Confined microenvironments formed in heterogeneous catalysts have recently been recognized as equally important as catalytically active sites. Understanding the fundamentals of confined catalysis has ...become an important topic in heterogeneous catalysis. Well-defined 2D space between a catalyst surface and a 2D material overlayer provides an ideal microenvironment to explore the confined catalysis experimentally and theoretically. Using density functional theory calculations, we reveal that adsorption of atoms and molecules on a Pt(111) surface always has been weakened under monolayer graphene, which is attributed to the geometric constraint and confinement field in the 2D space between the graphene overlayer and the Pt(111) surface. A similar result has been found on Pt(110) and Pt(100) surfaces covered with graphene. The microenvironment created by coating a catalyst surface with 2D material overlayer can be used to modulate surface reactivity, which has been illustrated by optimizing oxygen reduction reaction activity on Pt(111) covered by various 2D materials. We demonstrate a concept of confined catalysis under 2D cover based on a weak van der Waals interaction between 2D material overlayers and underlying catalyst surfaces.
During aging, deterioration in cardiac structure and function leads to increased susceptibility to heart failure. The need for interventions to combat this age-related cardiac decline is becoming ...increasingly urgent as the elderly population continues to grow. Our understanding of cardiac aging, and aging in general, is limited. However, recent studies of age-related decline and its prevention through interventions like exercise have revealed novel pathological and cardioprotective pathways. In this review, we summarize recent findings concerning the molecular mechanisms of age-related heart failure and highlight exercise as a valuable experimental platform for the discovery of much-needed novel therapeutic targets in this chronic disease.
This paper presents a framework based on multilayer bi-LSTM network (bidirectional Long Short-Term Memory) for multimodal sensor fusion to sense and classify daily activities' patterns and high-risk ...events such as falls. The data collected in this work are continuous activity streams from FMCW radar and three wearable inertial sensors on the wrist, waist, and ankle. Each activity has a variable duration in the data stream so that the transitions between activities can happen at random times within the stream, without resorting to conventional fixed-duration snapshots. The proposed bi-LSTM implements soft feature fusion between wearable sensors and radar data, as well as two robust hard-fusion methods using the confusion matrices of both sensors. A novel hybrid fusion scheme is then proposed to combine soft and hard fusion to push the classification performances to approximately 96% accuracy in identifying continuous activities and fall events. These fusion schemes implemented with the proposed bi-LSTM network are compared with conventional sliding window approach, and all are validated with realistic "leaving one participant out" (L1PO) method (i.e. testing subjects unknown to the classifier). The developed hybrid-fusion approach is capable of stabilizing the classification performance among different participants in terms of reducing accuracy variance of up to 18.1% and increasing minimum, worst-case accuracy up to 16.2%.
Selective conversion of syngas to light olefins Jiao, Feng; Li, Jinjing; Pan, Xiulian ...
Science (American Association for the Advancement of Science),
03/2016, Volume:
351, Issue:
6277
Journal Article
Peer reviewed
Although considerable progress has been made in direct synthesis gas (syngas) conversion to light olefins (C₂⁼−C₄⁼) via Fischer-Tropsch synthesis (FTS), the wide product distribution remains a ...challenge, with a theoretical limit of only 58% for C₂–C₄ hydrocarbons. We present a process that reaches C₂⁼−C₄⁼ selectivity as high as 80% and C₂–C₄ 94% at carbon monoxide (CO) conversion of 17%. This is enabled by a bifunctional catalyst affording two types of active sites with complementary properties. The partially reduced oxide surface (ZnCrOx) activates CO and H₂, and C–C coupling is subsequently manipulated within the confined acidic pores of zeolites. No obvious deactivation is observed within 110 hours. Furthermore, this composite catalyst and the process may allow use of coal- and biomass-derived syngas with a low H₂/CO ratio.
Encapsulation of metal nanocatalysts by support-derived materials is well known as a classical strong metal–support interaction (SMSI) effect that occurs almost exclusively with active oxide supports ...and often blocks metal-catalyzed surface reactions. In the present work this classical SMSI process has been surprisingly observed between metal nanoparticles, e.g., Ni, Fe, Co, and Ru, and inert hexagonal boron nitride (h-BN) nanosheets. We find that weak oxidizing gases such as CO2 and H2O induce the encapsulation of nickel (Ni) nanoparticles by ultrathin boron oxide (BO x ) overlayers derived from the h-BN support (Ni@BO x /h-BN) during the dry reforming of methane (DRM) reaction. In-situ surface characterization and theory calculations reveal that surface B–O and B–OH sites in the formed BO x encapsulation overlayers work synergistically with surface Ni sites to promote the DRM process rather than blocking the surface reactions.
Hydrogen production through water splitting has been considered as a green, pure and high-efficient technique. As an important half-reaction involved, hydrogen evolution reaction is a complex ...electrochemical process involving liquid-solid-gas three-phase interface behaviour. Therefore, new concepts and strategies of material design are needed to smooth each pivotal step. Here we report a multiscale structural and electronic control of molybdenum disulfide foam to synergistically promote the hydrogen evolution process. The optimized three-dimensional molybdenum disulfide foam with uniform mesopores, vertically aligned two-dimensional layers and cobalt atoms doping demonstrated a high hydrogen evolution activity and stability. In addition, density functional theory calculations indicate that molybdenum disulfide with moderate cobalt doping content possesses the optimal activity. This study demonstrates the validity of multiscale control in molybdenum disulfide via overall consideration of the mass transport, and the accessibility, quantity and capability of active sites towards electrocatalytic hydrogen evolution, which may also be extended to other energy-related processes.
Abstract
Acidic CO
2
-to-HCOOH electrolysis represents a sustainable route for value-added CO
2
transformations. However, competing hydrogen evolution reaction (HER) in acid remains a great challenge ...for selective CO
2
-to-HCOOH production, especially in industrial-level current densities. Main group metal sulfides derived S-doped metals have demonstrated enhanced CO
2
-to-HCOOH selectivity in alkaline and neutral media by suppressing HER and tuning CO
2
reduction intermediates. Yet stabilizing these derived sulfur dopants on metal surfaces at large reductive potentials for industrial-level HCOOH production is still challenging in acidic medium. Herein, we report a phase-engineered tin sulfide pre-catalyst (π-SnS) with uniform rhombic dodecahedron structure that can derive metallic Sn catalyst with stabilized sulfur dopants for selective acidic CO
2
-to-HCOOH electrolysis at industrial-level current densities. In situ characterizations and theoretical calculations reveal the π-SnS has stronger intrinsic Sn-S binding strength than the conventional phase, facilitating the stabilization of residual sulfur species in the Sn subsurface. These dopants effectively modulate the CO
2
RR intermediates coverage in acidic medium by enhancing *OCHO intermediate adsorption and weakening *H binding. As a result, the derived catalyst (Sn(S)-H) demonstrates significantly high Faradaic efficiency (92.15 %) and carbon efficiency (36.43 %) to HCOOH at industrial current densities (up to −1 A cm
−2
) in acidic medium.
RuO2 is considered as the state‐of‐the‐art electrocatalyst for the oxygen evolution reaction (OER) in acidic media. However, its practical application is largely hindered by both the high reaction ...overpotential and severe electrochemical corrosion of the active centers. To overcome these limitations, innovative design strategies are necessary, which remains a great challenge. Herein, robust interface Ru centers between RuO2 and graphene, via a controllable oxidation of graphene encapsulating Ru nanoparticles, are presented to efficiently enhance both the activity and stability of the acidic OER. Through precisely controlling the reaction interface, a much lower OER overpotential of only 227 mV at 10 mA cm−2 in acidic electrolyte, compared with that of 290 mV for commercial RuO2, but a significantly higher durability than the commercial RuO2, are achieved. Density functional theory (DFT) calculations reveal that the interface Ru centers between the RuO2 and the graphene can break the classic scaling relationships between the free energies of HOO* and HO* to reduce the limiting potential, rendering an enhancement in the intrinsic OER activity and the resistance to over‐oxidation and corrosion for RuO2.
The robust interface Ru centers between RuO2 and graphene are found to boost both activity and stability for the acidic oxygen evolution reaction (OER), exhibiting a much lower OER overpotential of only 227 mV at 10 mA cm−2 compared with that of 290 mV for commercial RuO2 but a significantly higher durability than the commercial RuO2.
The development of low-cost and high-performance electrocatalysts remains a challenge for the hydrogen oxidation reaction (HOR) in alkaline membrane fuel cells. Here, we have reported novel Ni@h-BN ...core-shell nanocatalysts consisting of nickel nanoparticles encapsulated in few-layer h-BN shells. The Ni@h-BN catalysts exhibit an improved HOR performance compared with the bare Ni nanoparticles.
characterization experiments and density functional theory calculations indicate that the interactions of the O, H, and OH species with the Ni surface under the h-BN shell are weakened, which helps to maintain the active metallic Ni phase both in air and in the electrolyte and strengthen the HOR processes occurring at the h-BN/Ni interfaces. These results suggest a new route for designing high-performance non-noble metal electrocatalysts with encapsulating two-dimensional material overlayers for HOR reactions.
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