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A Comprehensive Study of Formic Acid Oxidation on Palladium Nanocrystals with Different Types of Facets and Twin Defects
Palladium has been recognized as the best anodic, monometallic electrocatalyst for the formic acid oxidation (FAO) reaction in a direct formic acid fuel cell. Here we report a systematic study of FAO on a variety of Pd nanocrystals, including cubes, right bipyramids, octahedra, tetrahedra, decahedra, and icosahedra. These nanocrystals were synthesized with approximately the same size, but different types of facets and twin defects on their surfaces. Our measurements indicate that the Pd nanocrystals enclosed by {1 0 0} facets have higher specific activities than those enclosed by {1 1 1} facets, in agreement with prior observations for Pd single-crystal substrates. If comparing nanocrystals predominantly enclosed by a specific type of facet, {1 0 0} or {1 1 1}, those with twin defects displayed greatly enhanced FAO activities compared to their single-crystal counterparts. To rationalize these experimental results, we performed periodic, self-consistent DFT calculations on model single-crystal substrates of Pd, representing the active sites present in the nanocrystals used in the experiments. The calculation results suggest that the enhancement of FAO activity on defect regions, represented by Pd(2 1 1) sites, compared to the activity of both Pd(1 0 0) and Pd(1 1 1) surfaces, could be attributed to an increased flux through the HCOO-mediated pathway rather than the COOH-mediated pathway on Pd(2 1 1). Since COOH has been identified as a precursor to CO, a site-poisoning species, a lower coverage of CO at the defect regions will lead to a higher activity for the corresponding nanocrystal catalysts, containing those defect regions.
Impaired fatty acid oxidation as a cause for lipotoxicity in cardiomyocytes
A major cause for diabetic cardiomyopathy is excess lipid accumulation. To elucidate mechanisms of lipotoxicity mediated diabetic heart disease we need to further our understanding of how lipid metabolism is altered in the diabetic heart. Here we investigated the role of lipid clearance by oxidation as a regulator of lipid-mediated toxicity (lipotoxicity). We evaluated the effect of pre-treating rat neonatal cardiomyocytes (NCMs) with either oleate (mono-unsaturated fatty acid) or palmitate (saturated fatty acid) on fatty acid oxidation (FAO) by measuring {sup 14}C–CO{sub 2} production. We evaluated carnitine palmitoyltransferase (Cpt1b) expression by western blotting and mitochondrial membrane potential by quantitative and qualitative fluorescence analyses using the JC-1 dye. We inhibited the Cpt1b pharmacologically using etomoxir and genetically by knocking down its expression using LentiVector mediated transduction of siRNAs targeting the Cpt1b gene. We found that palmitate had a slower clearance rate from NCMs than oleate, and this was associated with a significant decrease in FAO. This impairment in FAO was not the result of either loss of Cpt1b protein or mitochondrial integrity. Enhancing FAO with either oleate or carnitine was associated with a significant attenuation of palmitate mediated lipotoxicity. In contrast impairing FAO in oleate treated NCMs caused lipotoxicity. Here we demonstrate that a major difference between non-toxic unsaturated fatty acids and toxic saturated fatty acids is there ability to stimulate or inhibit fatty acid oxidation, respectively. This has important implications for diabetic cardiomyopathy since diabetic hearts consistently exhibit elevated lipid accumulation. - Highlights: • Palmitate had a slower clearance rate from NCMs than oleate. • Palmitate caused a significant decrease in fatty acid oxidation in cardiomyocytes. • Impaired FAO was not due to loss of Cpt1b protein or mitochondrial integrity. • Enhancing FAO attenuated palmitate mediated lipotoxicity. • Impairing FAO caused lipotoxicity by non-toxic oleate.
Live imaging reveals a conserved role of fatty acid β-oxidation in early lymphatic development in zebrafish
Highlights: • Fatty acid β-oxidation (FAO) co-determines lymphatic development in the zebrafish. • Silencing of Cpt1a, key enzyme of FAO, disrupts initiation of lymphangiogenesis. • The importance of FAO for lymphatic development is conserved across species. During embryonic development, lymphatic endothelial cells (LECs) differentiate from venous endothelial cells (VECs), a process that is tightly regulated by several genetic signals. While the aquatic zebrafish model is regularly used for studying lymphangiogenesis and offers the unique advantage of time-lapse video-imaging of lymphatic development, some aspects of lymphatic development in this model differ from those in the mouse. It therefore remained to be determined whether fatty acid β-oxidation (FAO), which we showed to regulate lymphatic formation in the mouse, also co-determines lymphatic development in this aquatic model. Here, we took advantage of the power of the zebrafish embryo model to visualize the earliest steps of lymphatic development through time-lapse video-imaging. By targeting zebrafish isoforms of carnitine palmitoyltransferase 1a (cpt1a), a rate controlling enzyme of FAO, with multiple morpholinos, we demonstrate that reducing CPT1A levels and FAO flux during zebrafish development impairs lymphangiogenic secondary sprouting, the initiation of lymphatic development in the zebrafish trunk, and the formation of the first lymphatic structures. These findings not only show evolutionary conservation of the importance of FAO for lymphatic development, but also suggest a role for FAO in co-regulating the process of VEC-to-LEC differentiation in zebrafish in vivo.
Design of Advanced Thin-Film Catalysts for Electrooxidation of Formic Acid
Successful development of catalysts for electrochemical formic acid oxidation (FAO) requires finding an optimal balance between catalytic performance (activity, stability, and selectivity) and catalyst cost. While platinum is one of the most active catalyst materials for FAO, it suffers from performance loss at low overpotentials due to poisoning with CO, which is one of the intermediates formed in the so-called indirect path of FAO. In this work, we explored the synergistic effects of the supporting material and annealing temperature on the performance of Pt thin films for FAO in acidic media. Compared to the as-prepared Pt films, the annealed films show up to 5-fold and 15-fold improvement for FAO on Pt@Ni and Pt@Cr, respectively. In conclusion, while the most active Pt@Ni thin film shows the lowest stability, the most active Pt@Cr thin film is also the most stable, challenging conventional trade-offs in electrocatalysis and providing a promising candidate for FAO nanocatalyst synthesis.
Formic Acid Electrooxidation on Pt or Pd Monolayer on Transition-Metal Single Crystals: A First-Principles Structure Sensitivity Analysis
Here, we present a density functional theory analysis of trends for the electrooxidation of formic acid (FAO) on a single Pt or Pd monolayer supported on the close-packed (111) facet of transition metals (Pt*/M or Pd*/M): Au, Ag, Cu, Pt, Pd, Ir, and Rh, the close-packed (0001) facet of Os, Ru, and Re, and the open (100) facet of Au, Ag, Pt, Pd, Ir, and Rh. We show that the deposition of Pt or Pd pseudomorphic monolayers on these single crystals modifies the electronic structure of the Pt or Pd monolayer. Specifically, we found a direct correlation between the d-band center of the Pt and Pd monolayer and the free energy of adsorbed CO*, the latter being a reactivity descriptor for FAO. Together with the free energy of adsorbed OH* as a second reactivity descriptor, we depict the thermochemistry of the reaction network as phase diagrams showing calculated free energies across regions of rate-determining steps. We found that FAO is structure-sensitive on most surfaces studied. Pt*/Au(111) is predicted to be the most active among all Pt*/M(111/0001) surfaces studied, despite binding CO*, the strongest among the close-packed facets. This is the case because of its superiority in activating water to OH*, thus removing CO* at lower potentials than other surfaces. On similar grounds, Pt*/Pd(100), Pd*/Re(0001), Pd*/Au(111), Pd*/Ag(111), and Pd*/Pt(111) are predicted to show higher FAO activity than the corresponding monometallic Pt and Pd surfaces.
Activation of type 2 cannabinoid receptors (CB2R) promotes fatty acid oxidation through the SIRT1/PGC-1α pathway
Highlights: •TC, a CB2R specific agonist, stimulates SIRT1 activity by PKA/CREB pathway. •TC promotes PGC-1α transcriptional activity by increasing its deacetylation. •TC increases the expression of genes linked to FAO and promotes the rate of FAO. •The effects of TC in FAO are dependent on CB2R. •Suggesting CB2R as a target to treat diseases with lipid dysregulation. -- Abstract: Abnormal fatty acid oxidation has been associated with obesity and type 2 diabetes. At the transcriptional level, peroxisome proliferator-activated receptor-gamma coactivator 1α (PGC-1α) has been reported to strongly increase the ability of hormone nuclear receptors PPARα and ERRα to drive transcription of fatty acid oxidation enzymes. In this study, we report that a specific agonist of the type 2 cannabinoid receptor (CB2R) can lead to fatty acid oxidation through the PGC-1α pathway. We have found that CB2R is expressed in differentiated C2C12 myotubes, and that use of the specific agonist trans-caryophyllene (TC) stimulates sirtuin 1 (SIRT1) deacetylase activity by increasing the phosphorylation of cAMP response element-binding protein (CREB), thus leading to increased levels of PGC-1α deacetylation. This use of TC treatment increases the expression of genes linked to the fatty acid oxidation pathway in a SIRT1/PGC-1α-dependent mechanism and also drastically accelerates the rate of complete fatty acid oxidation in C2C12 myotubes, neither of which occur when CB2R mRNA is knocked down using siRNA. These results reveal that activation of CB2R by a selective agonist promotes lipid oxidation through a signaling/transcriptional pathway. Our findings imply that pharmacological manipulation of CB2R may provide therapeutic possibilities to treat metabolic diseases associated with lipid dysregulation.
NDRG2 overexpression suppresses hepatoma cells survival during metabolic stress through disturbing the activation of fatty acid oxidation
Because of the high nutrient consumption and inadequate vascularization, solid tumor constantly undergoes metabolic stress during tumor development. Oncogenes and tumor suppressor genes participated in cancer cells' metabolic reprogramming. N-Myc downstream regulated gene 2 (NDRG2) is a recently identified tumor suppressor gene, but its function in cancer metabolism, particularly during metabolic stress, remains unclear. In this study, we found that NDRG2 overexpression significantly reduced hepatoma cell proliferation and enhanced cell apoptosis under glucose limitation. Moreover, NDRG2 overexpression aggravated energy imbalance and oxidative stress by decreasing the intracellular ATP and NADPH generation and increasing ROS levels. Strikingly, NDRG2 inhibited the activation of fatty acid oxidation (FAO), which preserves ATP and NADPH purveyance in the absence of glucose. Finally, mechanistic investigation showed that NDRG2 overexpression suppressed the glucose-deprivation induced AMPK/ACC pathway activation in hepatoma cells, whereas the expression of a constitutively active form of AMPK abrogated glucose-deprivation induced AMPK activation and cell apoptosis. Thus, as a negative regulator of AMPK, NDRG2 disturbs the induction of FAO genes by glucose limitation, leading to dysregulation of ATP and NADPH, and thus reduces the tolerance of hepatoma cells to glucose limitation. - Highlights: • NDRG2 overexpression reduces the tolerance of hepatoma cells to glucose limitation. • NDRG2 overexpression aggravates energy imbalance and oxidative stress under glucose deprivation. • NDRG2 overexpression disturbs the activation of FAO in hepatoma cells under glucose limitation. • NDRG2 overexpression inhibits the activation of AMPK/ACC pathway in hepatoma cells during glucose starvation.
Platinum and Palladium Monolayer Electrocatalysts for Formic Acid Oxidation
The direct formic acid fuel cell holds great promise as a next generation portable power source. In this paper we report an experimental study on Pt and Pd monolayer (Pt* and Pd*) atop the close-packed facet of transition metal substrates (denoted Pt*/M or Pd*/M, where M = Pt, Pd, Ir, Au, Rh and Ru) model catalysts for formic acid oxidation (FAO) and demonstrate a promotional effect on Pt*/Au(111) and Pd*/Pt(111) surfaces. Contrary to findings on monometallic surfaces, in situ infrared reflection adsorption spectroscopy collected during formic acid oxidation at potentials anodic of 375 mV reveal that the poisoning reaction intermediate CO is not formed on the monolayer surfaces, suggesting a promotion of the direct mechanisms of FAO at the expense of the indirect mechanism through CO. Our density functional theory calculations on model surfaces with 1:1 stoichiometry for overlayer to support metal atoms for the thermochemistry of the elementary steps defined by adsorbed CO, OH, COOH, and HCOO on the (111) facet of Pt, PtML/Au, Pd, and PdML/Pt largely attribute the promotional effect observed for the monolayer catalysts to easier removal of CO brought about by easier activation of water, relative to the monometallic catalysts. This synergy between experiments and theory brings us closer to a fundamental understanding of FAO electrocatalysts under reaction conditions, paving the way to achieving more active electrocatalysts possibly with less Pt or Pd; a pre-requisite for the mass commercialization of this technology.
Cardiomyocyte specific expression of Acyl-coA thioesterase 1 attenuates sepsis induced cardiac dysfunction and mortality
Compromised cardiac fatty acid oxidation (FAO) induced energy deprivation is a critical cause of cardiac dysfunction in sepsis. Acyl-CoA thioesterase 1 (ACOT1) is involved in regulating cardiac energy production via altering substrate metabolism. This study aims to clarify whether ACOT1 has a potency to ameliorate septic myocardial dysfunction via enhancing cardiac FAO. Transgenic mice with cardiomyocyte specific expression of ACOT1 (αMHC-ACOT1) and their wild type (WT) littermates were challenged with Escherichia coli lipopolysaccharide (LPS; 5 mg/kg i.p.) and myocardial function was assessed 6 h later using echocardiography and hemodynamics. Deteriorated cardiac function evidenced by reduction of the percentage of left ventricular ejection fraction and fractional shortening after LPS administration was significantly attenuated by cardiomyocyte specific expression of ACOT1. αMHC-ACOT1 mice exhibited a markedly increase in glucose utilization and cardiac FAO compared with LPS-treated WT mice. Suppression of cardiac peroxisome proliferator activated receptor alpha (PPARa) and PPARγ-coactivator-1α (PGC1a) signaling observed in LPS-challenged WT mice was activated by the presence of ACOT1. These results suggest that ACOT1 has potential therapeutic values to protect heart from sepsis mediated dysfunction, possibly through activating PPARa/PGC1a signaling. - Highlights: • ACOT1 has potential therapeutic values to protect heart from sepsis mediated dysfunction. • ACOT1 can regulate PPARa/PGC1a signaling pathway. • We first generate the transgenic mice with cardiomyocyte specific expression of ACOT1.
The role of coverage effects on the structure–sensitivity of formic acid electrooxidation on Pd surfaces
Direct formic acid (FA) fuel cells (DFAFCs) with Pd anode catalysts are promising for small portable applications. During the electrooxidation of formic acid (FAO), CO accumulates on the Pd electrocatalyst, thereby decreasing its performance. In this work, we use density functional theory (DFT; RPBE) to elucidate the significance of coverage effects on the structure–sensitivity of FAO over four low–index Pd surfaces: Pd(1 1 1), Pd(1 0 0), Pd(1 1 0), and Pd(2 1 1). We construct coverage–dependent Gibbs free energy diagrams and in agreement with experiment, predict that Pd(1 0 0) and Pd(2 1 1) are the most active surfaces. Additionally, we find that the presence of CO spectator species can alter the preferred electrooxidation pathway under different applied potentials. Furthermore, such pathway transitions appear to be critical for rationalizing experimental trends regarding electrocatalytic activity and are only captured when coverage effects are accounted for. Insights derived from this work may facilitate the design of improved FAO electrocatalysts.
Regional carbon fluxes from land use and land cover change in Asia, 1980–2009
We present a synthesis of the land-atmosphere carbon flux from land use and land cover change (LULCC) in Asia using multiple data sources and paying particular attention to deforestation and forest regrowth fluxes. The data sources are quasi-independent and include the U.N. Food and Agriculture Organization-Forest Resource Assessment (FAO-FRA 2015; country-level inventory estimates), the Emission Database for Global Atmospheric Research (EDGARv4.3), the 'Houghton' bookkeeping model that incorporates FAO-FRA data, an ensemble of 8 state-of-the-art Dynamic Global Vegetation Models (DGVM), and 2 recently published independent studies using primarily remote sensing techniques. The estimates are aggregated spatially to Southeast, East, and South Asia and temporally for three decades, 1980–1989, 1990–1999 and 2000–2009. Since 1980, net carbon emissions from LULCC in Asia were responsible for 20%–40% of global LULCC emissions, with emissions from Southeast Asia alone accounting for 15%–25% of global LULCC emissions during the same period. In the 2000s and for all Asia, three estimates (FAO-FRA, DGVM, Houghton) were in agreement of a net source of carbon to the atmosphere, with mean estimates ranging between 0.24 to 0.41 Pg C yr -1 , whereas EDGARv4.3 suggested a net carbon sink of -0.17 Pg C yr -1 . Three of 4 estimates suggest that LULCC carbon emissions declined by at least 34% in the preceding decade (1990–2000). Spread in the estimates is due to the inclusion of different flux components and their treatments, showing the importance to include emissions from carbon rich peatlands and land management, such as shifting cultivation and wood harvesting, which appear to be consistently underreported.
Land-use harmonization datasets for annual global carbon budgets
Abstract. Land-use change has been the dominant source of anthropogenic carbon emissions for most of the historical period and is currently one of the largest and most uncertain components of the global carbon cycle. Advancing the scientific understanding on this topic requires that the best data be used as input to state-of-the-art models in well-organized scientific assessments. The Land-Use Harmonization 2 dataset (LUH2), previously developed and used as input for simulations of the 6th Coupled Model Intercomparison Project (CMIP6), has been updated annually to provide required input to land models in the annual Global Carbon Budget (GCB) assessments. Here we discuss the methodology for producing these annual LUH2-GCB updates and extensions which incorporate annual wood harvest data updates from the Food and Agriculture Organization (FAO) of the United Nations for dataset years after 2015 and the History Database of the Global Environment (HYDE) gridded cropland and grazing area data updates (based on annual FAO cropland and grazing area data updates) for dataset years after 2012, along with extrapolations to the current year due to a lag of 1 or more years in the FAO data releases. The resulting updated LUH2-GCB datasets have provided global, annual gridded land-use and land-use-change data relating to agricultural expansion, deforestation, wood harvesting, shifting cultivation, regrowth and afforestation, crop rotations, and pasture management and are used by both bookkeeping models and dynamic global vegetation models (DGVMs) for the GCB. For GCB 2019, a more significant update to LUH2 was produced, LUH2-GCB2019 (https://doi.org/10.3334/ORNLDAAC/1851, Chini et al., 2020b), to take advantage of new data inputs that corrected cropland and grazing areas in the globally important region of Brazil as far back as 1950. From 1951 to 2012 the LUH2-GCB2019 dataset begins to diverge from the version of LUH2 used for the World Climate Research Programme's CMIP6, with peak differences in Brazil in the year 2000 for grazing land (difference of 100 000 km2) and in the year 2009 for cropland (difference of 77 000 km2), along with significant sub-national reorganization of agricultural land-use patterns within Brazil. The LUH2-GCB2019 dataset provides the base for future LUH2-GCB updates, including the recent LUH2-GCB2020 dataset, and presents a starting point for operationalizing the creation of these datasets to reduce time lags due to the multiple input dataset and model latencies.
Impact of Surface Roughness and Soil Texture on Mineral Dust Emission Fluxes Modeling
Dust production models (DPM) used to estimate vertical fluxes of mineral dust aerosols over arid regions need accurate data on soil and surface properties. The Laboratoire Inter-Universitaire des Systemes Atmospheriques (LISA) data set was developed for Northern Africa, the Middle East, and East Asia. This regional data set was built through dedicated field campaigns and include, among others, the aerodynamic roughness length, the smooth roughness length of the erodible fraction of the surface, and the dry (undisturbed) soil size distribution. Recently, satellite-derived roughness length and high-resolution soil texture data sets at the global scale have emerged and provide the opportunity for the use of advanced schemes in global models. This paper analyzes the behavior of the ERS satellite-derived global roughness length and the State Soil Geographic data base-Food and Agriculture Organization of the United Nations (STATSGO-FAO) soil texture data set (based on wet techniques) using an advanced DPM in comparison to the LISA data set over Northern Africa and the Middle East. We explore the sensitivity of the drag partition scheme (a critical component of the DPM) and of the dust vertical fluxes (intensity and spatial patterns) to the roughness length and soil texture data sets. We also compare the use of the drag partition scheme to a widely used preferential source approach in global models. Idealized experiments with prescribed wind speeds show that the ERS and STATSGO-FAO data sets provide realistic spatial patterns of dust emission and friction velocity thresholds in the region. Finally, we evaluate a dust transport model for the period of March to July 2011 with observed aerosol optical depths from Aerosol Robotic Network sites. Results show that ERS and STATSGO-FAO provide realistic simulations in the region.
Land-Use Harmonization Datasets for Global Carbon Budget 2019 and Beyond
Land-use change has been the dominant source of anthropogenic carbon emissions for most of the historical period, and is currently one of the largest and most uncertain components of the global carbon cycle. Advancing the scientific understanding on this topic requires that the best data be used as input to the best models in well-organized scientific assessments. The Land-Use Harmonization dataset (LUH2), previously developed and used as input for CMIP6 simulations, has been updated annually to provide required input to land models in the annual Global Carbon Budget (GCB) assessment. These annual LUH2-GCB updates and extensions have incorporated annual FAO wood harvest data updates for dataset years after 2015 and HYDE gridded agriculture area data updates (based on annual FAO agricultural area data updates) for dataset years after 2012, along with extrapolations to the current year due to a lag of one or more years in the FAO data releases. The resulting updated LUH2-GCB datasets have provided global, annual gridded land-use and land-use change data relating toagricultural expansion, deforestation, wood harvesting, shifting cultivation, regrowth and afforestation, and crop rotationsand pasture managementand are used by both book-keeping models and Dynamic Global Vegetation Models (DGVMs) for the GCB. For GCB 2019,a more significant update to LUH2 was produced (LUH2-GCB2019) to correct cropland and grazing area errors in the underlying input datasets for the globally important region of Brazil, as far back as 1950. From 1951-2012 the LUH2-GCB2019 dataset begins to diverge from the LUH2 v2hdataset, with peak differences in Brazil in the year 2000 for grazing land (difference of 100,000 km2) and in the year 2009 for cropland (difference of 77,000 km2), along with significant sub-national reorganization of agricultural land-use patterns within Brazil. These LUH2-GCB2019 corrections for Brazil provide the base for future LUH2-GCB updates including the recent LUH2-GCB2020 dataset, and present a starting point for operationalizing the creation of these datasets toreduce time-lags due to the multiple input dataset and model latencies.
Carbon Nanospheres Loaded with Ir Single Atoms: Enhancing the Activity toward Formic Acid Oxidation by Increasing the Porosity
Theoretically, single-atom catalysts (SACs) offer 100 % atom utilization, making them strong candidates to replace expensive nanoparticles for catalysis. However, the structural supports used to anchor the SACs dramatically reduce the utilization efficiency of atoms ( i. e ., the percent of atoms actually accessible by reactants) by either encapsulating the SACs completely or creating severe diffusion limitation. Either of which leads to an overall low atom utilization and thus poor electrocatalytic activity similar to that of nanoparticles. In addressing this issue, we systematically investigated how the porous structure of carbon nanospheres affects the activity of Ir-SACs toward formic acid oxidation (FAO). Specifically, we utilized a kinetically-controlled growth strategy to produce uniform carbon nanospheres featuring yolk-shell, mesoporous, and hollow structures with Ir-SACs loaded throughout the structure. At a high specific surface area of 441 m 2 g -1 and exposed metal content of 1.82 wt %, the Ir-SACs based on mesoporous carbon nanospheres showed a remarkable FAO peak current density of 30.6 mA cm -2 , which was 283 and 46 times greater when benchmarked against the catalysts based on solid carbon nanospheres and 20 wt % Ir/C, respectively.
Solution-Phase Synthesis of PdH 0.706 Nanocubes with Enhanced Stability and Activity toward Formic Acid Oxidation
We report palladium is one of the few metals capable of forming hydrides, with the catalytic properties being dependent on the elemental composition and spatial distribution of H atoms in the lattice. Herein, we report a facile method for the complete transformation of Pd nanocubes into a stable phase made of PdH 0.706 by treating them with aqueous hydrazine at a concentration as low as 9.2 mM. Using formic acid oxidation (FAO) as a model reaction, we systematically investigated the structure–catalytic property relationship of the resultant nanocubes with different degrees of hydride formation. The current density at 0.4 V was enhanced by four times when the nanocubes were completely converted from Pd to PdH 0.706 . On the basis of a set of slab models with PdH(100) overlayers on Pd(100), we conducted density functional theory calculations to demonstrate that the degree of hybrid formation could influence both the activity and selectivity toward FAO by modulating the relative stability of formate (HCOO) and carboxyl (COOH) intermediates. Furthermore, this work provides a viable strategy for augmenting the performance of Pd-based catalysts toward various reactions without altering the loading of this scarce metal.
A Facile Synthesis of MPd (M=Co, Cu) Nanoparticles and Their Catalysis for Formic Acid Oxidation
Monodisperse CoPd nanoparticles (NPs) were synthesized and studied for catalytic formic acid (HCOOH) oxidation (FAO). The NPs were prepared by coreduction of Co(acac)2 (acac = acetylacetonate) and PdBr2 at 260 C in oleylamine and trioctylphosphine, and their sizes (5-12 nm) and compositions (Co10Pd90 to Co60Pd40) were controlled by heating ramp rate, metal salt concentration, or metal molar ratios. The 8 nm CoPd NPs were activated for HCOOH oxidation by a simple ethanol wash. In 0.1 M HClO4 and 2 M HCOOH solution, their catalytic activities followed the trend of Co50Pd50 > Co60Pd40 > Co10Pd90 > Pd. The Co50Pd50 NPs had an oxidation peak at 0.4 V with a peak current density of 774 A/gPd. As a comparison, commercial Pd catalysts showed an oxidation peak at 0.75 V with peak current density of only 254 A/gPd. The synthesis procedure could also be extended to prepare CuPd NPs when Co(acac)2 was replaced by Cu(ac)2 (ac = acetate) in an otherwise identical condition. The CuPd NPs were less active catalysts than CoPd or even Pd for FAO in HClO4 solution. The synthesis provides a general approach to Pd-based bimetallic NPs and will enable further investigation of Pd-based alloy NPs for electro-oxidation and other catalytic reactions.