Deciphering Doping Effects in a V-Doped Ni Catalyst for Hydrogen Electrooxidation.

The improved performance of soluble metal-doped Ni catalysts is perplexed by the evolvable surface structures in the alkaline electrolytes for hydrogen oxidation reaction (HOR). Herein, V-doped Ni nanoparticles, as a proof of concept, were carefully evaluated to explore the intrinsic function of the enthetic V-species in assisting the HOR kinetic improvement. As expected, it exhibits a mass-normalized kinetic current density of 50.34 mA mgNi-1, more than 12 times that of the Ni counterpart without the introduction of V. Systematic investigations prove that the surface V-species, including the V-oxides and the doped V atoms at the outmost layer, would be dissolved into the electrolytes during the alkaline HOR process. The remaining V-dopants inside the nanoparticles would rationally weaken the hydroxyl binding energy (OHBE) of the Ni-based surfaces, thereby accelerating the formation of water molecules. We also uncover that Ni is located at the overstrong branch of the OHBE-described volcano plot through theoretical calculations and alkali-metal cation probe experiments, and weakening the OHBE by internal V-doping can leave the activity to the volcanic apex.

Breaking Surface Atomic Monogeneity of Rh2 P Nanocatalysts by Defect-Derived Phosphorus Vacancies for Efficient Alkaline Hydrogen Oxidation.

Breaking atomic monogeneity of catalyst surfaces is promising for constructing synergistic active centers to cope with complex multi-step catalytic reactions. Here, we report a defect-derived strategy for creating surface phosphorous vacancies (P-vacancies) on nanometric Rh2 P electrocatalysts toward drastically boosted electrocatalysis for alkaline hydrogen oxidation reaction (HOR). This strategy disrupts the monogeneity and atomic regularity of the thermodynamically stable P-terminated surfaces. Density functional theory calculations initially verify that the competitive adsorption behavior of Had and OHad on perfect P-terminated Rh2 P{200} facets (p-Rh2 P) can be bypassed on defective Rh2 P{200} surfaces (d-Rh2 P). The P-vacancies enable the exposure of sub-surface Rh atoms to act as exclusive H adsorption sites. Therein, the Had cooperates with the OHad on the peripheral P-sites to effectively accelerate the alkaline HOR. Defective Rh2 P nanowires (d-Rh2 P NWs) and perfect Rh2 P nanocubes (p-Rh2 P NCs) are then elaborately synthesized to experimentally represent the d-Rh2 P and p-Rh2 P catalytic surfaces. As expected, the P-vacancy-enriched d-Rh2 P NWs catalyst exhibits extremely high catalytic activity and outstanding CO tolerance for alkaline HOR electrocatalysis, attaining 5.7 and 14.3 times mass activity that of p-Rh2 P NCs and commercial Pt/C, respectively. This work sheds light on breaking the surface atomic monogeneity for the development of efficient heterogeneous catalysts.

Equilibrated PtIr/IrOx Atomic Heterojunctions on Ultrafine 1D Nanowires Enable Superior Dual-Electrocatalysis for Overall Water Splitting.

Dual-active-sites atomically coupled on ultrafine 1D nanowires (NWs) can offer synergic atomic heterojunctions (AHJs) and high atomic-utilization toward multipurpose and superior catalysis. Here, ≈2-nm-thick PtIr/IrOx hybrid NWs are elaborately synthesized with equilibrated Pt/IrOx AHJs as high-efficiency bifunctional electrocatalysts for overall water splitting. Mechanism studies reveal the atomically coupled Pt-IrOx dual-sites are favorable for facilitating water dissociation, alleviating the binding of H* on Pt sites and inversely regulating the *OH adsorption and oxidation on bridge Ir-Ir sites. By simply equilibrating the Pt-IrOx ratio, the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) can be substantially accelerated. In particular, Pt-rich PtIr/IrOx -30 NWs attain 11-fold enhancements for HER compared to Pt/C in 1.0 m KOH, while IrOx -rich PtIr/IrOx -50 NWs express about five times mass activity referring to Ir/C for OER. Remarkably, the ratio-optimized PtIr/IrOx NWs electrode couple achieves a durably continuous H2 production under a substantially low cell voltage.

Poor recovery of cardiac function in myocardial infarction patients with metabolic syndrome and microalbuminuria.

BACKGROUND: This study aimed to investigate the impact of metabolic syndrome (MetS) with microalbuminuria on the improvement of cardiac function after acute myocardial infarction (AMI). METHODS: Nondiabetic patients with acute ST segment elevation MI (STEMI) who underwent coronary revascularization from 2013 to 2017 were included. They were grouped according to history of MetS and microalbuminuria test results as follows: microalbuminuria/MetS group, normoalbuminuria/MetS group, microalbuminuria/no MetS group, and normoalbuminuria/no MetS group. Left ventricular ejection fraction (LVEF) and serum N-terminal pro-brain natriuretic peptide (NT-proBNP) levels at the 6­month follow-up were measured and the predictive value of MetS with microalbuminuria on recovery of cardiac function was assessed by multivariable logistic regression modeling. RESULTS: A total of 530 STEMI patients were included (average age = 66.6 years). Analysis of covariance showed that LVEF recovery in the normoalbuminuria/no MetS group was better than that of the normoalbuminuria/MetS, microalbuminuria/no MetS, and microalbuminuria/MetS groups (49.22% vs. 48.92% vs. 47.48% vs. 46.99%, respectively, p < 0.001) when acute phase LVEF was the covariable. The NT-proBNP level of the normoalbuminuria/no MetS group at the 6­month follow-up was lower than that of the microalbuminuria/MetS group (p < 0.001). Further regression analysis revealed that there was a lower probability of complete cardiac function recovery after 6 months in patients with microalbuminuria (odds ratio: 0.455) than in patients without microalbuminuria (95% CI: 0.316-0.655, p < 0.001). CONCLUSION: Although post-AMI cardiac function in MetS patients with microalbuminuria can be improved after revascularization, the improvement is not as good as that of patients without microalbuminuria, suggesting that clinical attention should be paid to this subgroup.

Deciphering promotion of MoP over MoC in Pt catalysts for methanol-assisted water splitting reaction.

Molybdenum-based compounds show promising promotion effects on Pt catalysts for energy-relevant catalysis reactions. Herein, a more effective promotion effect of MoP than MoC was found in assisting Pt nanoparticles for methanol-assisted hydrogen generation in light of the strong metal-support interaction and synergistic effect between Pt and MoP/C nanospheres. Electrochemical analyses and theoretical calculations demonstrated that Pt-MoP/C facilitated the oxidation and removal of CO intermediates more effectively than Pt-MoC/C. This enhanced performance was attributed to the distinct 6-coordination environment of hexagonal MoP and the elevated electron density of Mo induced by phosphorus. These structural and electronic features significantly enhanced electron transfer to Pt, thereby creating strong metal-support interaction and synergistic effect to improve the overall catalytic efficiency. Especially, the unique activities of Moδ+ and Moδ- in the MoP modified the surface structure of Pt, lowered the Pt d-band center, and optimized the local chemical state of Pt atoms, which resulted in more optimized adsorption energy and charge transfer capabilities of intermediates. The Pt-MoP/C electrolyzer thus showed both lower cell voltage than that of Pt-MoC/C and Pt/C electrolyzers in water splitting and methanol-assisted water splitting for hydrogen generation. This study offers insightful information about the promotion effect of molybdenum-based compounds in Pt catalyst systems in energy-relevant catalysis reactions.

Coordination tuning of FeNi-HMT Framework derived effective hybrid catalysts for water oxidation.

FeNi-based hybrid materials are promising oxygen evolution reaction (OER) catalysts for water electrolysis in hydrogen generation. In this work, the coordination tuning of FeNi-HMT frameworks was achieved by simply changing the Fe/Ni ratios using hexamethylenetetramine (HMT) as an organic ligand, and the derived hybrid FeNi catalysts with varied compositions were probed for OER. Incorporating varying amounts of Fe3+ by adjusting the Ni/Fe ratio results in different metal-organic framework (MOF) structures, and higher Fe feed leads to the formation of amorphous structures due to the coordination structure destruction from the weaker coordination capacity of Fe3+ compared to Ni2+ combining with the tertiary amine ligand. Among them, the FeNi-HMT (with the Fe/Ni molar ratio of 1/1) derived catalyst, consisting of Fe0.36Ni0.64 alloy/Ni0.4Fe2.6O4 spinel oxide heterostructures supported by graphitized carbon matrix, exhibits the highest OER performance. The unique structure facilitates significant electron transfer at the alloy/spinel interface due to the large work function difference between each phase. This strong electronic effect downshifts the d-band center of the catalyst and optimizes the binding energies to the crucial oxygenated intermediates, thereby promoting the OER kinetics. This work highlights the importance of the coordination tuning of FeNi-HMT frameworks for highly efficient catalyst development.

Alleviating the competitive adsorption of hydrogen and hydroxyl intermediates on Ru by d-p orbital hybridization for hydrogen electrooxidation.

Strengthening the hydroxyl binding energy (OHBE) on Ru surfaces for efficient hydrogen oxidation reaction (HOR) in alkaline electrolytes at the expense of narrowing the effective potential window (EPW) increases the risk of passivation under transient conditions for the alkaline exchange membrane fuel cell technique. Herein, an effective Ru/NiSe2 catalyst was reported which exhibits a gradually enhanced intrinsic activity and slightly enlarged EPW with the increased degree of coupling between Ru and NiSe2. This promotion could be attributed to the optimized electron distribution and d-band structures of Ru surfaces weakening the hydrogen binding energy and especially the OHBE through the strong d-p orbital hybridization between Ru and NiSe2. Unlike the conventional way of strengthened OHBE enhancing the oxidative desorption of hydrogen intermediates (Had) via the bi-functional mechanism, the weakened OHBE on this Ru/NiSe2 model catalyst alleviates the competitive adsorption between Had and the hydroxyl intermediates (OHad), thereby accelerating the HOR kinetics at low overpotentials and hindering the full poisoning of the catalytic surfaces by strongly adsorbed OHad spectators at high overpotentials. The work reveals a missed but important approach for Ru-based catalyst development for the fuel cell technique.

Two-dimensional template-directed synthesis of one-dimensional kink-rich Pd3Pb nanowires for efficient oxygen reduction.

Developing facile synthetic strategies toward ultrafine one-dimensional (1D) nanowires (NWs) with rich catalytic hot spots is pivotal for exploring effective heterogeneous catalysts. Herein, we demonstrate a two-dimensional (2D) template-directed strategy for synthesizing 1D kink-rich Pd3Pb NWs with abundant grain boundaries to serve as high-efficiency electrocatalysts toward oxygen reduction reaction (ORR). In this one-pot synthesis, ultrathin Pd nanosheets were initially generated, which then served as self-sacrificial 2D nano-templates. A dynamic equilibrium growth was subsequently established on the 2D Pd nanosheets through the center-selected etching of Pd atoms and edge-preferred co-deposition of Pd/Pb atoms. This was followed by the oriented attachment of the generated Pd/Pb alloy nanograins and fragments. Thus, kink-rich Pd3Pb NWs with rich grain boundary defects were obtained in high yield, and these NWs were used as electrocatalytic active catalysts. The surface electronic interaction between Pd and Pb atoms effectively decreased the surface d-band center to weaken the binding of oxygen-containing intermediates toward improved ORR kinetics. Specifically, the kink-rich Pd3Pb NWs/C catalyst delivered outstanding ORR mass activity and specific activity (2.26 A⋅mgPd-1 and 2.59 mA⋅cm-2, respectively) in an alkaline solution. These values were respectively 13.3 and 10.8 times those of state-of-the-art commercial Pt/C catalyst. This study provides an innovative strategy for fabricating defect-rich low-dimensional nanocatalysts for efficient energy conversion catalysis.

Discrepant roles of adsorbed OH* species on IrWOx for boosting alkaline hydrogen electrocatalysis.

Improving the slow kinetics of alkaline hydrogen electrode reactions, involving hydrogen oxidation and evolution reactions (HOR/HER) is highly desirable for accelerating the commercialization of alkaline exchange membrane-based fuel cells (AEMFCs) and water electrolyzers (AEMWEs). However, fundamental understanding of the mechanism for HOR/HER catalysis under alkaline media is still debatable. Here we develop an amorphous tungsten oxide clusters modified iridium-tungsten nanocrystallines (IrWOx) which exhibited by far the highest exchange current density and mass activity, about three times higher than the commercial Pt/C toward alkaline HOR/HER. Density functional theory (DFT) calculations reveal the WOx clusters act as a pivotal role to boost reversible hydrogen electrode reactions in alkaline condition but via different mechanisms, which are, hydrogen binding energy (HBE) mechanism for HOR and bi-functional mechanism for HER. This work is expected to promote our fundamental understanding about the alkaline HOR/HER catalysis and provide a new avenue for rational design of highly efficient electrocatalysts toward HOR/HER under alkaline electrolytes.

IrW nanobranches as an advanced electrocatalyst for pH-universal overall water splitting.

Developing highly efficient and durable electrocatalysts for overall water splitting over a wide pH range is of great interest for practical applications, but still remains a challenge. Specifically, to the best of our knowledge, a 3-in-1 electrocatalyst that can efficiently catalyze overall water splitting in acidic, alkaline, and neutral electrolytes has not been reported so far. Herein, we report the colloidal synthesis of well-dispersed IrW nanobranches with branch architectures and describe how the morphology varies with the amount of W doping. As expected, they exhibit outstanding catalytic performance and durability for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) at all pH values, which are much higher than those of Ir nanoparticles (NPs), and most reported state-of-the-art electrocatalysts. More importantly, when further used as both an anode and cathode for overall water splitting in 0.1 M HClO4, 0.1 M KOH, and 1.0 M PBS (phosphate buffer solution), cell voltages of 1.58, 1.60, and 1.73 V, respectively, were achieved at a current density of 10 mA cm-2. The present work opens up a new avenue for designing electrocatalysts for pH-universal overall water splitting, especially for application in highly corrosive acidic media and neutral media with limited ionic concentrations.

[Reduced cardiopulmonary exercise capacity in patients with essential hypertension: impact of left ventricular hypertrophy].

OBJECTIVE: To evaluate the cardiopulmonary exercise capacity in patients with essential hypertension (EH) complicating with or without left ventricular hypertrophy (LVH). METHODS: Graded maximal exercise test on the bicycle ergometer with respiratory gas analysis were performed in 30 gender and age matched normotensive controls, 40 EH patients without LVH and 30 EH patients with LVH (LVMI>125 g/m2 in males and > 120 g/m2 in females). Metabolic equivalents (METs), oxygen uptake (VO2), oxygen uptake to body mass ratio (VO2/kg) and oxygen uptake to heart beat ratio (VO2/HR) at time of reaching anaerobic threshold (AT) and at maximal oxygen uptake (VO2max) were measured and compared. RESULTS: METs and VO2/kg were significantly reduced in EH patients with or without LVH compared with controls [at AT, METs: 3.57 +/- 0.8 and 4.34 +/- 1.47 vs. 5.21 +/- 1.45; VO2/kg: 12.38 +/- 2.85 and 14.42 +/- 4.33 vs. 18.48 +/- 4.52, all P < 0.01; at VO2max, METs: 4.94 +/- 1.24 and 5.90 +/- 1.51 vs. 6.96 +/- 1.85; VO(2)/kg: (17.20 +/- 4.34) mlxmin(-1)xkg(-1) and (20.41 +/- 4.59) mlxmin(-1)xkg(-1) vs. (24.04 +/- 5.21) mlxmin(-1)xkg(-1), all P < 0.01]. METs and VO2/kg at both time points were also significantly reduced in EH patients with LVH compared EH patients without LVH (all P < 0.05). The lower VO2/kg in hypertensive patients was significantly correlated to higher LVMI (P < 0.05). CONCLUSIONS: Cardiopulmonary exercise capacity was reduced in hypertensive patients, especially in hypertensive patients with LVH.

IrCo Nanodendrite as an Efficient Bifunctional Electrocatalyst for Overall Water Splitting under Acidic Conditions.

Investigation of high-efficiency electrocatalysts for acidic overall water splitting is of great significance toward fulfillment of proton exchange membrane (PEM) electrolyzers but still remains challenging. Herein, we report the colloidally synthesis of IrCo alloy nanodendrites with petal-like architecture (NDs). Benefiting from unique hierarchical architecture and strong electronic interaction arising from synergistic alloying effect of IrCo at the atomic level, the resultant IrCo0.65 NDs display remarkable hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) performances with overpotentials of 17 and 281 mV to achieve 10 mA cm-2 in 0.1 M HClO4, respectively. Moreover, when further used as bifunctional electrocatalyst toward acidic overall splitting, a low cell voltage of 1.593 V is achieved at 10 mA cm-2.

Ultrathin Ir nanowires as high-performance electrocatalysts for efficient water splitting in acidic media.

The search for active and stable bifunctional electrocatalysts toward acidic overall water splitting is under increasing demand for the development of polymer electrolyte membrane (PEM) electrolyzers. However, developing bifunctional electrocatalysts with Pt-like activity and superior stability under acidic media still remains a big challenge. Herein, we report a successful synthesis of Ir wavy nanowires with an ultrathin diameter of 1.7 nm through a simple wet-chemical approach. Benefiting from the unique morphology with high aspect ratios and a large specific surface area, the as-synthesized ultrathin Ir wavy nanowires exhibit enhanced activity and durability for both the oxygen evolution reaction and the hydrogen evolution reaction in acidic electrolytes. Moreover, when used for overall acidic water splitting, a current density of 10 mA cm-2 is achieved at only a cell voltage of 1.62 V in 0.1 M HClO4 electrolyte with long-term stability. In view of the excellent electrochemical water splitting performance and superior stability in acidic electrolytes, we believe that the obtained Ir wavy nanowires could be potential alternative catalysts toward PEM water electrolysis.

Multiple pulmonary adenomas in the lung of transgenic mice overexpressing the RON receptor tyrosine kinase. Recepteur d'origine nantais.

The receptor tyrosine kinase RON (recepteur d'origine nantais), a member of the MET proto-oncogene family, has been implicated in the pathogenesis of certain epithelial cancers including lung adenocarcinomas. To determine the oncogenic potential of RON, transgenic mice were generated using the surfactant protein C promoter to express human wild-type RON in the distal lung epithelial cells. The mice were born normal without morphological defects in the lung, however, multiple lung adenomas with distinct morphology and growth pattern were observed. Tumors appeared as a single mass in the lung around 2 months of age and gradually developed into multiple nodules throughout the lung. Most of the tumors were characterized as cuboidal epithelial cells with type II cell phenotypes. They grew along the alveolar walls and projected into the alveolar septa. A transition from pre-malignant adenomas to adenocarcinomas was observed. The RON transgene is highly expressed and constitutively activated in the tumors as evident by immunohistochemical staining and western blot analyses. Moreover, we found that Ras expression was dramatically increased in the majority of tumors. However, no mutation in the 'hot spots' of the K-Ras or p53 gene was observed, although limited genomic instability occurs in individual tumors. Taken together, this is a mouse lung tumor model with unique biological characteristics. The model may provide an opportunity to study the role of RON in lung tumors and to elucidate the mechanisms underlying this distinct lung tumor.