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LaFe1-xMnxO3−δ as effective redox catalysts for CO2 splitting and methane partial oxidation in a cyclic redox scheme LaFe1-xMnxO3−δ作为循环氧化还原方案中CO2裂解和甲烷部分氧化的有效氧化还原催化剂
IF 5.3 2区 化学 Q1 CHEMISTRY, APPLIED Pub Date : 2026-02-01 Epub Date: 2025-09-04 DOI: 10.1016/j.cattod.2025.115546
Sherafghan Iftikhar , William Martin , Andrew Pedersen, Sam Portillo, Junchen Liu, Fanxing Li
The current study reports LaFe1-xMnxO3−δ redox catalysts (RCs) for CO2-splitting and methane partial oxidation (CH4-POx) in a cyclic redox scheme. Lanthanum (La) was chosen as the A-site cation whereas iron (Fe) and manganese (Mn) were chosen as the B-site cations, respectively. La, Fe, and Mn were incorporated into the perovskite structure (LaFe1-xMnxO3−δ) at various Fe/Mn ratios to tailor the equilibrium oxygen partial pressures for CO2-splitting and methane partial oxidation. Compared to the standalone redox pairs of Fe and Mn (i.e., Fe2O3/Fe3O4, Fe3O4/FeO, and Mn2O3/Mn3O4) which, from a thermodynamic standpoint, favor the complete combustion of CH4, the perovskite structured redox catalysts (RCs, i.e., LaFe1-xMnxO3−δ) favored the selective oxidation of CH4 to syngas. In addition, impregnating the RCs with 1 wt% ruthenium (Ru) led to a significant improvement in their redox kinetics without affecting their redox thermodynamics. The Ru-impregnated, perovskite structured RCs (i.e., LaFeO3, LaFe0.625Mn0.375O3, and LaFe0.5Mn0.5O3 ) exhibited excellent redox performance in terms of the syngas yield (92 – 100 %) and CO2 conversion (95–98 %). Long-term redox testing over Ru-impregnated LaFeO3 and LaFe0.5Mn0.5O3 demonstrated relatively stable performance for 100 redox cycles whereas activity loss was observed for LaFe0.625Mn0.375O3, LaFe0.375Mn0.625O3, and LaMnO3 respectively. Among RCs containing both Mn and Fe, LaFe0.5Mn0.5O3 exhibited the best performance, maintaining satisfactory activity over 100 cycles and higher oxygen capacity. XRD and XPS analysis suggest that the ability to regenerate the perovskite phase under a CO2 environment and a near surface A:B site cation ratio close to the perovskite stoichiometry would likely correspond to more stable performance. Additionally, the inclusion of Mn on the B-site enhances the coke resistance of the redox catalyst when compared to undoped LaFeO3.
本研究报道了LaFe1-xMnxO3−δ氧化还原催化剂(RCs)在循环氧化还原方案中用于co2裂解和甲烷部分氧化(CH4-POx)。选择镧(La)作为a位阳离子,选择铁(Fe)和锰(Mn)分别作为b位阳离子。将La, Fe和Mn以不同的Fe/Mn比掺入钙钛矿结构(LaFe1-xMnxO3−δ)中,以调整二氧化碳分裂和甲烷部分氧化的平衡氧分压。从热力学角度来看,Fe和Mn的独立氧化还原对(即Fe2O3/Fe3O4, Fe3O4/FeO和Mn2O3/Mn3O4)有利于CH4的完全燃烧,而钙钛矿结构的氧化还原催化剂(即LaFe1-xMnxO3−δ)有利于CH4的选择性氧化生成合成气。此外,用1 wt%钌(Ru)浸渍RCs,在不影响其氧化还原热力学的情况下,显著改善了它们的氧化还原动力学。钌浸透的钙钛矿结构rc(即LaFeO3、lafe0.625 mn0.3750 o3和LaFe0.5Mn0.5O3)在合成气收率(92 - 100 %)和CO2转化率(95-98 %)方面表现出优异的氧化还原性能。钌浸渍LaFeO3和LaFe0.5Mn0.5O3的长期氧化还原测试表明,lafe0.625 mn0.3750 o3、LaFe0.375Mn0.625O3和LaMnO3的氧化还原循环在100次循环中表现出相对稳定的性能,而lafe0.625 mn0.3750 o3和LaMnO3的氧化还原活性分别出现损失。在含锰和铁的rc中,LaFe0.5Mn0.5O3表现最好,在100次循环中仍保持令人满意的活性和较高的氧容量。XRD和XPS分析表明,在CO2环境下再生钙钛矿相的能力和接近钙钛矿化学计量的近表面a:B位阳离子比可能对应更稳定的性能。此外,与未掺杂的LaFeO3相比,b位上Mn的加入提高了氧化还原催化剂的抗焦性。
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引用次数: 0
Synthesis of hydroxyapatite – containing catalysts from bone waste – conventional route versus microwaves 用骨废物合成含羟基磷灰石催化剂的传统方法与微波法比较
IF 5.3 2区 化学 Q1 CHEMISTRY, APPLIED Pub Date : 2026-02-01 Epub Date: 2025-08-30 DOI: 10.1016/j.cattod.2025.115538
Gabriela Petcu , Mariana Patrascu , Virginia-Cora Gheorghe , Gabriela Ionescu , Marilena Radoiu , Aneta Magdziarz , Cosmin Mărculescu
The use of the hydroxyapatite (HA) contained in animal bone residues for the synthesis of active catalysts is an innovative solution to manage large quantities of bone waste (BW). In this study, two methods of preparing HA - containing catalysts were explored: i) conventional route using bone char (BC) from BW calcined at 500–900 °C, and ii) microwaves route using aqueous phase extraction from BW by a microwave (MW) -assisted process at 95 °C. BC mainly consisted of B-type HA, in which carbonate groups replace phosphate in the structure; however, its low surface area limited its catalytic performance. Modification with silica, MW treatment and surfactant charge had a critical effect on the formation of the porous structure, and consequently, on increasing the surface area of the composite catalysts. Cationic surfactants promoted silica network formation and resulted in improved porous structures due to their weaker interaction with the positively charged BC. The obtained HA-containing catalysts were demonstrated to be effective platforms for immobilising metallic species. Incorporating Ti and Zn by direct synthesis generated highly dispersed active sites, as confirmed by physicochemical characterization. Notably, an increase in sea buckthorn pyrolysis temperature (from 250 °C to 600 °C) was observed after just 5 min of MW irradiation using catalysts produced via the MW-assisted method, indicating enhanced heat transfer within the reactor. Meanwhile, catalysts produced via the conventional method significantly impacted the composition of the pyrolysis gas phase by promoting the formation of CO2 and hydrocarbons ≥C2, such as C2H2, C2H6, C3H8, C4H10, C5H12, and C6H14.
利用动物骨残留物中含有的羟基磷灰石(HA)合成活性催化剂是处理大量骨废物(BW)的创新解决方案。在本研究中,探索了两种制备含HA催化剂的方法:i)在500-900°C下煅烧BW中的骨炭(BC)的常规方法,ii)在95°C下通过微波(MW)辅助工艺从BW中水相萃取的微波方法。BC主要由b型HA组成,其中碳酸盐基团取代了结构中的磷酸盐;但其较低的比表面积限制了其催化性能。二氧化硅改性、MW处理和表面活性剂电荷对多孔结构的形成有重要影响,从而增加了复合催化剂的表面积。由于阳离子表面活性剂与带正电的BC相互作用较弱,促进了二氧化硅网络的形成,并改善了多孔结构。得到的含ha催化剂是固定化金属的有效平台。通过物理化学表征证实,直接合成Ti和Zn产生了高度分散的活性位点。值得注意的是,使用MW辅助法生产的催化剂,经过5 min的MW辐照后,沙棘热解温度从250°C提高到600°C,表明反应器内的传热增强。同时,常规方法制备的催化剂通过促进C2H2、C2H6、C3H8、C4H10、C5H12、C6H14等≥C2的碳氢化合物的生成,显著影响热解气相的组成。
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引用次数: 0
Amine-incorporated bridged polysilsesquioxane as a catalyst support for aqueous phase phenol hydrogenation 氨基桥接聚硅氧烷作为水相苯酚加氢的催化剂载体
IF 5.3 2区 化学 Q1 CHEMISTRY, APPLIED Pub Date : 2026-02-01 Epub Date: 2025-09-17 DOI: 10.1016/j.cattod.2025.115567
Snehal S. Patil , James Nana Gyamfi , Luke Gillespie , Yehia Khalifa , Seval Gunduz , Paul L. Edmiston , Umit S. Ozkan
Cyclohexanone is an important chemical used predominantly as an intermediate in nylon manufacturing. Phenol hydrogenation, a key route for producing cyclohexanone, results in a mixture of cyclohexanone and cyclohexanol. In this work, we have attempted to enhance the selectivity of phenol hydrogenation to cyclohexanone by doping amine functionalities in aryl-bridged polysilsesquioxane (ABPS), an organosilica support for palladium catalyst. Amine sites were successfully incorporated without compromising the textural properties and the structure of the organosilica via co-condensation of bis(trimethoxysilylethyl)benzene and bis(trimethoxysilylpropyl)amine, bridged organosilane precursors. Phenol hydrogenation activity experiments were conducted in an autoclave batch reactor at 200 °C and 50 bar. Amine-doping led to a significant increase in the cyclohexanone selectivity. CO2 TPD, phenol TPD, and aqueous phase adsorption experiments revealed that the enhanced strength of phenol adsorption in non-planar mode and preferential adsorption of phenol over cyclohexanone on basic amine-doped catalysts were responsible for the increase in cyclohexanone selectivity.
环己酮是一种重要的化学品,主要用作尼龙制造的中间体。苯酚加氢是生产环己酮的关键途径,可制得环己酮和环己醇的混合物。在这项工作中,我们试图通过在芳基桥接的聚硅氧烷(ABPS)中掺杂胺官能团来提高苯酚加氢到环己酮的选择性,ABPS是钯催化剂的有机二氧化硅载体。通过双(三甲氧基乙基)苯和双(三甲氧基丙基)胺的共缩合,成功地结合了胺位,而不影响有机硅的结构和结构。在200 °C和50 bar的高压间歇釜反应器中进行了苯酚加氢活性实验。胺掺杂导致环己酮选择性显著提高。CO2 TPD、苯酚TPD和水相吸附实验表明,在碱胺掺杂的催化剂上,苯酚在非平面模式下的吸附强度增强和苯酚对环己酮的优先吸附是环己酮选择性提高的原因。
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引用次数: 0
Effect of membrane properties on CO2 methanation reaction by using distributor type membrane reactor 分布式膜反应器中膜性能对CO2甲烷化反应的影响
IF 5.3 2区 化学 Q1 CHEMISTRY, APPLIED Pub Date : 2026-02-01 Epub Date: 2025-09-17 DOI: 10.1016/j.cattod.2025.115569
Yuka Shimizu , Hiroto Tsuyuki , Marcin Moździerz , Grzegorz Brus , Shinichi Ookawara , Keita Yabe , Aleksandra Roszko , Elzbieta Fornalik-Wajs , Mikihiro Nomura
CO2 methanation by using distributor type membrane reactor was investigated to control the reaction rate by distributed reactant feeding through membrane. Accurate evaluation of the thermal conductivity of the porous Al2O3 membrane, considering its fine physical and chemical structures, was achieved by measurements using Laser Flash Analysis. In the solid part of the 1TC sample, the thermal conductivity was found to be 36.4 % lower than that of non-porous alumina. A catalytic membrane with a silica separation layer, having an H₂ permeance of 1.4 × 10⁻⁶ mol m−2 s−1 Pa−1 and an H₂/CO₂ selectivity of 35.9, was used in the distributor type membrane reactor test, and a CO2 conversion of 92.3 % was obtained at 350 ℃. Based on these results, simulation was performed using Ansys Fluent to investigate the influence of membrane thermal conductivity and permselectivity. The CO2 permeance of the membrane was set equal to 3.91 × 10−8 mol m−2 s−1 Pa−1 for all conditions. It was shown that the CO2 permselective membrane (H2/CO2 selectivity = 35.9) produced about 1.4 times CH4 than the H2 permselective membrane (H2/CO2 selectivity = 0.10), and that higher thermal conductivity of the membrane suppressed the temperature rise in the reactor.
采用分布式膜反应器对CO2甲烷化反应进行了研究,通过膜给料来控制反应速率。考虑到多孔氧化铝膜的良好物理和化学结构,通过激光闪光分析实现了对多孔氧化铝膜导热系数的准确评价。在1TC样品的固体部分,热导率比无孔氧化铝低36.4% %。采用具有二氧化硅分离层的催化膜进行分布式膜反应器试验,其H₂透过率为1.4 × 10⁻26 mol m−2 s−1 Pa−1,H₂/CO₂选择性为35.9,在350℃下的CO2转化率为92.3 %。在此基础上,利用Ansys Fluent软件进行了模拟,研究了膜导热系数和透性的影响。在所有条件下,膜的CO2透过率设为3.91 × 10−8 mol m−2 s−1 Pa−1。结果表明,CO2膜(H2/CO2选择性= 35.9)比H2膜(H2/CO2选择性= 0.10)产生的CH4约为1.4倍,且膜的高热导率抑制了反应器内的升温。
{"title":"Effect of membrane properties on CO2 methanation reaction by using distributor type membrane reactor","authors":"Yuka Shimizu ,&nbsp;Hiroto Tsuyuki ,&nbsp;Marcin Moździerz ,&nbsp;Grzegorz Brus ,&nbsp;Shinichi Ookawara ,&nbsp;Keita Yabe ,&nbsp;Aleksandra Roszko ,&nbsp;Elzbieta Fornalik-Wajs ,&nbsp;Mikihiro Nomura","doi":"10.1016/j.cattod.2025.115569","DOIUrl":"10.1016/j.cattod.2025.115569","url":null,"abstract":"<div><div>CO<sub>2</sub> methanation by using distributor type membrane reactor was investigated to control the reaction rate by distributed reactant feeding through membrane. Accurate evaluation of the thermal conductivity of the porous Al<sub>2</sub>O<sub>3</sub> membrane, considering its fine physical and chemical structures, was achieved by measurements using Laser Flash Analysis. In the solid part of the 1TC sample, the thermal conductivity was found to be 36.4 % lower than that of non-porous alumina. A catalytic membrane with a silica separation layer, having an H₂ permeance of 1.4 × 10⁻⁶ mol m<sup>−2</sup> s<sup>−1</sup> Pa<sup>−1</sup> and an H₂/CO₂ selectivity of 35.9, was used in the distributor type membrane reactor test, and a CO<sub>2</sub> conversion of 92.3 % was obtained at 350 ℃. Based on these results, simulation was performed using Ansys Fluent to investigate the influence of membrane thermal conductivity and permselectivity. The CO<sub>2</sub> permeance of the membrane was set equal to 3.91 × 10<sup>−8</sup> mol m<sup>−2</sup> s<sup>−1</sup> Pa<sup>−1</sup> for all conditions. It was shown that the CO<sub>2</sub> permselective membrane (H<sub>2</sub>/CO<sub>2</sub> selectivity = 35.9) produced about 1.4 times CH<sub>4</sub> than the H<sub>2</sub> permselective membrane (H<sub>2</sub>/CO<sub>2</sub> selectivity = 0.10), and that higher thermal conductivity of the membrane suppressed the temperature rise in the reactor.</div></div>","PeriodicalId":264,"journal":{"name":"Catalysis Today","volume":"462 ","pages":"Article 115569"},"PeriodicalIF":5.3,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145227247","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Operando IR of catalytic reactions under microwaves at 5.8 GHz 5.8 GHz微波下催化反应的Operando IR
IF 5.3 2区 化学 Q1 CHEMISTRY, APPLIED Pub Date : 2026-02-01 Epub Date: 2025-09-18 DOI: 10.1016/j.cattod.2025.115571
Frédéric Thibault-Starzyk , Ana Neto , Sébastien Thomas , Carlos Henriques , Gary Bond
A new spectroscopic cell was designed for operando IR observation of heterogeneous catalysis under microwave irradiation. Oxidation of CO on Pt-H-BEA zeolite was performed under conventional and microwave heating at the same space velocity to assess the efficiency of microwave heating, which was confirmed by an infrared in-situ temperature scale. A temperature of 230–240°C was obtained after 2 min microwave irradiation. Infrared monitoring evidences a moderate sintering of the platinum particles after microwave irradiation, probably due to hotspots on the metal. Infrared observation indicates a strong perturbation of electron density in the Pt particles by microwave during catalysis.
设计了一种新的微波辐照多相催化操作红外光谱观察池。在相同的空速下,采用常规加热和微波加热对Pt-H-BEA沸石上的CO进行氧化,以评价微波加热的效率,并通过红外原位温标对其进行了验证。微波辐照2 min后温度为230-240℃。红外监测表明,微波辐照后铂颗粒有中度烧结,可能是由于金属上有热点。红外观测表明,在催化过程中,微波对铂粒子中的电子密度有很强的扰动。
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引用次数: 0
Revisiting rate-determining stage and prime activator for selective water-gas shift acceleration via redox mechanism 通过氧化还原机制重新考察了选择性水气转换加速的速率决定阶段和主要激活剂
IF 5.3 2区 化学 Q1 CHEMISTRY, APPLIED Pub Date : 2026-02-01 Epub Date: 2025-09-02 DOI: 10.1016/j.cattod.2025.115541
So Hyeon Park , Tao Zhou , Seonggeun Park , Taekyung Yu , Jongsik Kim
Halloysite can be deprotonated and dehydrated to transform into polymorphic Kaolinite, whose non-reducible Al3+/Al4+ (MII3+/4+) are positioned adjacent to reducible Pdδ+/Agδ+ (MIδ+; δ≤2) to facilitate •H confinement in PdXAg4-X alloys (X=1–3) functioning as MIδ+ reservoirs for expediting H2 release. This is conducive to provoke water-gas shift (WGS) preferentially via redox mechanism that has been controversial in terms of rate-determining step (RDS) and major activator. To this end, Kaolinite-supported PdXAg4-X alloys were synthesized to impart MII3+/4+-O2--MIδ+-O2--MII3+/4+ interfaces, where the redox mechanism can be accelerated using MIδ+ or proximal oxygen vacancy (OV) as the main activator. The amounts and electron (e-) affinity of MIδ+/OV species varied with dissimilar X values or their exposure to hydro-thermal aging (HT) environments, thereby linking with WGS kinetic parameters of the catalysts. The hierarchies of the energy barriers for the HT-unsubjected/subjected catalysts were con-current to their trends on e- affinity with OV species rather than those with MIδ+ counterparts. This demonstrated that the RDS is either CO2 desorption from MIδ+/OV or H2O homolysis on OV. Moreover, the ranks of the collision frequencies for the HT-unsubjected/subjected catalysts exactly matched their trends on OV quantities rather than those on MIδ+ quantities. This indicated that OV sites outweigh MIδ+ species to accelerate the redox mechanism as the prime activators. This study uncovers how to design or regulate the catalytic surfaces for prompting the WGS exclusively via the redox mechanism.
高岭土可以脱质子脱水转化为多晶高岭石,其不可还原性Al3+/Al4+ (MII3+/4+)位于可还原性Pdδ+/Agδ+ (MIδ+; δ≤2)附近,有利于将•H约束在PdXAg4-X合金(X= 1-3)中,作为MIδ+储层加速H2释放。这有利于通过氧化还原机制优先引发水气转换(WGS),这一机制在速率决定步骤(RDS)和主要活化剂方面一直存在争议。为此,合成了高岭石负载的PdXAg4-X合金,赋予MII3+/4+-O2—MIδ+-O2—MII3+/4+界面,其中以MIδ+或近端氧空位(OV)为主要活化剂可加速氧化还原机制。不同X值或暴露于水热老化(HT)环境中,MIδ+/OV的数量和电子亲和力不同,从而与催化剂的WGS动力学参数有关。未受ht影响/受ht影响的催化剂的能垒等级与它们与OV的e亲和趋势一致,而与MIδ+的e亲和趋势不同。这表明,RDS要么是MIδ+/OV对CO2的解吸,要么是OV对H2O的均解。此外,未受ht /受ht催化剂的碰撞频率的排列完全符合OV量的趋势,而不是MIδ+量的趋势。这表明OV位点比MIδ+位点更能加速氧化还原机制。本研究揭示了如何设计或调节催化表面,使其完全通过氧化还原机制促进WGS。
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引用次数: 0
Zeolite-supported palladium nanoparticles as universal heterogeneous Tsuji–Trost allylic alkylation catalysts 沸石负载的钯纳米颗粒作为通用多相Tsuji-Trost烯丙基烷基化催化剂
IF 5.3 2区 化学 Q1 CHEMISTRY, APPLIED Pub Date : 2026-02-01 Epub Date: 2025-08-29 DOI: 10.1016/j.cattod.2025.115537
Adéla Olšovská , Martin Kamlar , Subhajyoti Samanta , Jan Veselý , Jiří Čejka , Michal Mazur
The Tsuji–Trost allylic alkylation is mainly performed in homogeneous systems; however, developing efficient alternative, heterogeneous catalysts remains crucial for sustainable synthesis. This study introduces zeolite-supported palladium catalysts as viable heterogeneous catalysts in this reaction. The active catalysts, Pd@USY and Pd@deAl-USY, were synthesized via controlled impregnation and reduction to achieve ultrasmall Pd nanoparticles (2.2 nm and 2.5 nm in diameter, respectively). Pd@lay-MFI, serving as a reference material containing large nanoparticles (>20 nm), proved inactive in the reaction. Among the prepared materials, Pd@USY exhibited optimal performance in the model Tsuji–Trost reaction between diethyl malonate and allyl acetate, achieving complete conversion within 2 h under mild conditions (room temperature, dichloromethane, K₂CO₃), with activity directly correlated to nanoparticle size: inactive Pd@lay-MFI featured substantially bigger particles, while sub-3 nm particles in active catalysts enabled efficient substrate activation. The reaction scope demonstrated broad substrate compatibility, though nucleophilicity and α-substitution heavily influenced reactivity, and bulky substituents reduced conversion due to zeolite pore diffusion constraints and steric hindrance during nucleophilic attack. Catalyst reuse was feasible for at least two cycles before the catalyst became deactivated. The analysis of the deactivation mechanism is ongoing. Notably, the loss of activity was reversible, as regeneration successfully restored catalytic performance. The catalyst was stable against sintering, leaching, or poisoning. In conclusion, Pd@USY represents a promising heterogeneous alternative for Tsuji–Trost allylic alkylation, combining high activity, selectivity, and operational simplicity.
Tsuji-Trost烯丙基烷基化反应主要在均相体系中进行;然而,开发高效的替代多相催化剂对于可持续合成仍然至关重要。本研究介绍了沸石负载的钯催化剂作为该反应中可行的多相催化剂。通过控制浸渍和还原法制备了活性催化剂Pd@USY和Pd@deAl-USY,得到了直径分别为2.2 nm和2.5 nm的超小Pd纳米颗粒。Pd@lay-MFI作为含有大纳米颗粒(>20 nm)的参比物质,在反应中被证明是无活性的。在制备的材料中,Pd@USY在丙二酸二乙酯和醋酸烯丙酯之间的模型Tsuji-Trost反应中表现出最佳的性能,在温和的条件下(室温、二氯甲烷、K₂CO₃)在2 h内完成转化,其活性与纳米颗粒大小直接相关:不活跃的Pd@lay-MFI具有较大的颗粒,而活性催化剂中的亚3纳米颗粒能够有效地激活底物。尽管亲核性和α-取代严重影响反应活性,但反应范围具有广泛的底物相容性,而且在亲核攻击过程中,由于沸石孔扩散限制和位阻,体积大的取代基降低了转化。在催化剂失活之前,催化剂至少可以重复使用两个循环。对失活机理的分析正在进行中。值得注意的是,活性的丧失是可逆的,因为再生成功地恢复了催化性能。该催化剂对烧结、浸出或中毒都很稳定。总之,Pd@USY是Tsuji-Trost烯丙基烷基化的一种很有前途的异质替代品,具有高活性、选择性和操作简单的特点。
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引用次数: 0
Hydrogen production from aqueous formic acid solution using Pt/Cs with different preparation methods 不同制备方法下Pt/Cs在甲酸水溶液中制氢
IF 5.3 2区 化学 Q1 CHEMISTRY, APPLIED Pub Date : 2026-02-01 Epub Date: 2025-09-23 DOI: 10.1016/j.cattod.2025.115575
Shuka Murakami, Hiroyasu Fujitsuka, Motoaki Kawase
Formic acid is a promising hydrogen carrier because of its high hydrogen content and small enthalpy of dehydrogenation. Hydrogen is generally produced from formic acid via liquid-phase decomposition over catalysts. Catalysts consisting of noble metals that are stable in acidic solutions and carbon supports without acidic sites causing side reactions have several advantages, such as the high activity and ease of separation. To enhance catalytic activity, the surface area of the active metal should be increased. However, conventional impregnation methods are not completely suitable for this purpose because of the weak metal–carbon interactions. To solve this problem, a preparation method using an ion-exchange resin as a precursor for the carbon support was employed. In this study, we investigated the effect of the preparation method of carbon-supported Pt catalysts on their catalytic activity for the liquid-phase decomposition of formic acid. The catalysts prepared from ion-exchange resins exhibited Pt loadings of approximately 26–28 wt% and Pt particle sizes of 2–3 nm; therefore, this method can realize a higher dispersion degree of Pt nanoparticles than an impregnation method. Moreover, the produced catalysts demonstrated a higher activity for the dehydrogenation of formic acid than those of the catalysts prepared by the impregnation method. Additionally, the carbonization temperature strongly affected the catalyst properties, such as the pore size and metal accessibility. Consequently, the catalyst activity for the decomposition of formic acid varied depending on the carbonization temperature. We also formulated a new reaction model considering hydrogen adsorption.
甲酸具有氢含量高、脱氢焓小等优点,是一种很有前途的氢载体。氢通常是由甲酸通过催化剂的液相分解产生的。由在酸性溶液中稳定的贵金属和不产生副反应的碳载体组成的催化剂具有高活性和易于分离等优点。为了提高催化活性,必须增加活性金属的表面积。然而,由于金属-碳相互作用弱,传统的浸渍方法并不完全适用于这一目的。为了解决这一问题,采用离子交换树脂作为碳载体前驱体的制备方法。在本研究中,我们研究了碳负载Pt催化剂的制备方法对其液相分解甲酸催化活性的影响。离子交换树脂制备的催化剂的Pt负载约为26-28 wt%, Pt粒度为2-3 nm;因此,该方法可以实现比浸渍法更高的Pt纳米颗粒分散程度。制备的甲酸脱氢催化剂比浸渍法制备的甲酸脱氢催化剂具有更高的脱氢活性。此外,炭化温度对催化剂的孔径和金属可及性等性能也有较大影响。因此,甲酸分解的催化剂活性随炭化温度的变化而变化。我们还建立了一个考虑氢吸附的新反应模型。
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引用次数: 0
Guest editorial: Trends in catalyst design and novel catalytic materials 嘉宾评论:催化剂设计和新型催化材料的发展趋势
IF 5.3 2区 化学 Q1 CHEMISTRY, APPLIED Pub Date : 2026-02-01 Epub Date: 2025-09-01 DOI: 10.1016/j.cattod.2025.115539
József S. Pap, Andrzej Kotarba, Małgorzata Witko, David Kubička
While target reactions in catalysis remain consistent, the approach to designing and developing new catalysts continually evolves. This evolution is driven by advancements in materials science and investigative methods, leading to a deeper understanding of structure-reactivity relationships. This interdisciplinary synergy is fundamental to catalyst design and the creation of novel catalytic materials.
虽然催化中的目标反应保持不变,但设计和开发新催化剂的方法不断发展。这种演变是由材料科学和研究方法的进步驱动的,导致对结构-反应性关系的更深层次的理解。这种跨学科的协同作用是催化剂设计和新型催化材料创造的基础。
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引用次数: 0
Electrochemical hydrogen evolution and its reaction mechanism of hydroxypyridinate-bridged dirhodium(II) phenanthroline complex 羟基吡啶-桥接菲咯啉二钠配合物的电化学析氢及其反应机理
IF 5.3 2区 化学 Q1 CHEMISTRY, APPLIED Pub Date : 2026-02-01 Epub Date: 2025-09-02 DOI: 10.1016/j.cattod.2025.115542
Natsumi Yano, Kozo Sato, Makoto Handa, Yusuke Kataoka
A new 6-fluoro-2-hydroxypyridinate (fhp)-bridged dirhodium(II) complex containing a 1,10-phenanthroline (phen) ligand, [Rh2(μ-fhp)31-fhp)(phen)] (1), was prepared and characterized using nuclear magnetic resonance spectroscopy, electrospray ionization mass spectroscopy, elemental analysis, and synchrotron single crystal X-ray diffraction (SCXRD) analyses. In DMF, 1 was found to catalyze electrochemical proton reduction to evolve hydrogen in the presence of trifluoroacetic acid (Htfa) as a proton source. The turnover frequency and overpotential for hydrogen evolution catalyzed by 1 were 13263 s−1 and 457 mV, respectively. Interestingly, the intermediate species for the hydrogen evolution reaction, [Rh2(μ-fhp)3(phen)(η1-tfa)] (1-IM), could be crystallized from DMF solution of 1 in the presence of Htfa and was also characterized by synchrotron SCXRD. The reaction mechanism for the hydrogen evolution was thoroughly investigated based on the theoretically predicted redox potentials, pKa values, free energies, and binding energies. The findings are as follows: (i) the formation of the one-electron reduced species [1-IM] serves as an initial trigger for hydrogen evolution; (ii) 1-IM transforms into a protonated species, which immediately undergoes one-electron reduction; (iii) initial protonation occurs at the axial position of the Rh2 core, followed by a second one-electron reduction, possibly through a concerted proton-electron transfer (CPET); and (iv) the final reaction intermediate was identified as [2Hax-Rh2(μ-fhp)3(phen)(η1-tfa)] ([2Hax-1-IM]), in which two protons are bound in a side-on fashion at the axial position of the Rh2 core, their coordination being assisted by the tfa ligand. These results indicated that 1-IM promotes the electrochemical hydrogen evolution via an ECEC mechanism (E: electron transfer, C: chemical reaction).
摘要制备了一种含1,10-菲罗啉(phen)配体的6-氟-2-羟基吡啶(fhp)-桥接dihodium (II)配合物[Rh2(μ-fhp)3(η -fhp)(phen)](1),并用核磁共振、电喷雾质谱、元素分析和同步单晶x射线衍射(SCXRD)对其进行了表征。在DMF中,1被发现在三氟乙酸(Htfa)作为质子源存在的情况下催化电化学质子还原生成氢。1催化析氢的周转频率为13263 s−1,过电位为457 mV。有趣的是,析氢反应的中间产物[Rh2(μ-fhp)3(phen)(η -tfa)] (1- im)在Htfa存在下可以从DMF溶液中结晶,并通过同步加速器SCXRD进行了表征。基于理论预测的氧化还原电位、pKa值、自由能和结合能,对析氢反应机理进行了深入研究。结果表明:(1)单电子还原态[1-IM]−的形成是氢演化的初始触发;(ii) 1-IM转化为质子化态,立即发生单电子还原;(iii)初始质子化发生在Rh2核的轴向位置,随后是第二次单电子还原,可能是通过协调的质子-电子转移(CPET);(iv)最终反应中间体鉴定为[2Hax-Rh2(μ-fhp)3(phen)(η -tfa)] ([2Hax-1-IM]),其中两个质子在Rh2核的轴向位置侧对结合,tfa配体辅助它们的配位。这些结果表明,1-IM通过ECEC机制(E:电子转移,C:化学反应)促进电化学析氢。
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Catalysis Today
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