HEA NPs for MOR is 4.7 mA cm−2 (2874 mA mg(Pd+Pt)−1), about 1.7 (5.9) and 1.5 (4.8) times higher than that of commercial Pd/C and Pt/C catalysts, respectively. Additional to high‐entropy effect, Pt sites and Pd sites on the interface of the HEA act synergistically to facilitate the multi‐step process towards EOR. This study offers a promising way to find a feasible route for scalable HEA manufacturing with promising applications.

Pd-Enriched-Core/Pt-Enriched-Shell High-Entropy Alloys Nanoparticles with a Face-Centred Cubic Structure for C1 and C2 Alcohol Oxidation.

Recently, high-entropy alloy nanoparticles (HEA NPs) have aroused great interest globally with their unique electrochemical, catalytic, and mechanical properties, as well as diverse activity and multielement tunability for multi-step reactions. Herein, a facile low-temperature synthesis method at atmospheric pressure is employed to synthesize Pd-enriched-HEA-core and Pt-enriched-HEA-shell NPs with a single phase of face-centred cubic structure for promoting the oxidation of C1 and C2 alcohols. Interestingly, the lattice of both Pd-enriched-HEA-core and Pt-enriched-HEA-shell enlarge during the formation process of HEA, with tensile strains included in the core and shell of HEA. Strikingly, the as-made PdAgSn/PtBi HEA NPs show excellent electrocatalytic activity and durability for methanol oxidation reaction (MOR) and ethanol oxidation reaction (EOR). Especially, the specific (mass) activity of PdAgSn/PtBi HEA NPs for MOR is 4.7 mA/cm2 (2874 mA mg(Pd+Pt)-1), about 1.7 (5.9) and 1.5 (4.8) times higher than that of commercial Pd/C and Pt/C catalysts, respectively. Combined with high-entropy effect, Pt sites and Pd sites on the interface of the HEA act synergistically to facilitate the multi-step process towards EOR. This study offers a promising way to find a feasible route for scalable HEA manufacturing with promising applications.

Pd sub-nanolayer on Au core for enhanced catalytic hydrogenation reduction of oxyanions pollutants: Synergistic effect of Pd and Au

Oxyanion pollutants in industrial wasterwater, such as (Cr(VI)), BrO3− (Br(V)) and SeO32− (Se(IV)) have detrimental or toxic effects on individual health when their concentrations accumulated to a certain level. The conversion of these oxyanions into harmless/industrial-valuable products or removal from wastewater is of significance. Herein, we designed Pd sub-nanolayer on Au core catalysts supported on Al2O3 (sub-Pd-Au/Al2O3) for highly effective catalytic hydrogenation reduction of oxyanions under ambient conditions. The sub-Pd(0.049)-Au(0.927)/Al2O3 catalyst exhibited the highest catalytic activity and TOF value for Cr(VI), Br(V) and Se(IV) reduction, respectively, by optimizing the Pd loading amount. The synergistic effect between Pd sub-nanolayer and Au core enhanced catalytic activity by regulating the Pd dispersion and site property, according to thorough characterizations that included high-angle annular dark-field transmission electron microscopy (HAADF-TEM) image, in-situ CO-IR adsorption, CO chemisorption, and X-ray photoelectron spectroscopy (XPS). This work might provide some new lights on design of highly efficient catalysts for the elimination of oxyanion pollutants.

Pd Nanoparticles Supported on N-Incorporated Hybrid Organosilica as an Active and Selective Low-Temperature Phenol Hydrogenation Catalyst

A heterogeneous Pd-NPMO hybrid-silica catalyst is synthesized and its application for aqueous phase selective hydrogenation of phenol to cyclohexanone at near ambient temperature (40 °C) and under atmospheric hydrogen pressure is demonstrated. The homogeneously distributed Pd nanoparticles on N-bridged hybrid mesoporous organosilica showed remarkable activity and selectivity for cyclohexanone compared to the unmodified Pd-SBA-15 catalyst. Control experiments strongly claim the role of nitrogen domains in the organic framework of hybrid silica support in stabilizing small Pd nanoparticles and possibly modifying the Pd sites responsible for catalysis to activate the substrate molecules in water. The hybrid silica catalyst was stable and reused several times without any significant drop-in activity, proving the heterogeneity of the bifunctional Pd catalyst. Based on the density functional theory study and experimental interventions, a possible reaction mechanism for the low-temperature phenol hydrogenation explaining the role of organic domains in the hybrid-silica framework is proposed.

Designed Nanomaterials for Electrocatalytic Organic Hydrogenation Using Water as the Hydrogen Source.

ConspectusThe hydrogenation reaction is one of the most frequently used transformations in organic synthesis. Electrocatalytic hydrogenation by using water (H2O) as the hydrogen source offers an efficient and sustainable approach to synthesize hydrogenated products under ambient conditions. Such a technique can avoid the use of high-pressure and flammable hydrogen gas or other toxic/expensive hydrogen donors, which usually cause environmental, safety, and cost concerns. Interestingly, utilizing easily available heavy water (D2O) for deuterated syntheses is also attractive due to the widespread applications of deuterated molecules in organic synthesis and the pharmaceutical industry. Despite impressive achievements, electrode selection mainly relies on trial-and-error modes, and how electrodes dictate reaction outcomes remains elusive. Therefore, the rational design of nanostructured electrodes for driving the electrocatalytic hydrogenation of a series of organics via H2O electrolysis is developed.In this Account, we review recent advances in the electrocatalytic hydrogenation of different types of organic functional groups, including C≡C, C≡N, C═C, C═O, and C-Br/I bonds, -NO2, and N-heterocycles, with H2O over nanostructured cathodes. First, the general reaction steps (reactant/intermediate adsorption, active atomic hydrogen (H*) formation, surface hydrogenation reaction, product desorption) are analyzed, and key factors are proposed to optimize hydrogenation performance (e.g., selectivity, activity, Faradaic efficiency (FE), reaction rate, and productivity) and inhibit side reactions. Then, ex situ and in situ spectroscopic tools to study key intermediates and interpret mechanisms are introduced. Third, based on the knowledge of key reaction steps and mechanisms, we introduce catalyst design principles in detail on how to optimize the adoption of reactants and key intermediates, promote the formation of H* from water electrolysis, inhibit hydrogen evolution and side reactions, and improve the selectivity, reaction rate, FEs, and space-time productivity of products. We then introduce some typical examples. (i) P- and S-modified Pd can decrease C═C adsorption and promote H* formation, enabling semihydrogenation of alkynes with high selectivity and FEs at lower potentials. Then, creating high-curvature nanotips to concentrate the substrates further speeds up the hydrogenation process. (ii) By introducing low-coordination sites into Fe and combining low-coordination sites and surface fluorine to modify Co to optimize the adsorption of intermediates and facilitate H* formation, hydrogenation of nitriles and N-heterocycles with high activity and selectivity is obtained. (iii) By forming isolated Pd sites to induce a specific σ-alkynyl adsorption of alkynes and steering S vacancies of Co3S4-x to preferentially adsorb -NO2, hydrogenation of easily reduced group-decorated alkynes and nitroarenes with high chemoselectivity is realized. (iv) For gas reactant participated reactions, by designing hydrophobic gas diffusion layer-supported ultrasmall Cu nanoparticles to enhance mass transfer, improve H2O activation, inhibit H2 formation, and decrease ethylene adsorption, ampere-level ethylene production with a 97.7% FE is accomplished. Finally, we provide an outlook on the current challenges and promising opportunities in this area. We believe that the electrode selection principles summarized here provide a paradigm for designing highly active and selective nanomaterials to achieve electrocatalytic hydrogenation and other organic transformations with fascinating performances.