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Pt3Mn/SiO2 + ZSM-5 Bifunctional Catalyst for Ethane Dehydroaromatization 用于乙烷脱氢芳构化的 Pt3Mn/SiO2 + ZSM-5 双功能催化剂
IF 3.9 3区 化学 Q1 Environmental Science Pub Date : 2024-06-04 DOI: 10.3390/catal14060365
Shan Jiang, Che-Wei Chang, William A Swann, Christina W. Li, Jeffrey T. Miller
Ethane dehydroaromatization (EDA) is a potentially attractive process for converting ethane to valuable aromatics such as benzene, toluene, and xylene (BTX). In this study, a Pt3Mn/SiO2 + ZSM-5 bifunctional catalyst was used to investigate the effect of dehydrogenation and the Brønsted acid catalyst ratio, hydrogen partial pressure, and reaction temperature on the product distributions for EDA. Pt3Mn/SiO2 + ZSM-5 with a 1/1 weight ratio showed the highest ethane conversion rate and BTX formation rate. Ethylene is initially formed by dehydrogenation by the Pt3Mn catalyst, which undergoes secondary reactions on ZSM-5, forming C3+ reaction intermediates. The latter form final products of CH4 and BTX. At conversions from 15 to 30%, the BTX selectivities are 82–90%. For all bifunctional catalysts, the ethane conversion significantly exceeds the ethane–ethylene equilibrium conversion due to reaction to secondary products. Low H2 partial pressures did not significantly alter the product selectivity or conversion. However, higher H2 partial pressures resulted in increased methane and decreased BTX selectivity. The excess hydrogen saturated the olefin intermediates to form alkanes, which produced methane by monomolecular cracking on ZSM-5. With an increasing reaction temperature from 550 °C to 650 °C, the benzene selectivity increased, while the highest BTX selectivity was obtained at 600 to 650 °C.
乙烷脱氢芳构化(EDA)是将乙烷转化为苯、甲苯和二甲苯(BTX)等有价值芳烃的一种具有潜在吸引力的工艺。本研究使用 Pt3Mn/SiO2 + ZSM-5 双功能催化剂研究了脱氢、布氏酸催化剂比例、氢分压和反应温度对 EDA 产物分布的影响。重量比为 1/1 的 Pt3Mn/SiO2 + ZSM-5 的乙烷转化率和 BTX 生成率最高。乙烯最初由 Pt3Mn 催化剂脱氢生成,在 ZSM-5 上发生二次反应,形成 C3+ 反应中间产物。后者形成 CH4 和 BTX 的最终产物。当转化率为 15% 至 30% 时,BTX 的选择性为 82%-90%。对于所有双官能催化剂,乙烷转化率都大大超过乙烷-乙烯平衡转化率,原因是反应生成了副产品。较低的 H2 分压不会显著改变产品选择性或转化率。然而,较高的氢气分压导致甲烷增加,BTX 选择性降低。过量的氢使烯烃中间体饱和,形成烷烃,在 ZSM-5 上通过单分子裂解产生甲烷。随着反应温度从 550 ℃ 升至 650 ℃,苯的选择性增加,而在 600 至 650 ℃ 时,BTX 的选择性最高。
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引用次数: 0
TiO2-Based Catalysts with Various Structures for Photocatalytic Application: A Review 用于光催化应用的各种结构的 TiO2 基催化剂:综述
IF 3.9 3区 化学 Q1 Environmental Science Pub Date : 2024-06-04 DOI: 10.3390/catal14060366
Cheng Song, Lanqing Xiao, Yan Chen, Fan Yang, Huiying Meng, Wanying Zhang, Yifan Zhang, Yang Wu
TiO2-based catalysts with various surface heterostructures (0D, 1D, 2D, and 3D) have been widely researched owing to their cost-effectiveness, high stability, and environmentally friendly nature, and can be used for many applications in various fields, including hydrogen production and pollutant degradation. However, there are also many existing problems limiting their practical application, such as their large band gap and rapid electron–hole recombination rate. Owing to the abundance of recent achievements in materials science, we will summarize the recent structural engineering strategies which provide favorable photocatalytic activity enhancements, such as enhanced visible light absorption, stability, an increased charge–carrier separation rate and improved specific surface area. Among the various structural engineering methods in this review, we will introduce TiO2-based materials with different dimensional structures. Meanwhile, we also discuss recent achievements in synthesis methods and application of TiO2-based catalysts in various fields. We aim to display a comprehensive overview which can be a guide for the development of a new generation of TiO2-based catalysts according to their structural design for enhanced solar energy conversion.
具有各种表面异质结构(0D、1D、2D 和 3D )的 TiO2 基催化剂因其成本效益高、稳定性强和环境友好等特点而被广泛研究,并可用于制氢和污染物降解等多个领域。然而,目前也存在许多问题限制了它们的实际应用,例如它们的带隙过大、电子-空穴重组速率过快等。鉴于近年来材料科学领域取得的丰硕成果,我们将总结近期的结构工程策略,这些策略可提高光催化活性,如增强可见光吸收、稳定性、提高电荷载流子分离率和改善比表面积。在综述的各种结构工程方法中,我们将介绍具有不同尺寸结构的基于 TiO2 的材料。同时,我们还将讨论基于 TiO2 的催化剂在合成方法和各领域应用方面的最新成果。我们的目的是提供一个全面的综述,为根据结构设计开发新一代基于 TiO2 的催化剂提供指导,以提高太阳能转化率。
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引用次数: 0
Modification of NiSe2 Nanoparticles by ZIF-8-Derived NC for Boosting H2O2 Production from Electrochemical Oxygen Reduction in Acidic Media 用 ZIF-8 衍生的 NC 对 NiSe2 纳米粒子进行改性,以提高酸性介质中电化学氧还原法产生 H2O2 的能力
IF 3.9 3区 化学 Q1 Environmental Science Pub Date : 2024-06-03 DOI: 10.3390/catal14060364
Qiaoting Cheng, Hu Ding, Lang Chen, Jiatong Dong, Hao Yu, Shen Yan, Hua Wang
The two-electron oxygen reduction reaction (2e− ORR) has emerged as an attractive alternative for H2O2 production. Developing efficient earth-abundant transition metal electrocatalysts and reaction mechanism exploration for H2O2 production are important but remain challenging. Herein, a nitrogen-doped carbon-coated NiSe2 (NiSe2@NC) electrocatalyst was prepared by successive annealing treatment. Benefiting from the synergistic effect between the NiSe2 nanoparticles and NC, the 2e− ORR activity, selectivity, and stability of NiSe2@NC in 0.1 M HClO4 was greatly enhanced, with the yield of H2O2 being 4.4 times that of the bare NiSe2 nanoparticles. The in situ Raman spectra and density functional theory (DFT) calculation revealed that the presence of NC was beneficial for regulating the electronic state of NiSe2 and optimizing the adsorption free energy of *OOH, which could enhance the adsorption of O2, stabilize the O-O bond, and boost the production of H2O2. This work provides an effective strategy to improve the performance of the transition metal chalcogenide for 2e− ORR to H2O2.
双电子氧还原反应(2e- ORR)已成为生产 H2O2 的一种极具吸引力的替代方法。开发高效的富土过渡金属电催化剂和探索 H2O2 生成的反应机理非常重要,但仍然具有挑战性。本文通过连续退火处理制备了氮掺杂碳包覆的 NiSe2(NiSe2@NC)电催化剂。得益于NiSe2纳米颗粒与NC之间的协同效应,NiSe2@NC在0.1 M HClO4中的2e- ORR活性、选择性和稳定性大大提高,H2O2的产率是裸NiSe2纳米颗粒的4.4倍。原位拉曼光谱和密度泛函理论(DFT)计算表明,NC的存在有利于调节NiSe2的电子态,优化*OOH的吸附自由能,从而增强对O2的吸附,稳定O-O键,促进H2O2的产生。这项工作为提高过渡金属铬化物 2e- ORR 生成 H2O2 的性能提供了一种有效的策略。
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引用次数: 0
Non-Oxidative Coupling of Methane Catalyzed by Heterogeneous Catalysts Containing Singly Dispersed Metal Sites 含有单分散金属位点的异质催化剂催化甲烷的非氧化偶联反应
IF 3.9 3区 化学 Q1 Environmental Science Pub Date : 2024-06-02 DOI: 10.3390/catal14060363
Yuting Li, Jie Zhang
Direct upgrading of methane into value-added products is one of the most significant technologies for the effective transformation of hydrocarbon feedstocks in the chemical industry. Both oxidative and non-oxidative methane conversion are broadly useful approaches, though the two reaction pathways are quite distinguished. Oxidative coupling of methane (OCM) has been widely studied, but suffers from the low selectivity to C2 hydrocarbons because of the overoxidation leading to undesired byproducts. Therefore, non-oxidative coupling of methane is a worthy alternative approach to be developed for the efficient, direct utilization of methane. Recently, heterogeneous catalysts comprising singly dispersed metal sites, such as single-atom catalysts (SAC) and surface organometallic catalysts (SOMCat), have been proven to be effectively active for direct coupling of methane to product hydrogen and C2 products. In this context, this review summarizes recent discoveries of these novel catalysts and provides a perspective on promising catalytic processes for methane transformation via non-oxidative coupling.
将甲烷直接升级为增值产品是化工行业有效转化碳氢化合物原料的最重要技术之一。氧化和非氧化甲烷转化都是非常有用的方法,但这两种反应途径有很大区别。甲烷的氧化偶联(OCM)已被广泛研究,但由于过度氧化会产生不良副产品,因此对 C2 碳氢化合物的选择性较低。因此,甲烷的非氧化偶联是一种值得开发的高效直接利用甲烷的替代方法。最近,单原子催化剂(SAC)和表面有机金属催化剂(SOMCat)等由单个分散金属位点组成的异相催化剂已被证明可有效地将甲烷直接偶联为氢气和 C2 产物。在此背景下,本综述总结了这些新型催化剂的最新发现,并对通过非氧化偶联转化甲烷的前景广阔的催化过程进行了展望。
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引用次数: 0
Investigation and Comparison of Catalytic Methods to Produce Green CO2-Containing Monomers for Polycarbonates 研究和比较催化方法以生产用于聚碳酸酯的绿色含二氧化碳单体
IF 3.9 3区 化学 Q1 Environmental Science Pub Date : 2024-06-01 DOI: 10.3390/catal14060362
D. Brüggemann, P. Isbrücker, Dzenna Zukova, Franz Robert Otto Heinrich Schröter, Yen Hoang Le, Reinhard Schomäcker
The preparation of CO2-containing polymers with improved degradation properties is still very challenging. An elegant method for preparing these polymers is to use CO2-containing monomers in ring-opening polymerizations (ROP) which are particularly gentle and energy-saving methods. However, cyclic carbonates are required for this which are not readily available. This paper therefore aims to present the optimization and comparison of two synthesis methods to obtain cyclic carbonates for ROP. Within this work, cyclic styrene carbonate was synthesized from readily available raw materials by using a Jacobsen catalyst for the reaction of styrene oxide and carbon dioxide or an organocatalyst for the transesterification of methyl carbonate with 1-phenyl-1,2-ethanediol. The latter performed with 100% selectivity to the desired styrene carbonate, which was succesfully tested in ROP, producing an amorphous thermoplastic polymer with a TG of 185 ∘C.
制备具有更好降解性能的含二氧化碳聚合物仍然是一项非常具有挑战性的工作。制备这些聚合物的一种有效方法是在开环聚合(ROP)中使用含二氧化碳的单体,这是一种特别温和且节能的方法。然而,这种方法需要环状碳酸盐,而环状碳酸盐并不容易获得。因此,本文旨在对两种合成方法进行优化和比较,以获得用于 ROP 的环状碳酸盐。在这项工作中,使用雅各布森催化剂(用于氧化苯乙烯与二氧化碳的反应)或有机催化剂(用于碳酸甲酯与 1-苯基-1,2-乙二醇的酯交换反应),从现成的原材料中合成环状碳酸苯乙烯。后者对所需的碳酸苯乙烯具有 100% 的选择性,并成功地在 ROP 中进行了测试,产生了一种 TG 为 185 ∘C 的无定形热塑性聚合物。
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引用次数: 0
Efficient Charge Transfer of p-n Heterojunction UiO-66-NH2/CuFe2O4 Composite for Photocatalytic Hydrogen Production 用于光催化制氢的 p-n 异质结 UiO-66-NH2/CuFe2O4 复合材料的高效电荷转移
IF 3.9 3区 化学 Q1 Environmental Science Pub Date : 2024-05-24 DOI: 10.3390/catal14060341
M. Shanmugam, Nithish Agamendran, Karthikeyan Sekar
Using a p-n heterojunction is one of the efficient methods to increase charge transfer in photocatalysis applications. So, herein, p-type UiO-66 (NH2) and n-type CuFe2O4 (CFO) are used to form an effective p-n heterojunction. Due to their poor charge separation in their pristine form, both UiO-66 (NH2) and CFO materials cannot produce hydrogen; however, the composite p-n heterojunction formed between these materials makes fast charge separation and so hydrogen is efficiently produced. The optimized catalyst UCFO 25% produces a maximum of 62.5 µmol/g/h hydrogen in an aqueous methanol solution. The formation of a p-n heterojunction is confirmed by Mott–Schottky analysis and optical properties, crystallinity and the local atomic environment of the material was analyzed by various analytical tools like UV-Vis spectroscopy, XRD, and XANES.
在光催化应用中,使用 p-n 异质结是增加电荷转移的有效方法之一。因此,本文使用 p 型 UiO-66 (NH2) 和 n 型 CuFe2O4 (CFO) 形成有效的 p-n 异质结。由于原始形式的 UiO-66 (NH2) 和 CFO 材料的电荷分离能力较差,因此不能产生氢气;但是,这些材料之间形成的复合 p-n 异质结可以快速分离电荷,因此可以高效地产生氢气。经过优化的催化剂 UCFO 25% 在甲醇水溶液中最多可产生 62.5 µmol/g/h 的氢气。Mott-Schottky 分析证实了 p-n 异质结的形成,紫外可见光谱、XRD 和 XANES 等各种分析工具分析了材料的光学特性、结晶度和局部原子环境。
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引用次数: 0
Engineering the Integration of Titanium and Nickel into Zinc Oxide Nanocomposites through Nanolayered Structures and Nanohybrids to Design Effective Photocatalysts for Purifying Water from Industrial Pollutants 通过纳米层结构和纳米杂化技术将钛和镍整合到氧化锌纳米复合材料中,设计出有效的光催化剂来净化水中的工业污染物
IF 3.9 3区 化学 Q1 Environmental Science Pub Date : 2024-05-24 DOI: 10.3390/catal14060340
O. Saber, A. Osama, N. Shaalan, Mostafa Osama
Water pollution is one of the main challenges currently facing scientists around the world because of the rapid growth in industrial activities. On this basis, 2D nanolayered and nanohybrid structures, which are based on a ternary system of nickel–titanium–zinc, are considered favorable sources for designing effective nanocomposites for the photocatalytic degradation of industrial pollutants in a short period of time. These nanocomposites were designed by modifying two-dimensional nanolayers to produce a three-dimensional porous structure of multi-doped Ni/Ti-ZnO nanocomposites. Additionally, another additive was produced by constructing nanohybrids of nickel–titanium–zinc combined with a series of hydrocarbons (n-capric acid, myristic acid, stearic acid, suberic acid, and sebacic acid). Energy-dispersive X-ray spectrometry, X-ray diffraction, scanning electron microscopy, infrared spectroscopy, and thermal analyses confirmed the growth of the nanolayered and nanohybrid materials in addition to the production of nanocomposites. The positive role of the dopants (nickel and titanium) in producing an effective photocatalyst was observed through a significant narrowing of the band gap of zinc oxide to 3.05–3.10 eV. Additionally, the high photocatalytic activity of this nanocomposite enabled the complete removal of colored dye from water after 25 min of UV radiation. In conclusion, this study proposes an unconventional approach for designing new optical nanocomposites for purifying water. Additionally, it suggests a novel supporting method for designing new kinds of nanohybrids based on multi-metals and organic acids.
由于工业活动的快速增长,水污染是全球科学家目前面临的主要挑战之一。在此基础上,基于镍-钛-锌三元体系的二维纳米层和纳米杂化结构被认为是设计有效纳米复合材料的有利来源,可在短时间内光催化降解工业污染物。这些纳米复合材料是通过修改二维纳米层来设计的,以产生多掺杂镍/钛锌纳米复合材料的三维多孔结构。此外,通过构建镍-钛-锌与一系列碳氢化合物(正辛酸、肉豆蔻酸、硬脂酸、辛二酸和癸二酸)结合的纳米杂化物,还制备了另一种添加剂。能量色散 X 射线光谱、X 射线衍射、扫描电子显微镜、红外光谱和热分析证实了纳米层状和纳米杂化材料的生长,以及纳米复合材料的生产。通过将氧化锌的带隙显著缩小至 3.05-3.10 eV,可以观察到掺杂剂(镍和钛)在产生有效光催化剂方面的积极作用。此外,这种纳米复合材料具有很高的光催化活性,在紫外线照射 25 分钟后就能完全去除水中的有色染料。总之,本研究提出了一种非常规的方法来设计用于净化水的新型光学纳米复合材料。此外,它还为设计基于多金属和有机酸的新型纳米混合物提出了一种新颖的辅助方法。
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引用次数: 0
On-Purpose Oligomerization by 2-t-Butyl-4-arylimino-2,3-dihydroacridylnickel(II) Bromides 2-t-丁基-4-芳基亚氨基-2,3-二氢吖啶基镍(II)溴化物的通用低聚物作用
IF 3.9 3区 化学 Q1 Environmental Science Pub Date : 2024-05-24 DOI: 10.3390/catal14060342
Song Zou, Zheng Wang, Yizhou Wang, Yanping Ma, Yang Sun, Wen-Hua Sun
In this study, 2-t-butyl-4-arylimino-2,3-dihydroacridylnickel dibromides were synthesized by nickel-template one-pot condensation, and well characterized along with the single-crystal X-ray diffraction to one representative complex, revealing a distorted tetrahedral geometry around nickel. When activated with modified methylaluminoxane (MMAO), all nickel complexes exhibited high activities (up to 1.91 × 106 g mol−1 (Ni) h−1) toward major trimerization of ethylene. When activated with ethylaluminum dichloride (EtAlCl2), however, the title complexes performed good activities (up to 1.05 × 106 g mol−1 (Ni) h−1) for selective dimerization of ethylene. In comparison to analogous nickel complexes, higher activities were achieved with the substituent of t-butyl group, especially in the rare case of nickel complexes performing trimerization of ethylene.
本研究通过镍模板一锅缩合法合成了 2-t-丁基-4-芳基亚氨基-2,3-二氢吖啶基镍二溴化物,并对其中一个代表性络合物进行了单晶 X 射线衍射表征,发现镍周围存在扭曲的四面体几何形状。当用改性甲基铝氧烷(MMAO)激活时,所有镍络合物都表现出很高的活性(高达 1.91 × 106 g mol-1 (Ni) h-1),可实现乙烯的主要三聚化。然而,当用二氯化铝(EtAlCl2)激活时,标题络合物在乙烯的选择性二聚化方面表现出良好的活性(高达 1.05 × 106 g mol-1 (Ni) h-1)。与类似的镍络合物相比,以叔丁基为取代基的镍络合物具有更高的活性,尤其是在镍络合物对乙烯进行三聚的罕见情况下。
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引用次数: 0
Editorial: Biomass Derived Heterogeneous and Homogeneous Catalysts, 2nd Edition 编辑:生物质衍生异相和均相催化剂》,第 2 版
IF 3.9 3区 化学 Q1 Environmental Science Pub Date : 2024-05-23 DOI: 10.3390/catal14060339
José María Encinar Martín, S. Nogales-Delgado
There are plenty of challenges related to the current energy situation [...]
当前的能源形势面临诸多挑战 [...]
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引用次数: 0
Efficient Electron Transfer in g-C3N4/TiO2 Heterojunction for Enhanced Photocatalytic CO2 Reduction 在 g-C3N4/TiO2 异质结中实现高效电子转移以增强光催化二氧化碳还原能力
IF 3.9 3区 化学 Q1 Environmental Science Pub Date : 2024-05-22 DOI: 10.3390/catal14060335
Peng Jiang, Yang Yu, Kun Wang, Wenrui Liu
Excessive emissions of carbon dioxide have led to the greenhouse effect and global warming. Reducing carbon dioxide into high-value-added chemicals through solar energy is a promising approach. Herein, a g-C3N4/TiO2 heterojunction photocatalyst with efficient electron transfer is designed for photocatalytic CO2 reduction. The CH4 (18.32 µmol·h−1·g−1) and CO (25.35 µmol·h−1·g−1) evolution rates of g-C3N4/TiO2 are higher than those of g-C3N4 and TiO2. The enhanced photocatalytic CO2 reduction performance is attributed to the efficient charge carrier transfer in the g-C3N4/TiO2 heterojunction. The electron transfer route was verified by in situ irradiated X-ray photoelectron spectroscopy (XPS). The photocatalytic CO2 reduction mechanism on g-C3N4/TiO2 was investigated by in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). This work provides a strategy for designing a polymer/metallic oxide heterojunction with efficient electron transfer for enhanced photocatalytic CO2 reduction.
二氧化碳的过度排放导致了温室效应和全球变暖。通过太阳能将二氧化碳还原成高附加值化学品是一种前景广阔的方法。本文设计了一种具有高效电子传递功能的 g-C3N4/TiO2 异质结光催化剂,用于光催化还原二氧化碳。g-C3N4/TiO2 的 CH4(18.32 µmol-h-1-g-1)和 CO(25.35 µmol-h-1-g-1)演化率高于 g-C3N4 和 TiO2。光催化还原 CO2 性能的提高归功于 g-C3N4/TiO2 异质结中高效的电荷载流子转移。原位辐照 X 射线光电子能谱(XPS)验证了电子转移途径。通过原位漫反射红外傅里叶变换光谱(DRIFTS)研究了 g-C3N4/TiO2 光催化还原 CO2 的机理。这项研究为设计具有高效电子传递功能的聚合物/金属氧化物异质结以增强光催化还原 CO2 提供了一种策略。
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引用次数: 0
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