Synthesis of Pt-Ni alloy nanocrystals with high-index facets and enhanced electrocatalytic properties.

The shape-controlled synthesis of multicomponent metal nanocrystals (NCs) bounded by high-index facets (HIFs) is of significant importance in the design and synthesis of high-activity catalysts. We report herein the preparation of Pt-Ni alloy NCs by tuning their shape from concave-nanocubic (CNC) to nanocubic and hexoctahedral (HOH). Owing to the synergy of the HIFs and the electronic effect of the Pt-Ni alloy, the as-prepared CNC and HOH Pt-Ni alloy NCs exhibited excellent catalytic properties for the electrooxidation of methanol and formic acid, as well as for the oxygen reduction reaction (ORR).

Turn the dust into glory: Hierarchical porous carbon cubes derived from waste tire pyrolysis oil exhibits high capability in symmetric capacitors.

Fabricating suitable porous carbon materials that are simultaneously applied in various electrochemical energy storage (EES) systems including supercapacitors (SCs) and lithium-ion capacitors (LICs) has an important significance in meeting the increasing demands in high energy density, high power density along with ultra-long life. Herein, cubic hierarchical porous carbon (CHPC) with abundant micro-mesoporous structures and moderate S, N co-doped atoms has been rationally designed by using MgO cubes as the templates and waste tire pyrolysis oil (WTPO) as carbon source and dopant. Attributed to the unique microstructures, the CHPC materials have been successfully utilized in different EES systems. In the aqueous electrolyte system, the assembled CHPC-2//CHPC-2 with 2 mg cm-2 delivered high specific capacitance of 199.0 at 1 A/g, along with 98.5 % capacity retention rate for 20,000 cycles at 6 A/g. Even at high mass loading of 12 mg cm-2, CHPC-12//CHPC-12 still can deliver high gravimetric and areal capacitances of 187.0 F g-1 and 2.24 F cm-2 at 10 A/g, showing an excellent high-loading performance. Even under extreme conditions of -40 and 60 °C, the assembled SCs still can deliver an ultrahigh capacity retention rate of 97.9 % and 100 % at 10 A/g for 2000 and 8000 cycles, respectively. In addition, the symmetric CHPC//CHPC LICs also have been assembled and displayed a maximal energy density of 133.5 Wh Kg-1 at 1178.2 W Kg-1. This work provides new insight into the high-value utilization of WTPO for prepared porous carbon with excellent electrochemical performance in various EES systems.

Pd cluster nanowires as highly efficient catalysts for selective hydrogenation reactions.

Palladium is a key catalyst invaluable to many industrial processes and fine-chemical synthesis. Although recent progress has allowed the synthesis of Pd nanoparticles with various shapes by using different techniques, the facile synthesis of Pd nanocrystals and turning them into a highly active, selective, and stable catalyst systems still remain challenging. Herein, we report the highly selective one-pot synthesis of monodisperse Pd cluster nanowires in aqueous solution; these consist of interconnected nanoparticles and may serve as highly active catalysts because of the enrichment of high index facets on the surface, including {443}, {331}, and {221} steps. For the first time, carbon nanotube and γ-Al(2)O(3) immobilized Pd cluster nanowires showed highly enhanced catalytic performance in the liquid-phase selective hydrogenation of cinnamaldehyde and gas-phase hydrogenation of 1,3butadiene relative to immobilized Pd icosahedra and nanocubes, as well as commercial Pd catalysts.

Effect of temperature on the diffusion mechanism of xylene isomers in a FAU zeolite: a molecular dynamics study.

The diffusion of o-, m-, and p-xylene in a FAU zeolite at 300-900 K was investigated using molecular dynamics simulations. Calculated self-diffusion coefficients of xylene isomers showed that the mobility of p-xylene was the fastest, m-xylene the second fastest, and o-xylene the slowest in the FAU zeolite at the same temperature. The diffusion activation energy of o-xylene, m-xylene and p-xylene was, respectively, determined to be 9.04, 7.45 and 6.44 kJ mol(-1) within the temperature range of 400 to 900 K, while to be 14.12, 13.59 and 15.47 kJ mol(-1) within the temperature range of 300 to 400 K. Xylene density profiles and orientational analysis suggested that this can be attributed to the xylene molecules that diffuse in the FAU zeolite by two different mechanisms at high and low temperatures. The behavior of motion for xylene in the FAU zeolite exhibits a "fluid-like" mode at high temperatures and exhibits a "jump-like" mode at low temperatures.

Theoretical investigation of water gas shift reaction catalyzed by iron group carbonyl complexes M(CO)5 (M = Fe, Ru, Os).

We have investigated the mechanism of M(CO)(5) (M = Fe, Ru, Os) catalyzed water gas shift reaction (WGSR) by using density functional theory and ab initio calculations. Our calculation results indicate that the whole reaction cycle consists of six steps: 1 → 2 → 3 → 4 → 5 → 6 → 2. In this stepwise mechanism the metals Fe, Ru, and Os behave generally in a similar way. However, crucial differences appear in steps 3 → 4 → 5 which involve dihydride M(H)(2)(CO)(3)COOH(-) (4') and/or dihydrogen complex MH(2)(CO)(3)COOH(-) (4). The stability of the dihydrogen complexes becomes weaker down the iron group. The dihydrogen complex 4_Fe is only 11.1 kJ/mol less stable than its dihydride 4'_Fe at the B3LYP/II(f)++//B3LYP/II(f) level. Due to very low energy barrier it is very easy to realize the transform from 4_Fe to 4'_Fe and vice versa, and thus for Fe there is no substantial difference to differentiate 4 and 4' for the reaction cycle. The most possible key intermediate 4'_Ru is 38.2 kJ/mol more stable than 4_Ru. However, the barrier for the conversion 3_Ru → 4'_Ru is 23.8 kJ/mol higher than that for 3_Ru → 4_Ru. Additionally, 4'_Ru has to go through 4_Ru to complete dehydrogenation 4'_Ru → 5_Ru. The concerted mechanism 4'_Ru → 6_Ru, in which the CO group attacks ruthenium while H(2) dissociates, can be excluded. In contrast to Fe and Ru, the dihydrogen complex of Os is too unstable to exist at the level of theory. Moreover, we predict Fe and Ru species are more favorable than Os species for the WGSR, because the energy barriers for the 4 → 5 processes of Fe and Ru are only 38.9 and 16.2 kJ/mol, respectively, whereas 140.5 kJ/mol is calculated for the conversion 4' → 5 of Os, which is significantly higher. In general, the calculations are in good agreement with available experimental data. We hope that our work will be beneficial to the development and design of the WGSR catalyst with high performance.

Template-Directing Coupled with Chemical Activation Methodology-Derived Hexagon-like Porous Carbon Electrode with Outstanding Compatibility to Electrolytes and Low-Temperature Performance.

The conversion of asphalt into hexagon-like porous carbon (HPC) with a micro-mesoporous structure is realized by the coupling of template-directing and chemical activation methodologies. The specific surface area of HPC can reach up to 1356 m2 g-1 even at such a low-proportioned dosage of activator (0.5-fold) and is also larger than those of template-directed carbon and activation-derived carbon, as it benefited from the coupling merits of template-directing and chemical activation. Excellent capacitive-energy-storage behavior with respect to rate capability, capacitance retention, and durability are delivered by HPC//HPC symmetric supercapacitors assembled with aqueous and organic electrolytes. This great compatibility for different kinds of electrolytes and electrode properties is owed to the robust hexagon-like microarchitecture feature associated with hierarchical pore structure, which not only hinders the stacking between each other but also provides a buffer function for the volume variation and sufficient active sites for the storage of electrolyte ions. The drastic temperature variation has almost no influence on the diffusion and transfer rate of electrolyte ions, further evidencing the advanced feature of the hierarchical pore structure. Additionally, HPC//Li4Ti5O12 LIC assembled with the Li-based electrolyte also presents a superior Ragone performance. The coexistence of micro- and mesopores for the HPC makes it an attractive electrode material for various capacitive-energy-storage devices. This work provides a promising way to realize the plasticity of pore channels and mass production of high capacitive storage ability of electrode material via the combination of template-directing and chemical activation strategies.

High Capacitive Energy Storage of Nest-Like Porous Graphene Microspheres Electrode with High Mass Loading.

Nest-like porous graphene microspheres (NPGMs) are grown by using a chemical vapor deposition (CVD) method in a fluidized bed reactor from methane and basic magnesium carbonate microspheres (synthesized by a stirring-induced crystallization approach) as carbon source and template, respectively. The CVD-derived NPGMs have a few-layer structure and high electrical conductivity, as well as a three-dimensional individual macroarchitecture accompanied with well-developed pore channels and great structural integrity. As the electrode for a symmetric supercapacitor, the effect of different mass loadings for NPGMs-based electrodes on the capacitive energy-storage performance is investigated. Superior electrochemical properties with respect to gravimetric, areal, and total capacitances, rate capability, and durability are shown by the NPGMs-based symmetric supercapacitors, even at mass loadings up to 10 mg cm-2 . Moreover, the electrochemical behavior of the NPGMs-based electrode is much superior to those of two-dimensional lamella-like graphene and commercial activated carbon.

Amino-modified molecular sieves for adsorptive removal of H2S from natural gas.

Amine-modified MCM-41 adsorbents (APTMS/MCM-41, PEI/MCM-41 and AAPTS/MCM-41) were prepared and characterized by XRD, N2 adsorption-desorption, FT-IR, TEM, SEM and TG-DTA. The performance of each adsorbent in a fixed adsorption bed for H2S removal was measured using a mixture of oxygen, nitrogen and hydrogen sulfide gases. It was found that the specific surface area decreased and the topography changed significantly after the use of each modified adsorbent. Nevertheless, all amine-modified MCM-41 adsorbents retained mesoporous silica of MCM-41. The H2S removal rate and saturated H2S capacity of APTMS/MCM-41 improved from 32.3% to 54.2% and 119.5 to 134.4 mg g-1, respectively, compared with that of MCM-41, and it showed the best performance among all adsorbents. APTMS/MCM-41, PEI/MCM-41 and AAPTS/MCM-41 were regenerated by maintaining at 423, 523 and 373 K in nitrogen for 3 h, respectively, and thus possessed high regenerability.

Excellent Compatibility of the Gravimetric and Areal Capacitances of an Electric-Double-Layer Capacitor Configured with S-Doped Activated Carbon.

Coffee grounds were converted into S-doped activated carbon (SAC) in the presence of an active agent and S dopant through a one-step synthesis approach. Carbonization, activation, and S doping was achieved through this one-step methodology. The SAC was used as an electrode material for the preparation of a symmetric electrical-double-layer capacitor (EDLC), and the influence of the loading mass of the active materials on the capacitive behaviors was investigated. The assembled SAC-based symmetric EDLC not only yielded a high capacitance but it also afforded a satisfactory capacitance retention. The symmetric EDLC constructed with loading mass SAC of 7.5 mg cm-2 was capable of delivering a maximum gravimetric and areal capacitance of 200 F g-1 and 1.5 F cm-2 , respectively. The compatibility of the gravimetric and areal capacitances of SAC was mainly attributed to the high abundance of interconnected pore channels, which were beneficial for the increased contact area between electrode and electrolyte ions, fast charge transfer, and fast diffusion of the electrolyte ions. In addition to the well-developed porous networks, the introduction of S into the carbon frameworks significantly enhanced the electrical conductivity, storage capacity, and rate capability. The developed one-step synthesis provides a facile and effective route for obtaining high-performance capacitive electrode materials and realizing high value-added utilization of biomass.

Competitive adsorption desulfurization performance over K - Doped NiY zeolite.

NiY and KNiY were successfully prepared by impregnation method and characterized by X-ray diffraction (XRD), N2 sorption (BET), scanning electron microscope (SEM), infrared spectrum (IR) and X-ray Photoelectron Spectroscopy (XPS). The competitive adsorption mechanisms of adsorbents were studied by in situ FTIR to explain different desulfurization performance which was evaluated in a miniature fixed-bed flow by gasoline model compounds with 1-hexene or toluene. NiY and KNiY adsorbents showed better desulfurization performance than HY zeolite due to the high selectivity of loaded active metals. Especially, KNiY adsorbent showed its advantages in desulfurization performance with 5vol% olefins or 5vol% aromatics involvement. It could be assigned that introduced K cation enhanced dispersion and content of active Ni species on the surface which made Ni species reduce easily. On the other hand, adsorption mechanisms showed that the protonation reactions of thiophene and 1-hexene occurred on the Brönsted acid sites of NiY, which resulted in pore blockage and the coverage of adsorption active centers. By doping K cation on NiY, the amount of the Brönsted acid sites of NiY was decreased and protonation reactions were weaken. Therefore, the negative effects of Brönsted acid sites were reduced.

Unraveling the adsorption mechanism of mono- and diaromatics in faujasite zeolite.

Monte Carlo simulations are performed to study the adsorption of aromatic molecules (toluene, styrene, o-xylene, m-xylene, p-xylene, 1,3,5-trimethylbenzene, and naphthalene) in all-silica faujasite (FAU) zeolite. For monoaromatics, a two-stage "ideal adsorption" and "insertion adsorption" mechanism is found by careful inspection of locations and distributions of the adsorbed toluene molecules. The validity of this mechanism is confirmed for all monoaromatics considered in the current study. Remarkably, the number of C atoms per unit cell corresponding to the inflection point of adsorbate loading (CI-P) is defined as a valid and convenient characterizing factor in the packing efficiency of monoaromatics in the FAU zeolite. For the case of naphthalene, a type of diaromatic, the three-stage mechanism is proposed, which consists of the first two stages and a third stage of "overideal adsorption". The so-called overideal adsorption is labeled because the naphthalene molecules start to occupy the S site nonideally at loadings that approach saturation, leading to a more localized feature of the adsorbates. The explicit adsorption mechanism can be used to understand the loading dependence of isosteric adsorption heat for the aromatics concerned.

Phosphorus and nitrogen dual-doped few-layered porous graphene: a high-performance anode material for lithium-ion batteries.

Few-layered graphene networks composed of phosphorus and nitrogen dual-doped porous graphene (PNG) are synthesized via a MgO-templated chemical vapor deposition (CVD) using (NH4)3PO4 as N and P source. P and N atoms have been substitutionally doped in graphene networks since the doping takes place at the same time with the graphene growth in the CVD process. Raman spectra show that the amount of defects or disorders increases after P and N atoms are incorporated into graphene frameworks. The doping levels of P and N measured by X-ray photoelectron spectroscopy are 0.6 and 2.6 at %, respectively. As anodes for Li ion batteries (LIBs), the PNG electrode exhibits high reversible capacity (2250 mA h g(-1) at the current density of 50 mA g(-1)), excellent rate capability (750 mA h g(-1) at 1000 mA g(-1)), and satisfactory cycling stability (no capacity decay after 1500 cycles), showing much enhanced electrode performance as compared to the undoped few-layered porous graphene. Our results show that the PNG is a promising candidate for anode materials in high-rate LIBs.

Enhancing the Li storage capacity and initial coulombic efficiency for porous carbons by sulfur doping.

Here, we report a new approach to synthesizing S-doped porous carbons and achieving both a high capacity and a high Coulombic efficiency in the first cycle for carbon nanostructures as anodes for Li ion batteries. S-doped porous carbons (S-PCs) were synthesized by carbonization of pitch using magnesium sulfate whiskers as both templates and S source, and a S doping up to 10.1 atom % (corresponding to 22.5 wt %) was obtained via a S doping reaction. Removal of functional groups or highly active C atoms during the S doping has led to formation of much thinner solid-electrolyte interface layer and hence significantly enhanced the Coulombic efficiency in the first cycle from 39.6% (for the undoped porous carbon) to 81.0%. The Li storage capacity of the S-PCs is up to 1781 mA h g(-1) at the current density of 50 mA g(-1), more than doubling that of the undoped porous carbon. Due to the enhanced conductivity, the hierarchically porous structure and the excellent stability, the S-PC anodes exhibit excellent rate capability and reliable cycling stability. Our results indicate that S doping can efficiently promote the Li storage capacity and reduce the irreversible Li combination for carbon nanostructures.

Hierarchical macro-meso-microporous ZSM-5 zeolite hollow fibers with highly efficient catalytic cracking capability.

Zeolite fibers have attracted growing interest for a range of new applications because of their structural particularity while maintaining the intrinsic performances of the building blocks of zeolites. The fabrication of uniform zeolite fibers with tunable hierarchical porosity and further exploration of their catalytic potential are of great importance. Here, we present a versatile and facile method for the fabrication of hierarchical ZSM-5 zeolite fibers with macro-meso-microporosity by coaxial electrospinning. Due to the synergistic integration of the suitable acidity and the hierarchical porosity, high yield of propylene and excellent anti-coking stability were demonstrated on the as-prepared ZSM-5 hollow fibers in the catalytic cracking reaction of iso-butane. This work may also provide good model catalysts with uniform wall thickness and tunable porosity for studying a series of important catalytic reactions.

Catalytic conversion wood syngas to synthetic aviation turbine fuels over a multifunctional catalyst.

A continuous process involving gasification, syngas cleaning, and Fischer-Tropsch (FT) synthesis was developed to efficiently produce synthetic aviation turbine fuels (SATFs). Oak-tree wood chips were first gasified to syngas over a commercial pilot plant downdraft gasifier. The raw wood syngas contains about 47% N(2), 21% CO, 18% H(2), 12% CO(2,) 2% CH(4) and trace amounts of impurities. A purification reaction system was designed to remove the impurities in the syngas such as moisture, oxygen, sulfur, ammonia, and tar. The purified syngas meets the requirements for catalytic conversion to liquid fuels. A multi-functional catalyst was developed and tested for the catalytic conversion of wood syngas to SATFs. It was demonstrated that liquid fuels similar to commercial aviation turbine fuels (Jet A) was successfully synthesized from bio-syngas.

High capacity gas storage in corrugated porous graphene with a specific surface area-lossless tightly stacking manner.

We report for the first time an experimental investigation of gas storage in porous graphene with nanomeshes. High capacity methane storage (236 v(STP)/v) and a high selectivity to carbon dioxide adsorption were obtained in the nanomesh graphene with a high specific surface area (SSA) and a SSA-lossless tightly stacking manner.

Solvothermal synthesis of Pt-Pd alloys with selective shapes and their enhanced electrocatalytic activities.

Pt-Pd bimetallic alloy nanostructures with highly selective morphologies such as cube, bar, flower, concave cube, and dendrite have been achieved through a facile one-pot solvothermal synthesis. The effects of shape-controllers (sodium dodecyl sulfate (SDS), ethylenediamine-tetraacetic acid disodium salt (EDTA-2Na), NaI) and solvents (water/DMF) on the morphologies were systematically investigated. The electrocatalytic activities of these Pt-Pd alloy nanostructures toward formic acid oxidation were tested. The results indicated that these alloy nanocrystals exhibited enhanced and shape-dependent electrocatalytic activity toward formic acid oxidation compared to commercial Pt black and Pt/C catalysts.

Gram-scale synthesis of nanomesh graphene with high surface area and its application in supercapacitor electrodes.

Graphene that had nanomeshes, only one to two graphene layers, and specific surface areas of up to 1654 m(2) g(-1) was produced on gram-scale by template growth on porous MgO layers. Its unique porous structure gave excellent electrochemical capacitance (up to 255 F g(-1)), cycle stability and rate performance.