还原终温对磷化物催化剂加氢脱硫反应性能的影响

以全硅MCM-41为载体,制备负载Ni_2P和MoP型催化剂,考察了还原终温对催化剂制备和加氢脱硫反应性能的影响。对于Ni_2P/MCM-41,NiO负载质量分数为12%,通过XRD和加氢脱硫反应评价得出最佳还原终温为500℃;对于MoP/MCM-41,MoO_3负载质量分数为40%,通过XRD和加氢脱硫反应评价得出最佳还原终温为650℃。

磷化物催化剂体系下二苯并噻吩加氢反应网络研究

为考察二苯并噻吩在磷化物体系下催化加氢的反应网络,以分子筛SBA-15为空白载体,利用等体积浸渍制取了一系列磷化物催化剂,Ni/P摩尔比为1.25,对不同Ni金属担载量的磷化物催化剂的性质进行了分析。采用含有1%二苯并噻吩的模型化合物为原料进行加氢脱硫试验,利用20 m L连续固定床加氢精制装置对制备的磷化物催化剂进行了活性评价。结果表明,相对于商业催化剂,低温和磷化物催化剂体系下二苯并噻吩具有更高的转化率,280℃转化率可达80%以上;碱性氮化物喹啉的存在抑制了二苯并噻吩加氢反应,转化率在320℃时由接近100%降至70%左右,此条件下,产物中联苯以及环己烷基苯的选择性随温度变化不大,二苯并噻吩大部分通过直接脱硫路径进行转化。评价结果显示,磷化物催化剂具有更高的氢解活性和更好的直接加氢脱硫效果。

噻吩基硫化物催化加氢脱硫研究进展

综述了噻吩基硫化物加氢脱硫的反应特点,以及硫化钼基脱硫催化剂、氮化物催化剂和过渡金属磷化物催化剂的加氢脱硫性能。指出过渡金属磷化物催化剂的制备、组成、加氢脱氮(HDN)和加氢脱硫(HDS)活性的系统研究是一个新的领域。

Mass Spectrometric Studies of Selective Oxidation of n-Butane over a Vanadium Phosphorus Oxide Catalyst

The selective oxidation of n-butane to maleic anhydride (MA) on a vanadium-phosphorus oxide (VPO) catalyst was studied using on-line gas-chromatography combined with mass spectrometry(GC-MS) and transient response technique. The reaction intermediates, buterie and furan, were found in the reaction effluent under near industrial feed condition (3% butane+15%O2), while dihydrofuran was detected at high butane concentration (12% butane, 5%O2). Some intermediates of MA decomposition were also identified. Detection of these intermediates shows that the vanadium phosphorus oxides are able to dehydrogenate butane to butene, and butene further to form MA. Based on these observations, a modified scheme of reaction network is proposed. The transient experiments show that butane in the gas phase may directly react with oxygen both on the surface and from the metal oxide lattice, without a proceeding adsorption step. Gas phase oxygen can be adsorbed and transformed to surface lattice oxygen but it can not participate in selective oxidation. Adsorbed oxygen leads to deep oxidation, while lattice oxygen leads to selective oxidation.

Large-scale synthesis of noble-metal-free phosphide/CdS composite photocatalysts for enhanced H_2 evolution under visible light irradiation

Photocatalytic H2evolution under visible light irradiation is an ideal process for solving energy shortage.The low cost of photocatalysts and high efficiency of hydrogen evolution are the two key factors to realize the industrialization of the process.The substitution of a noble‐metal cocatalyst with a non‐noble‐metal catalyst can significantly reduce the cost of the photocatalyst.The largescale synthesis and assembly of semiconductors and non‐noble‐metal cocatalysts to form photocatalysts through a simple method can further decrease the cost of photocatalysis.Here,we report a large‐scale and low‐cost coprecipitation method to form phosphide/CdS photocatalysts to realize photocatalytic H2evolution.CoP and MoP cocatalysts significantly enhanced the photocatalytic production of hydrogen.The optimal H2production rates on CoP/CdS and MoP/CdS were140and78μmol/h,which were7.0and4.0times higher than those obtained with bare CdS,respectively,and2.0times and1.1times higher than those obtained with1.0%Pt/CdS,respectively.This work provides a practical method for the large‐scale preparation of low‐cost photocatalysts.

Recent developments in metal phosphide and sulfide electrocatalysts for oxygen evolution reaction

Oxygen evolution reaction(OER),as an important half‐reaction involved in water splitting,has been intensely studied since the last century.Transition metal phosphide and sulfide‐based compounds have attracted increasing attention as active OER catalysts due to their excellent physical and chemical characters,and massive efforts have been devoted to improving the phosphide and sulfide‐based materials with better activity and stability in recent years.In this review,the recent progress on phosphide and sulfide‐based OER electrocatalysts in terms of chemical properties,synthetic methodologies,catalytic performances evaluation and improvement strategy is reviewed.The most accepted reaction pathways as well as the thermodynamics and electrochemistry of the OER are firstly introduced in brief,followed by a summary of the recent research and optimization strategy of phosphide and sulfide‐based OER electrocatalysts.Finally,some mechanistic studies of the active phase of phosphide and sulfide‐based compounds are discussed to give insight into the nature of active catalytic sites.It is expected to indicate guidance for further improving the performances of phosphide and sulfide‐based OER electrocatalysts.

Cerium phosphate-supported Au catalysts for CO oxidation

LaPO_4 and hydroxyapatite(Ca_(10)(PO_4)_6(OH)_2)are typical metal phosphates recently found to be useful for making supported metal or metal oxide catalysts,but CePO_4(also belonging to the metal phosphate family)has been rarely used to make supported catalysts.It would be interesting to develop CePO_4-supported catalysts and explore their catalytic applications.Herein,hexagonal CePO_4 nanorods(denoted as CePO_4-H),hexagonal CePO_4 nanowires(CePO_4-HNW),monoclinic CePO_4 nanoparticles(CePO_4-M),and monoclinic CePO_4 nanowires(CePO_4-MNW)prepared by different methods were used to support gold via deposition-precipitation with urea(DPU).The gold contents of these catalysts were all around 1 wt%.The catalytic activities of these Au/CePO_4 catalysts in CO oxidation were found to follow the sequence of Au/CePO_4-MNW>Au/CePO_4-HNW> Au/CePO_4-M>Au/CePO_4-H.These catalysts were characterized by inductively coupled plasma-optical emission spectroscopy(ICP-OES),N_2 adsorption–desorption,X-ray diffraction(XRD),transmission electron microscopy(TEM),X-ray photoelectron spectroscopy(XPS),oxygen temperature-programmed desorption(O_2-TPD),and CO_2 temperature-programmed desorption(CO_2-TPD)to find possible correlations between the physicochemical properties and catalytic activities of these catalysts.

Temperature-controlled fabrication of Co-Fe-based nanoframes for efficient oxygen evolution

Transition metal phosphides(TMPs)have emerged as promising electrocatalysts to enhance the slow kinetic process of oxygen evolution reaction(OER).Framelike hollow nanostructures(nanoframes,NFs)provide the open structure with more accessible active sites and sufficient channels into the interior volume.Here,we report the fabrication of bimetallic Co-Fe phosphide NFs(Co-Fe-P NFs)via an intriguing temperature-controlled strategy for the preparation of precursors followed by phosphidation.The precursors,Co-Fe Prussian blue analogues(Co-Fe PBAs)are prepared by a precipitation method with Co^(2+)and[Fe(CN)_(6)]^(3−),which experience a structural conversion from nanocubes to NFs by increasing the aging temperature from 5 to 35℃.The experimental results indicate that this conversion is attributable to the preferentially epitaxial growth on the edges and corners of nanocubes,triggered by intramolecular electron transfer at an elevated aging temperature.The as-prepared Co-Fe-P NFs catalyst shows remarkable catalytic activity toward OER with a low overpotential of 276 mV to obtain a current density of 10 mA cm^(−2),which is superior to the reference samples(Co-Fe-P nanocubes)and most of the recently reported TMPs-based electrocatalysts.The synthetic strategy can be extended to fabricate Co-Fe dichalcogenide NFs,thereby holding a great promise for the broad applications in energy storage and conversion systems.

3D ordered mesoporous cobalt ferrite phosphides for overall water splitting

Developing low-cost and earth-abundant electrocatalysts with high performance for electrochemical water splitting is a challenging issue. Herein, we report a facile and effective way to fabricate three-dimension(3D) ordered mesoporous Co1-xFexP(x=0, 0.25, 0.5, 0.75) electrocatalyst.Benefiting from 3D ordered mesoporous pore channels and composition optimization, the Co0.75Fe0.25 P exhibits excellent electrocatalytic activities with low overpotentials of 270 and 209 mV at 10 mA cm^-2 for oxygen evolution reaction(OER)and hydrogen evolution reaction(HER), respectively, in the alkaline electrolyte along with a durable electrochemical stability. In addition, as both the cathode and anode, the Co0.75Fe0.25P also exhibits superior electrolysis water splitting performance with only an applied voltage of 1.63 V to attain a current density of 10 m A cm^-2 without obvious decay for 18 h,indicating that the Co0.75Fe0.25P is an efficient electrocatalyst for overall water splitting.