Showing papers on "Dehydrogenation published in 2020"

Comparative study of α-, β-, γ- and δ-MnO2 on toluene oxidation: Oxygen vacancies and reaction intermediates

Abstract: The structure-performance relationship of α-, β-, γ- and δ-MnO2 catalysts were studied. The four samples exhibited different activities of toluene oxidation in terms of distinct tunnel sizes, surface-active oxygen and redox properties. δ-MnO2 catalyst with K+ in the mezzanines of its layers presented the highest toluene oxidation activity under a GHSV of 60,000 mL·g−1 h−1, as well as good water resistance. HAADF images and EELS results showed that oxygen vacancies preferred to form on δ-MnO2 lattice with layer stack dislocations via Mn4+ reduction rather than β-MnO2 with good crystallization. These inherent-distorted structures with heterocations K+ improved the emerge-annihilate cycling of oxygen vacancies. In-situ DRIFTS results showed that toluene adsorption was facilitated via rapid dehydrogenation of methyl due to abundant surface adsorbed oxygen on δ-MnO2. In addition, benzoate, maleic and manganese carbonate on δ-MnO2 were the key intermediate species during toluene oxidation at relatively low temperatures.

Manipulating dehydrogenation kinetics through dual-doping Co 3 N electrode enables highly efficient hydrazine oxidation assisting self-powered H 2 production

Abstract: Replacing sluggish oxygen evolution reaction (OER) with hydrazine oxidation reaction (HzOR) to produce hydrogen has been considered as a more energy-efficient strategy than water splitting. However, the relatively high cell voltage in two-electrode system and the required external electric power hinder its scalable applications, especially in mobile devices. Herein, we report a bifunctional P, W co-doped Co3N nanowire array electrode with remarkable catalytic activity towards both HzOR (−55 mV at 10 mA cm−2) and hydrogen evolution reaction (HER, −41 mV at 10 mA cm−2). Inspiringly, a record low cell voltage of 28 mV is required to achieve 10 mA cm−2 in two-electrode system. DFT calculations decipher that the doping optimized H* adsorption/desorption and dehydrogenation kinetics could be the underlying mechanism. Importantly, a self-powered H2 production system by integrating a direct hydrazine fuel cell with a hydrazine splitting electrolyzer can achieve a decent rate of 1.25 mmol h−1 at room temperature. While facile hydrazine oxidation could replace the sluggish H2O oxidation reaction in renewable H2 production, few bifunctional catalysts exist. Here, authors explore a dual-doping strategy for Co3N nanowires that bestows bifunctionality toward both hydrazine oxidation and H2 evolution catalysis.

Subnanometer Bimetallic Platinum-Zinc Clusters in Zeolites for Propane Dehydrogenation

Abstract: Propane dehydrogenation (PDH) has great potential to meet the increasing global demand for propylene, but the widely used Pt-based catalysts usually suffer from short-term stability and unsatisfactory propylene selectivity. Herein, we develop a ligand-protected direct hydrogen reduction method for encapsulating subnanometer bimetallic Pt-Zn clusters inside silicalite-1 (S-1) zeolite. The introduction of Zn species significantly improved the stability of the Pt clusters and gave a superhigh propylene selectivity of 99.3 % with a weight hourly space velocity (WHSV) of 3.6-54 h-1 and specific activity of propylene formation of 65.5 mol C 3 H 6 gPt -1 h-1 (WHSV=108 h-1 ) at 550 °C. Moreover, no obvious deactivation was observed over PtZn4@S-1-H catalyst even after 13000 min on stream (WHSV=3.6 h-1 ), affording an extremely low deactivation constant of 0.001 h-1 , which is 200 times lower than that of the PtZn4/Al2 O3 counterpart under the same conditions. We also show that the introduction of Cs+ ions into the zeolite can improve the regeneration stability of catalysts, and the catalytic activity kept unchanged after four continuous cycles.

Revealing electrolyte oxidation via carbonate dehydrogenation on Ni-based oxides in Li-ion batteries by in situ Fourier transform infrared spectroscopy

Abstract: Understanding (electro-)chemical reactions at the electrode–electrolyte interface (EEI) is crucial to promote the cycle life of lithium-ion batteries. In this study, we developed an in situ Fourier-transform infrared spectroscopy (FT-IR) method, which provided unprecedented information on the oxidation of carbonate solvents via dehydrogenation on LiNixMnyCo1−x−yO2 (NMC). While ethylene carbonate (EC) was stable against oxidation on Pt up to 4.8 VLi, unique evidence for dehydrogenation of EC on LiNi0.8Co0.1Mn0.1O2 (NMC811) at voltages as low as 3.8 VLi was revealed by in situ FT-IR measurements, which was supported by density functional theory (DFT) results. Unique dehydrogenated species from EC were observed on NMC811 surface, including dehydrogenated EC anchored on oxides, vinylene carbonate (VC) and dehydrogenated oligomers which could diffuse away from the surface. Similar dehydrogenation on NMC811 was noted for EMC-based and LP57 (1 M LiPF6 in 3 : 7 EC/EMC) electrolytes. In contrast, no dehydrogenation was found for NMC111 or surface-modified NMC by coatings such as Al2O3. In addition, while the dehydrogenation of solvents was observed in 1 M electrolytes with different anions, they were not observed on NMC811 in the concentrated electrolyte (EC/EMC with 3.1 M LiPF6), indicating lithium coordination could suppress dehydrogenation. Dehydrogenation of carbonates on NMC811 accompanied with rapid growth of interfacial impedance with increasing voltage revealed by electrochemical impedance spectroscopy (EIS), while the electrode–electrolyte combinations without dehydrogenation did not show significant impedance growth. Therefore, minimizing carbonate dehydrogenation on the NMC surface by tuning electrode reactivity and electrolyte reactivity is critical to develop high-energy Li-ion batteries with long cycle life.

Partially exposed RuP2 surface in hybrid structure endows its bifunctionality for hydrazine oxidation and hydrogen evolution catalysis.

Abstract: Replacing the sluggish anode reaction in water electrolysis with thermodynamically favorable hydrazine oxidation could achieve energy-efficient H2 production, while the shortage of bifunctional catalysts limits its scale development. Here, we presented the scalable one-pot synthesis of partially exposed RuP2 nanoparticle-decorated carbon porous microsheets, which can act as the superior bifunctional catalyst outperforming Pt/C for both hydrazine oxidation reaction and hydrogen evolution reaction, where an ultralow working potential of -70 mV and an ultrasmall overpotential of 24 mV for 10 mA cm-2 can be achieved. The two-electrode electrolyzer can reach 10 mA cm-2 with a record-low cell voltage of 23 mV and an ultrahigh current density of 522 mA cm-2 at 1.0 V. The DFT calculations unravel the notability of partial exposure in the hybrid structure, as the exposed Ru atoms are the active sites for hydrazine dehydrogenation, while the C atoms exhibit a more thermoneutral value for H* adsorption.

Single-atom Pt in intermetallics as an ultrastable and selective catalyst for propane dehydrogenation.

Abstract: Propylene production via propane dehydrogenation (PDH) requires high reaction temperatures to obtain sufficient propylene yields, which results to prominent catalyst deactivation due to coke formation. Developing highly stable catalysts for PDH without deactivation even at high temperatures is of great interest and benefit for industry. Here, we report that single-atom Pt included in thermally stable intermetallic PtGa works as an ultrastable and selective catalyst for PDH at high temperatures. Intermetallic PtGa displays three-hold-Pt ensembles and single Pt atoms isolated by catalytically inert Ga at the surface, the former of which can be selectively blocked and disabled by Pb deposition. The PtGa-Pb/SiO2 catalyst exhibits 30% conversion with 99.6% propylene selectivity at 600 °C for 96 h without lowering the performance. The single-atom Pt well catalyzes the first and second C–H activation, while effectively inhibits the third one, which minimizes the side reactions to coke and drastically improves the selectivity and stability. Propylene production via propane dehydrogenation demands a highly stable catalyst that works without deactivation even at high temperatures. Here, the authors show that single-atom Pt included in thermally stable intermetallic PtGa works as an active and selective catalyst for propane dehydrogenation even at 600 °C for 96 h without deactivation.

Formation and stabilization of colloidal ultra-small palladium nanoparticles on diamine-modified Cr-MIL-101: Synergic boost to hydrogen production from formic acid.

Abstract: Ultra-small nano-sized palladium particles were successfully stabilized within the pores of diamine groups grafted open metal site metal-organic frameworks of Cr-MIL-101; coordinated diamine groups of ethylene diamine (ED) and propyl diamine (PD) on the active site of chromium units of Cr-MIL-101. The physiochemical properties of the Pd@Cr-MOFs were investigated using FTIR, XRD, SEM/EDX mapping, TEM, BET, and AAS. The Cr-MIL-101 stabilized ultra-small Pd nanoparticles, Pd@(ethylene diamine)/Cr-MIL-101, and Pd@(propyl diamine)/Cr-MIL-101, displayed catalytic activity for clean dehydrogenation of formic acid and generation of hydrogen at room temperature. The resultant Pd@ED/Cr-MIL-101 catalyst indicates high catalytic activity with turnover frequency (TOF) of 583 h−1 at 328 K, which is superior to most of the reported catalysts, including Pd@PD/Cr-MIL-101 with TOF 532 h−1. Our studies open up a new method to the design of an ultra-small metal nanoparticle for the catalytic dehydrogenation of HCOOH.

Plasma-assisted catalytic dry reforming of methane (DRM) over metal-organic frameworks (MOFs)-based catalysts

Abstract: Plasma-assisted dry reforming of methane (DRM) was performed in a dielectric barrier discharge (DBD) reactor. The effect of different packing materials including ZrO2, UiO-67 MOF and PtNP@UiO-67 on plasma discharge was investigated, showing that ZrO2 suppressed the plasma generation while UiO-67 improves it due to its porous nature which favours the formation of filamentary microdischarges and surface discharges. The improved plasma discharge increased the conversion of CH4 and CO2 by about 18% and 10%, respectively, compared to the plasma-alone mode. In addition, the distribution of hydrocarbon products changed from dominant C2H6 in the plasma-alone mode to C2H2 and C2H4 in the UiO-67 promoted plasma-assisted DRM. The UiO-67 MOF was stable in plasma, showing no significant changes in its properties under different treatment times, discharge powers and gases. Pt nanoparticles (NPs) on UiO-67 improved plasma-assisted DRM, especially the selectivity due to the presence of surface reactions. Due to the dehydrogenation of hydrocarbons over Pt NPs, the selectivity to hydrocarbons decreased by 30%, compared to the UiO-67 packing. In situ diffuse reflectance infrared Fourier transformed spectroscopy (DRIFTS) was carried out to probe the surface reactions on PtNP@UiO-67 catalyst, showing the decomposition of surface formats to CO and C2H4 dehydrogenation over the metallic Pt. The PtNP@UiO-67 catalyst showed good reusability in the plasma-assisted DRM, and H2 production was improved by high CH4/CO2 molar ratio and low feed flow rate.

Cobalt Single-Atom Catalysts with High Stability for Selective Dehydrogenation of Formic Acid.

Abstract: Metal-organic framework (MOF)-derived Co-N-C catalysts with isolated single cobalt atoms have been synthesized and compared with cobalt nanoparticles for formic acid dehydrogenation. The atomically dispersed Co-N-C catalyst achieves superior activity, better acid resistance, and improved long-term stability compared with nanoparticles synthesized by a similar route. High-angle annular dark-field-scanning transmission electron microscopy, X-ray photoelectron spectroscopy, electron paramagnetic resonance, and X-ray absorption fine structure characterizations reveal the formation of CoII Nx centers as active sites. The optimal low-cost catalyst is a promising candidate for liquid H2 generation.

Atomically Dispersed Co-P3 on CdS Nanorods with Electron-Rich Feature Boosts Photocatalysis.

Abstract: The development of highly efficient photocatalytic systems with rapid photogenerated charge separation and high surface catalytic activity is highly desirable for the storage and conversion of solar energy, yet remains a grand challenge. Herein, a conceptionally new form of atomically dispersed Co-P3 species on CdS nanorods (CoPSA-CdS) is designed and synthesized for achieving unprecedented photocatalytic activity for the dehydrogenation of formic acid (FA) to hydrogen. X-ray absorption near edge structure, X-ray photoelectron spectroscopy, and time-resolved photoluminescence results confirm that the Co-P3 species have a unique electron-rich feature, greatly improving the efficiency of photogenerated charge separation through an interface charge effect. The in situ attenuated total reflection infrared spectra reveal that the Co-P3 species can achieve much better dissociation adsorption of FA and activation of CH bonds than traditional sulfur-coordinated Co single atom-loaded CdS nanorods (CoSSA-CdS). These two new features make CoPSA-CdS exhibit the unprecedented 50-fold higher activity in the photocatalytic dehydrogenation of FA than CoSSA-CdS, and also much better activity than the Ru-, Rh-, Pd-, or Pt-loaded CdS. Besides, CoPSA-CdS also shows the highest mass activity (34309 mmol gCo -1 h-1 ) of Co reported to date. First-principles simulation reveals that the Co-P3 species herein can form an active PHCOO intermediate for enhancing the rate-determining dissociation adsorption of FA.

Size Dependence of Pt Catalysts for Propane Dehydrogenation: from Atomically Dispersed to Nanoparticles

Abstract: The structure–performance relationship is a critical fundamental issue in heterogeneous catalysis, and the size-dependent structure sensitivity of catalytic reactions has long been researched in ca...

Propane Dehydrogenation over Pt Clusters Localized at the Sn Single-Site in Zeolite Framework

Abstract: Catalytic dehydrogenation of propane over a Pt-based catalyst to propylene has received considerable interests in recent years because this route is able to provide an economical and efficient way ...

Zeolite-Encaged Pd-Mn Nanocatalysts for CO2 Hydrogenation and Formic Acid Dehydrogenation.

Abstract: A CO2 -mediated hydrogen storage energy cycle is a promising way to implement a hydrogen economy, but the exploration of efficient catalysts to achieve this process remains challenging. Herein, sub-nanometer Pd-Mn clusters were encaged within silicalite-1 (S-1) zeolites by a ligand-protected method under direct hydrothermal conditions. The obtained zeolite-encaged metallic nanocatalysts exhibited extraordinary catalytic activity and durability in both CO2 hydrogenation into formate and formic acid (FA) dehydrogenation back to CO2 and hydrogen. Thanks to the formation of ultrasmall metal clusters and the synergic effect of bimetallic components, the PdMn0.6 @S-1 catalyst afforded a formate generation rate of 2151 molformate molPd-1 h-1 at 353 K, and an initial turnover frequency of 6860 mol H2 molPd-1 h-1 for CO-free FA decomposition at 333 K without any additive. Both values represent the top levels among state-of-the-art heterogeneous catalysts under similar conditions. This work demonstrates that zeolite-encaged metallic catalysts hold great promise to realize CO2 -mediated hydrogen energy cycles in the future that feature fast charge and release kinetics.

Atomically dispersed Fe atoms anchored on COF-derived N-doped carbon nanospheres as efficient multi-functional catalysts

Abstract: Non-noble metal isolated single atom site (ISAS) catalysts have attracted much attention due to their low cost, ultimate atom efficiency and outstanding catalytic performance. Herein, atomically dispersed Fe atoms are prepared by a covalent organic framework (COF)-absorption-pyrolysis strategy. The obtained Fe ISASs anchored on COF-derived N-doped carbon nanospheres (Fe-ISAS/CN) served as a multi-functional catalyst in electro-catalysis and organic catalysis, exhibiting better catalytic performance than commercial Pt/C for the ORR with good stability and methanol tolerance. Besides electro-catalysis, the Fe-ISAS/CN also showed outstanding catalytic performance in organic reactions, such as the selective oxidation of ethylbenzene to acetophenone and dehydrogenation of 1,2,3,4-tetrahydroquinoline with excellent reactivity, selectivity, stability and recyclability. Co and Ni ISAS materials can also be prepared by this method, suggesting that it is a general strategy to obtain metal ISAS catalysts. This work will provide new insight into the design of COF-derived metal ISAS multi-functional catalysts for electro-catalysis and organic reactions using rationally designed synthetic routes and the optimized structure of substrates.

Coking-Resistant Iron Catalyst in Ethane Dehydrogenation Achieved through Siliceous Zeolite Modulation

Abstract: Nonoxidative dehydrogenation is promising for production of light olefins from shale gas, but current technology relies on precious Pt or toxic Cr catalysts and suffers from thermodynamically oriented coke formation. To solve these issues, the earth-abundant iron catalyst is employed, where Fe species are effectively modulated by siliceous zeolite, which is realized by the synthesis of Fe-containing MFI siliceous zeolite in the presence of ethylenediaminetetraacetic sodium (FeS-1-EDTA). Catalytic tests in ethane dehydrogenation show that this catalyst has a superior coke resistance in a 200 h run without any deactivation with extremely high activity and selectivity (e.g., 26.3% conversion and over 97.5% selectivity to ethene in at 873 K, close to the thermodynamic equilibrium limitation). Multiple characterizations demonstrate that the catalyst has uniformly and stably isolated Fe sites, which improves ethane dehydrogenation to facilitate the fast desorption of hydrogen and olefin products in the zeolite micropores and hinders the coke formation, as also identified by density functional calculations.

Catalytic Acceptorless Dehydrogenation of Aliphatic Alcohols

Abstract: We developed the first acceptorless dehydrogenation of aliphatic secondary alcohols to ketones under visible light irradiation at room temperature by devising a ternary hybrid catalyst system comprising a photoredox catalyst, a thiophosphate organocatalyst, and a nickel catalyst. The reaction proceeded through three main steps: hydrogen atom transfer from the α-C-H bond of an alcohol substrate to the thiyl radical of the photo-oxidized organocatalyst, interception of the generated carbon-centered radical with a nickel catalyst, and β-hydride elimination. The reaction proceeded in high yield under mild conditions without producing side products (except H2 gas) from various alcohols, including sterically hindered alcohols, a steroid, and a pharmaceutical derivative. This catalyst system also promoted acceptorless cross-dehydrogenative esterification from aldehydes and alcohols through hemiacetal intermediates.

Direct conversion of CO2 to aromatics with high yield via a modified Fischer-Tropsch synthesis pathway

Abstract: The direct conversion of CO2 to aromatics not only reduces carbon emissions but also provides an alternative way for value-added chemicals synthesis. Even though the hydrogenation of CO2 to aromatics has been realized via a methanol-mediated pathway or a modified Fischer-Tropsch synthesis route, low yield of aromatics is still the bottleneck of this strategy. Here, we develop a multifunctional catalyst composed of Na modified Fe-based catalyst and hollow acidic zeolite H-ZSM-5 to catalyze the hydrogenation of CO2 to aromatics by single pass. Na modified Fe-based catalyst prepared by pyrolysis of Fe-based metal-organic frameworks (Fe-MOFs) can boost the formation of alkenes intermediates because of its high active sites accessibility and precisely tailored catalytic interfaces. Thereafter, the produced alkenes can be converted to aromatics via the dehydrogenation and cyclization reactions when they diffuse to the acid sites of H-ZSM-5. The hollow H-ZSM-5 with short diffusional channels, appropriate density and strength of acid sites guaranteed the high yield of aromatics (203.8 gCH2 kgcat−1 h−1). Furthermore, the driving force in the tandem process can be attributed to the cooperative interplay between the multifunctional catalysts. The CO2 adsorbed on Fe-based catalyst can be employed as acceptors for H species produced from the dehydrogenation and cyclization reactions, thereby increasing the yield of aromatics by shifting the chemical thermodynamic equilibrium.

Using a Self-Assembled Two-Dimensional MXene-Based Catalyst (2D-Ni@Ti3C2) to Enhance Hydrogen Storage Properties of MgH2.

Abstract: In this work, we report the remarkable catalytic effects of a novel Ti3C2 MXene-based catalyst (Ni@Ti-MX), which was prepared via self-assembling of Ni nanoparticles onto the surface of exfoliated Ti3C2 nanosheets. The resultant Ni@Ti-MX catalyst, characterized by ultradispersed Ni nanoparticles being anchored on the monolayer Ti3C2 flakes, was introduced into MgH2 through ball milling. In situ transmission electron microscopy (TEM) analysis revealed that a synergetic catalytic effect of multiphase components (Mg2Ni, TiO2, metallic Ti, etc.) derived in the MgH2 + Ni@Ti-MX composite exhibits remarkable improvements in the hydrogen sorption kinetics of MgH2. In particular, the MgH2 + Ni@Ti-MX composite can absorb 5.4 wt % H2 in 25 s at 125 °C and release 5.2 wt % H2 in 15 min at 250 °C. Interestingly, it can uptake 4 wt % H2 in 5 h even at room temperature. Furthermore, the dehydrogenation peak temperature of the MgH2 + Ni@Ti-MX composite is about 221 °C, which is 50 and 122 °C lower than that of MgH2 + Ti-MX and MgH2, respectively. The excellent hydrogen sorption properties of the MgH2 + Ni@Ti-MX composite are primarily attributed to the peculiar core-shell nanostructured MgH2@Mg2NiH4 hybrid materials and the interfacial coupling effects from different catalyst-matrix interfaces. The results obtained in this study demonstrate that using self-assembling of transition-metal elements on two-dimensional (2D) materials as a catalyst is a promising approach to enhance the hydrogen storage properties of MgH2.

Mechanistic Analysis-Guided Pd-Based Catalysts for Efficient Hydrogen Production from Formic Acid Dehydrogenation

Abstract: Heterogeneous catalysis of formic acid dehydrogenation at room temperature is a promising tactic for safely storing and producing H2 as an efficient energy carrier. Up to now, the catalysts for thi...