Kake Zhu

Direct Conversion of Bio-ethanol to Isobutene on Nanosized ZnxZryOz Mixed Oxides with Balanced Acid–Base Sites

We report the design and synthesis of nanosized Zn(x)Zr(y)O(z) mixed oxides for direct and high-yield conversion of bio-ethanol to isobutene (~83%). ZnO is addded to ZrO(2) to selectively passivate zirconias strong Lewis acidic sites and weaken Brönsted acidic sites, while simultaneously introducing basicity. As a result, the undesired reactions of bio-ethanol dehydration and acetone polymerization/coking are suppressed. Instead, a surface basic site-catalyzed ethanol dehydrogenation to acetaldehyde, acetaldehyde to acetone conversion via a complex pathway including aldol-condensation/dehydrogenation, and a Brönsted acidic site-catalyzed acetone-to-isobutene reaction pathway dominates on the nanosized Zn(x)Zr(y)O(z) mixed oxide catalyst, leading to a highly selective process for direct conversion of bio-ethanol to isobutene.

In Situ Formation of Cobalt Oxide Nanocubanes as Efficient Oxygen Evolution Catalysts

Oxygen evolution from water poses a significant challenge in solar fuel production because it requires an efficient catalyst to bridge the one-electron photon capture process with the four-electron oxygen evolution reaction (OER). Here, a new strategy was developed to synthesize nonsupported ultrasmall cobalt oxide nanocubanes through an in situ phase transformation mechanism using a layered Co(OH)(OCH3) precursor. Under sonication, the precursor was exfoliated and transformed into cobalt oxide nanocubanes in the presence of NaHCO3-Na2SiF6 buffer solution. The resulting cobalt catalyst with an average particle size less than 2 nm exhibited a turnover frequency of 0.023 per second per cobalt in photocatalytic water oxidation. X-ray absorption results suggested a unique nanocubane structure, where 13 cobalt atoms fully coordinated with oxygen in an octahedral arrangement to form 8 Co4O4 cubanes, which may be responsible for the exceptionally high OER activity.

Crystalline WO3 nanowires synthesized by templating method

Abstract A new method is developed to obtain crystalline nanowires of WO 3 using mesoporous silica SBA-15 as template. The method includes aminosilylation of the surface silanols within SBA-15 channels, anchoring of the heteropoly acid (HPA) to the grafted amine groups, thermal decomposition of the HPA, and removal of the silica framework with HF. The formation of the crystalline nanowires is monitored by the in situ XRD technique. TEM images intuitively confirm that the nanowires are uniform in diameter and HRTEM images further indicate that each nanowire belongs to single crystal although the growth orientations of these nanowires are different.

Preparation of three-dimensional chromium oxide porous single crystals templated by SBA-15

Three-dimensional porous chromium oxide single crystals have been prepared by aminosilylation of the surface silanols of the template, SBA-15, anchoring of dichromic acid to the grafted amine groups, thermal decomposition of inorganic and organic compounds, and removal of the silica framework with HF.

Carbon as a hard template for nano material catalysts

Abstract As one of the naturally abundant elements, carbon can present in different molecular structures (allotropes) and thus lead to various physical/chemical properties of carbon-based materials which have found wide applications in a variety of fields including electrochemistry, optical, adsorption and catalysis, etc. On the other hand, its different allotropes also endow carbon-based materials with various morphostructures, which have been recently explored to prepare oxides and zeolites/zeotypes with tailored structures. In this review, we mainly summarize the recent advances in using carbon materials as hard templates to synthesize structural materials. Specifically, we focus on the development in the synthetic strategies, such as endotemplating, exotemplating approaches and using carbon materials as chemical reagents for the synthesis of metal carbides or nitrides, with an emphasis laid on the control of morphostructure. Meanwhile, the applications of the obtained materials will be highlighted, especially, in the field of heterogeneous catalysis where enhanced performances have been achieved with the materials derived from carbon-templated methods.

Characterization of Dispersed Heteropoly Acid on Mesoporous Zeolite Using Solid-State 31P NMR Spin―Lattice Relaxation

Dispersion and quantitative characterization of supported catalysts is a grand challenge in catalytic science. In this paper, heteropoly acid H(3)PW(12)O(40) (HPA) is dispersed on mesoporous zeolite silicalite-1 derived from hydrothermal synthesis using carbon black nanoparticle templates, and the catalytic activity is studied for 1-butene isomerization. The HPAs supported on conventional zeolite and on mesoporous zeolite exhibit very different activities and thus provide good model systems to investigate the structure dependence of the catalytic properties. The HPA on mesoporous silicalite-1 shows enhanced catalytic activity for 1-butene isomerization, while HPA on conventional silicalite-1 exhibits low activity. To elucidate the structural difference, supported HPA catalysts are characterized using a variety of techniques, including (31)P magic angle spinning nuclear magnetic resonance, and are shown to contain a range of species on both mesoporous and conventional zeolites. However, contrary to studies reported in the literature, conventional NMR techniques and chemical shifts alone do not provide sufficient information to distinguish the dispersed and aggregated surface species. The dispersed phase and the nondispersed phase can only be unambiguously and quantitatively characterized using spin-lattice relaxation NMR techniques. The HPA supported on mesoporous zeolite contains a fast relaxation component related to the dispersed catalyst, giving a much higher activity, while the HPA supported on conventional zeolite has essentially only the slow relaxation component with very low activity. The results obtained from this work demonstrate that the combination of spinning sideband fitting and spin-lattice relaxation techniques can provide detailed structural information on not only the Keggin structure for HPA but also the degree of dispersion on the support.

Synthesis of hierarchically porous ZSM-5 zeolites by steam-assisted crystallization of dry gels silanized with short-chain organosilanes

Three short-chain organosilanes, i.e., 3-aminopropyltrimethoxy-silane (APTMS), [3-(2-aminoethyl)aminopropyl]trimethoxysilane (AEAPTMS) and phenylaminopropyltrimethoxysilane (PHAPTMS), were used for the synthesis of hierarchically micro-/mesoporous ZSM-5 zeolites by steam-assisted crystallization of silanized dry gels. Corresponding to the different moieties of organosilanes, the obtained hierarchically porous ZSM-5 zeolites have different degrees of mesoporosity and exhibit spherical morphology composed of small nanounits. Among the three organosilanes, PHAPTMS with a bulky cross-section is the most excellent mesopore directing agent. Tracking the structural evolution of PHAPTMS-ZSM-5 during crystallization shows that a large number of mesopores are produced in the initial steaming, but it is confirmed that it does not occur due to the presence of PHAPTMS. This initial mesoporosity is mostly preserved by the PHAPTMS molecules which inhibit the growth of the crystalline phase and suppress the high mobility of aluminosilicate species under the steam atmosphere.

Nonclassical from-shell-to-core growth of hierarchically organized SAPO-11 with enhanced catalytic performance in hydroisomerization of n-heptane

Integrating hierarchical porosity over microporous zeotype materials is an effective way to promote their mass transfer properties and catalytic performances. A combined synthetic strategy using small molecular growth inhibitor 1,2,3-hexanetriol and tumbling crystallization condition to generate hierarchically organized SAPO-11 is herein presented. The addition of 1,2,3-hexanetriol in the synthetic gel of SAPO-11 under agitating conditions significantly altered its crystallization behaviour, resulting in the formation of a hierarchically organized architecture. An underlying nonclassical from-shell-to-core crystallization has been disclosed by time-dependent observation of the formation process. The hierarchically self-organized structure has been characterized by a suite of characterization techniques, such as XRD, N2 physisorption, SEM, TEM, mercury intrusion measurements, 27Al, 29Si, 31P MAS NMR and pyridine adsorption IR (Py-IR). The structure featuring barrel-shaped architecture is comprised of aligned 300–400 nm primary building blocks with voids in between, constructing an auxiliary macro-/meso-pore system open to external surfaces. The catalytic performance of Pt supported on hierarchical SAPO-11 in n-heptane hydroisomerization has been assessed, showing that both catalytic activity and isomer yield have been increased with respect to a conventional sample. As the acidity for the hierarchical SAPO-11 is comparable to the conventional sample, the enhancement in catalytic performance is attributed to the small primary crystal size and macro-/meso-pore-connectivity, that are important for mass transfer.

A solvent evaporation route towards fabrication of hierarchically porous ZSM-11 with highly accessible mesopores

A route to generate hierarchically porous zeolite ZSM-11 has been paved via solvent evaporation induced self-assembly assisted by hexadecyltrimethoxysilane to produce a preformed dry gel, followed by its subsequent transformation into zeolite via steam-assisted-crystallization. The crystallization in dry gel has been found to undergo an orientated attachment growth mechanism whereby hexadecyltrimethoxysilane directs the formation of auxiliary mesopores and inhibits the fusion of primary nucleates. Measurements such as XRD, SEM, TEM, N2-physisorption, and TEM for an inverse replica of Pt derived from hierarchical ZSM-11 have been conducted to characterize the textural properties of the material. Ammonia temperature-programmed-desorption (NH3-TPD) measurements and infrared spectra using probe molecules such as pyridine (Py-IR) and 2,4,6-collidine (Coll-IR) have been collected to investigate the acidic properties as well as the accessibility of the acid sites. The hierarchical ZSM-11 possesses more acid sites on the mesopore surfaces that are accessible towards large probe molecules such as 2,4,6-collidine. This improvement together with the enhanced pore-connectivity brings about an increase in 1,3,5-triisopropylbenzene cracking activity and benzene selectivity with respect to a conventional counterpart.

Tailoring the Structure of Hierarchically Porous Zeolite Beta through Modified Orientated Attachment Growth in a Dry Gel System

The crystallization of zeolite beta in a dry gel system is found to follow the orientated attachment growth route, escorted with a temporal morphology change from bulky gel, through aggregation of the particulate to large zeolitic crystals. Modification of the precrystallized gel with organosilanes can be used to tune the morphology of the ultimate beta. When hexadecyltrimethoxysilane (HTS) is employed to modify precrystallized gel, a resumed secondary growth produces a hybrid mesocrystal of agglomerated nanozeolites. Combustive removal of organics leads to the formation of hierarchically porous zeolite beta of 100 to 160 nm, composed of nanocrystal building units ranging from 20 to 40 nm, with a noticeable micropore volume of 0.19 mL g(-1) and a meso/macropore size between 5 and 80 nm. Conversely, when 1,8-bis(triethoxysilyl)octane (BTO) is utilized to modify the same precrystallized gel, assemblages of discrete beta nanozeolite of around 35 nm are generated. These assemblages construct a hierarchical zeolite beta with a micropore volume of 0.20 mL g(-1) and auxiliary pores ranging from 5 to 100 nm. Both organosilanes bring about well-connected hierarchical pore networks. HTS has little effect on the Brønsted/Lewis acidity, whereas BTO causes a substantial reduction of strong Brønsted acid sites. The hierarchical beta zeolite-supported Pt catalyst exhibits improved catalytic performance for the hydroisomerization of n-heptane.