Efficient C-C bond splitting on Pt monolayer and sub-monolayer catalysts during ethanol electro-oxidation: Pt layer strain and morphology effects

Efficient catalytic C–C bond splitting coupled with complete 12-electron oxidation of the ethanol molecule to CO2is reported on nanoscale electrocatalysts comprised of a Pt monolayer (ML) and sub-monolayer (sML) deposited on Au nanoparticles (Au@Pt ML/sML). The Au@Pt electrocatalysts were synthesized using surface limited redox replacement (SLRR) of an underpotentially deposited (UPD) Cu monolayer in an electrochemical cell reactor. Au@Pt ML showed improved catalytic activity for ethanol oxidation reaction (EOR) and, unlike their Pt bulk and Pt sML counterparts, was able to generate CO2at very low electrode potentials owing to efficient C–C bond splitting. To explain this, we explore the hypothesis that competing strain effects due to the Pt layer coverage/morphology (compressive) and the Pt–Au lattice mismatch (tensile) control surface chemisorption and overall activity. Control experiments on well-defined model Pt monolayer systems are carried out involving a wide array of methods such as high-energy X-ray diffraction, pair-distribution function (PDF) analysis,in situelectrochemical FTIR spectroscopy, andin situscanning tunneling microscopy. The vibrational fingerprints of adsorbed CO provide compelling evidence on the relation between surface bond strength, layer strain and morphology, and catalytic activity.BMBF, 16N11929, Netzwerk TU9/CN Elektromobilität - Teilvorhaben: Brennstoffzellen Range-Extende

Episodic Accretion in Protostars -- An ALMA Survey of Molecular Jets in the Orion Molecular Cloud

Protostellar outflows and jets are almost ubiquitous characteristics during the mass accretion phase, and encode the history of stellar accretion, complex-organic molecule (COM) formation, and planet formation. Episodic jets are likely connected to episodic accretion through the disk. Despite the importance, there is a lack of studies of a statistically significant sample of protostars via high-sensitivity and high-resolution observations. To explore episodic accretion mechanisms and the chronologies of episodic events, we investigated 42 fields containing protostars with ALMA observations of CO, SiO, and 1.3\,mm continuum emission. We detected SiO emission in 21 fields, where 19 sources are driving confirmed molecular jets with high abundances of SiO. Jet velocities, mass-loss rates, mass-accretion rates, and periods of accretion events are found to be dependent on the driving forces of the jet (e.g., bolometric luminosity, envelope mass). Next, velocities and mass-loss rates are positively correlated with the surrounding envelope mass, suggesting that the presence of high mass around protostars increases the ejection-accretion activity. We determine mean periods of ejection events of 20$-$175 years for our sample, which could be associated with perturbation zones of $\sim$ 2$-$25\,au extent around the protostars. Also, mean ejection periods are anti-correlated with the envelope mass, where high-accretion rates may trigger more frequent ejection events. The observed periods of outburst/ejection are much shorter than the freeze-out time scale of the simplest COMs like CH$_3$OH, suggesting that episodic events largely maintain the ice-gas balance inside and around the snowline.Comment: Submitted to Journal; 27 pages, 15 Figures and additional Appendix materia

The ALMA-QUARKS survey: -- I. Survey description and data reduction

This paper presents an overview of the QUARKS survey, which stands for `Querying Underlying mechanisms of massive star formation with ALMA-Resolved gas Kinematics and Structures'. The QUARKS survey is observing 139 massive clumps covered by 156 pointings at ALMA Band 6 ($\lambda\sim$ 1.3 mm). In conjunction with data obtained from the ALMA-ATOMS survey at Band 3 ($\lambda\sim$ 3 mm), QUARKS aims to carry out an unbiased statistical investigation of massive star formation process within protoclusters down to a scale of 1000 au. This overview paper describes the observations and data reduction of the QUARKS survey, and gives a first look at an exemplar source, the mini-starburst Sgr B2(M). The wide-bandwidth (7.5 GHz) and high-angular-resolution (~0.3 arcsec) observations of the QUARKS survey allow to resolve much more compact cores than could be done by the ATOMS survey, and to detect previously unrevealed fainter filamentary structures. The spectral windows cover transitions of species including CO, SO, N$_2$D$^+$, SiO, H$_{30}\alpha$, H$_2$CO, CH$_3$CN and many other complex organic molecules, tracing gas components with different temperatures and spatial extents. QUARKS aims to deepen our understanding of several scientific topics of massive star formation, such as the mass transport within protoclusters by (hub-)filamentary structures, the existence of massive starless cores, the physical and chemical properties of dense cores within protoclusters, and the feedback from already formed high-mass young protostars.Comment: 9 figures, 4 tables, accepted by RA

ALMA Survey of Orion Planck Galactic Cold Clumps (ALMASOP) : Evidence for a Molecular Jet Launched at an Unprecedented Early Phase of Protostellar Evolution

Protostellar outflows and jets play a vital role in star formation as they carry away excess angular momentum from the inner disk surface, allowing the material to be transferred toward the central protostar. Theoretically, low-velocity and poorly collimated outflows appear from the beginning of the collapse at the first hydrostatic core (FHSC) stage. With growing protostellar core mass, high-density jets are launched, entraininf an outflow from the infalling envelope. Until now, molecular jets have been observed at high velocity (greater than or similar to 100 km s(-1)) in early Class 0 protostars. We, for the first time, detect a dense molecular jet in SiO emission with low velocity (similar to 4.2 km s(-1), deprojected similar to 24 km s(-1)) from source G208.89-20.04Walma (hereafter G208Walma) using ALMA Band 6 observations. This object has some characteristics of FHSCs, such as a small outflow/jet velocity, extended 1.3 mm continuum emission, and N2D+ line emission. Additional characteristics, however, are typical of early protostars: collimated outflow and SiO jet. The full extent of the outflow corresponds to a dynamical timescale of similar to 930(-100)(+200) yr. The spectral energy distribution also suggests a very young source having an upper limit of T-bol similar to 31 K and L-bol similar to 0.8 L-circle dot. We conclude that G208Walma is likely in the transition phase from FHSC to protostar, and the molecular jet has been launched within a few hundred years of initial collapse. Therefore, G208Walma may be the earliest object discovered in the protostellar phase with a molecular jet.Peer reviewe

ALMA Survey of Orion Planck Galactic Cold Clumps (ALMASOP): How Do Dense Core Properties Affect the Multiplicity of Protostars?

During the transition phase from a prestellar to a protostellar cloud core, one or several protostars can form within a single gas core. The detailed physical processes of this transition, however, remain unclear. We present 1.3 mm dust continuum and molecular line observations with the Atacama Large Millimeter/submillimeter Array toward 43 protostellar cores in the Orion molecular cloud complex (λ Orionis, Orion B, and Orion A) with an angular resolution of ∼0.″35 (∼140 au). In total, we detect 13 binary/multiple systems. We derive an overall multiplicity frequency (MF) of 28% ± 4% and a companion star fraction (CSF) of 51% ± 6%, over a separation range of 300-8900 au. The median separation of companions is about 2100 au. The occurrence of stellar multiplicity may depend on the physical characteristics of the dense cores. Notably, those containing binary/multiple systems tend to show a higher gas density and Mach number than cores forming single stars. The integral-shaped filament of the Orion A giant molecular cloud (GMC), which has the highest gas density and hosts high-mass star formation in its central region (the Orion Nebula cluster), shows the highest MF and CSF among the Orion GMCs. In contrast, the λ Orionis GMC has a lower MF and CSF than the Orion B and Orion A GMCs, indicating that feedback from H ii regions may suppress the formation of multiple systems. We also find that the protostars comprising a binary/multiple system are usually at different evolutionary stages.T.L. acknowledges support from the National Natural Science Foundation of China (NSFC) through grants No. 12073061 and No. 12122307, the International Partnership Program of the Chinese Academy of Sciences (CAS) through grant No. 114231KYSB20200009, the Shanghai Pujiang Program (20PJ1415500), and science research grants from the China Manned Space Project with no. CMS-CSST-2021-B06. K.T. was supported by Japan Society for the Promotion of Science (JSPS) KAKENHI (grant No. 20H05645). D.J. and J.d.F. are supported by NRC Canada and by NSERC Discovery Grants. C.-F.L. acknowledge grants from the Ministry of Science and Technology of Taiwan (MoST 107-2119-M-001-040-MY3 and 110-2112-M-001-021-MY3) and Academia Sinica (Investigator Award AS-IA-108-M01). This research was carried out in part at the Jet Propulsion Laboratory, which is operated by the California Institute of Technology under a contract with the National Aeronautics and Space Administration (80NM0018D0004). J.-E.L. was supported by a National Research Foundation of Korea grant funded by the Korean government (MSIT) (grant No. 2021R1A2C1011718). J.H. acknowledges the support of NSFC projects 11873086 and U1631237. This work is sponsored (in part) by the CAS, through a grant to the CAS South America Center for Astronomy in Santiago, Chile. S.-L.Q. is supported by the NSFC with grant No. 12033005. S.Z. acknowledges the support of the China Postdoctoral Science Foundation through grant No. 2021M700248. L.B. gratefully acknowledges support by the ANID BASAL projects ACE210002 and FB210003. P.S. was supported by a Grant-in-Aid for Scientific Research (KAKENHI No. 18H01259) of JSPS. V.-M.P. acknowledges support by the grant PID2020-115892GB-I00 funded by MCIN/AEI/10.13039/501100011033

An Investigation of Ni2P Single Crystal Surfaces : Structure, Electronic State and Reactivity

Ni2P has demonstrated high catalytic activity for hydrodesulfurization and has recently been employed as a catalyst in a variety of other reactions. We have thoroughly reviewed the literature concerning Ni2P single crystal surfaces, with the aim of determining the relationship between surface structure and catalytic properties. Published results to date indicate that Ni2P single crystal surfaces exhibit reconstructed structures, and so the bulk terminated structure may not be stable. We have also reviewed the surface structures and electronic states of (1 x 1) and reconstructed Ni2P(0001) and (1010). Based on these reviews, this paper presents general rules regarding stabilization of the Ni2P surface structure and discusses the role of phosphorus in the single crystal surfaces

FINITE SIZE EFFECT ON ELECTROSORPTION AND CATALYTIC PROPERTIES OF CATALYST MONOLAYERS

The 2D monolayer catalysts obtained by surface-limited redox replacement (SLRR) reaction have found wide applications in fuel cell technology. Their properties are very dependent on the morphology of the catalysts monolayers, i.e., the size/shape and structure of 2D nanoclusters constituents of the catalyst monolayer. This renders the need for better understanding of all processes involved in catalyst synthesis via SLRR including reaction kinetics, underpotential deposition (UPD) and catalyst nucleation. The first part of this PhD work focuses on UPD phenomenon as a critical step in development of more sophisticated protocols for catalyst monolayer synthesis using SLRR reaction. The Pb UPD has been studied on Pt and Ru submonolayer modified Au(111) surface using conventional electrochemical techniques, in-situ and exsitu Scanning Tunneling Microscopy (STM) and statistical image processing. The results suggest two distinct UPD process on Pt and Ru modified Au(111) surfaces each providing an opportunity for synthesis of more complex bi-metallic monolayer catalyst nano structures using SLRR reaction (nanoclusters). As a continuation of this effort, the new protocol for synthesis of Ru-Pt core-shell “hybrid” 2D nanocluster structures on Au(111) have been demonstrated. Their properties are compared with Ru, Pt and Pt-Ru alloy catalyst monolayers/nanoclusters on Au(111) using CO monolayer oxidation and electrosorption as the model probe molecule/reaction. The IR spectroscopy data are used for qualitative comparison of the strength of the CO-catalyst bond. These results are correlated with the CO oxidative stripping results. In the second part, the Pt nucleation during SLRR replacement of Cu UPD has been studied in order to better understand and describe relevant parameters controlling the Pt monolayer morphology (nanocluster size). The exsitu STM and statistical image processing are used to characterize the morphology of deposited Pt monolayers obtained in experiments where the coverage of Cu UPD has been varied from 0 to 1. The Pt nucleation density and the average size (area) of Pt nanoclusters are used as the main descriptors of Pt monolayer morphology. Results are discussed within the framework of analytical model developed to describe qualitatively our data. The relevance of our work for design of Pt monolayer catalyst is illustrated by our IR data illustrating CO electrosorption on Pt monolayers with different nucleation densities and average size of Pt nanoclusters. In the third part of our work, the finite-size effects (nanocluster size) in a system with strong d-orbital mixing such as Pt monolayer on Pd(hkl) were studied. IR data are used to compare qualitatively the strength of the CO-metal bond on Pt(hkl), Pd(hkl) and Pt/Pd(hkl) surfaces which were characterized by STM and statistical image processing. Our results demonstrate that the finite size of Pt nanoclusters constituents of the Pt monolayer of Pd(hkl) has a dominant effect on their electrosorption properties. The results are discussed in terms of the active strain in Pt nanoclusters, which is very different than the one expected from epitaxial relation between Pt and Pd. In an effort for better control of the morphology of Pt monolayers on Pd, the effect of citrates is studied on reaction kinetics of Pt deposition via SLRR of Cu UPD monolayer on Pd nanoparticles. The analytical model has been developed having a good predictive capability of the reaction rate constant during an industrial scale batch-reactor catalyst synthesis process.Electrical and Computer Engineering, Department o

Polarization-dependent Total Reflection Fluorescence X-ray Absorption Fine Structure (PTRF-XAFS) Studies on the Structure of a Pt Monolayer on Au(111) Prepared by the Surface-limited Redox Replacement Reaction

We studied the initial stage of a Pt monolayer produced by surface-limited redox replacement (SLRR) using polarization-dependent total reflection fluorescence X-ray absorption fine structure (PTRF-XAFS). Different from the widely accepted understanding that metallic monolayer islands are formed, our XAFS showed that the Pt monolayer, initially present on the Au(111) substrate, was mainly in the form of a planar [PtCl4]2− complex with its molecular plane parallel to Au(111). This result provides a new insight into the mechanism of SLRR

Effect of Saturated Steam Heat Treatment on Physical and Chemical Properties of Bamboo

The aim of this study was to investigate the effects of the heat treatment time and initial moisture content of bamboo on the corresponding chemical composition, crystallinity, and mechanical properties after saturated steam heat treatment at 180 °C. The mechanism of saturated steam heat treatment of bamboo was revealed on the micro-level, providing a theoretical basis for the regulation of bamboo properties and the optimization of heat treatment process parameters. XRD patterns of the treated bamboo slices were basically the same. With the increase in the initial moisture content of bamboo, the crystallinity of bamboo increased first and then decreased after treatment. Due to the saturated steam heat treatment, the content of cellulose and lignin in bamboo slices increased while the content of hemicellulose decreased, but the content of cellulose in bamboo with a 40% initial moisture content increased first and then decreased. The shear strength of treated bamboo changed little within 10 min after saturated steam heat treatment, and then decreased rapidly. During the first 20 min with saturated steam heat treatment, the compressive strength, flexural strength, and flexural modulus of elasticity of the treated bamboo increased, and then decreased