Applied Catalysis A: General最新文献

英文中文

Covalent organic frameworks modified with imidazole units anchored Keggin-type heteropoly acids for production of furfural from xylose and corncob 以咪唑单元修饰的共价有机框架锚定keggin型杂多酸，用于木糖和玉米芯生产糠醛

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2026-02-05 Epub Date: 2025-12-19 DOI: 10.1016/j.apcata.2025.120754

Yunqing Liu , Xin Huang , Zhao Huang , Fang Su , Daiyu Song

A series of nitrogen-rich porous covalent imine network modified with imidazole units anchored Keggin-type H₃PW₁₂O₄₀ (PW-ICIN) were prepared via one-pot co-condensation strategy. The Keggin-type PW clusters can be in situ immobilized onto the ICIN support through physical confinement and hydrogen bonds. The synergistic catalytic effect between the N-rich units and the PW clusters of the catalyst was expected to boost catalytic activity. The catalytic performance of the PW-ICIN catalyst was systematically evaluated in the dehydration of xylose to furfural, with emphasis on the effects of reaction parameters, catalyst stability, and synergistic mechanisms. The catalytic activity of the PW-ICIN catalyst was higher than those of the commercial solid acids (e.g., Amberlyst-15 and HY zeolite) in production of furfural from xylose and corncob, respectively. The high yield of FF (52.7 % and 33.0 %) and TOF value (0.026 min^–1 and 0.054 min^–1) were obtained in the PW-ICIN-3-catalyzed xylose and corncob conversion, respectively, at 160 °C for 6 h. These advantages of appropriate acid properties, various N-rich units, and excellent porosity property of the PW-ICIN catalysts can significantly improve the catalytic activity. The reaction pathway and mechanism of production of FF from xylose have been reasonably speculated. The robust interaction between PW clusters and frameworks ensured the well reusability of PW-ICIN catalyst. This work aims to advance the rational design of COF-anchored heteropoly acids for sustainable biomass conversion.

采用一锅共缩聚法制备了咪唑基锚定keggin型H3PW12O40 （PW-ICIN）修饰的富氮多孔共价亚胺网络。keggin型PW簇可以通过物理约束和氢键原位固定在ICIN支架上。富n单元与PW簇之间的协同催化作用有望提高催化剂的催化活性。系统评价了PW-ICIN催化剂在木糖脱水制糠醛过程中的催化性能，重点考察了反应参数、催化剂稳定性和协同机理的影响。PW-ICIN催化剂在木糖和玉米芯制备糠醛过程中的催化活性分别高于商用固体酸（如Amberlyst-15和HY沸石）。pw - icin -3催化木糖和玉米芯转化，在160 °C、6 h下，FF的产率分别为52.7% %和33.0% %，TOF值分别为0.026 min-1和0.054 min-1。PW-ICIN催化剂具有适宜的酸性、丰富的富n单元和优异的孔隙性等优点，可显著提高催化剂的催化活性。对木糖生产FF的反应途径和机理进行了合理的推测。PW簇与框架之间的强相互作用保证了PW- icin催化剂的良好可重用性。本工作旨在促进cof锚定杂多酸的合理设计，以实现可持续的生物质转化。

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引用次数: 0

Catalytic glycolysis of polyethylene terephthalate over MgO/Y2O3 with reduced ethylene glycol consumption MgO/Y2O3催化糖酵解聚对苯二甲酸乙二醇酯，降低乙二醇用量

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2026-02-05 Epub Date: 2025-11-29 DOI: 10.1016/j.apcata.2025.120730

Hina Mehjabeen , Fuping Tian , Li Rui , Jicong Yan , Tao Hu , Xiang Wang

Chemical recycling provides a route for closed-loop recycling of polyethylene terephthalate (PET), in which post-consumer PET is depolymerized to bis(2-hydroxyethyl) terephthalate (BHET) via glycolysis and can subsequently be repolymerized to produce recycled PET (rPET). Herein, we have developed a heterogeneous catalytic approach using MgO/Y₂O₃, the first reported use of Y₂O₃ for polyester depolymerization to facilitate the glycolysis of PET. The catalyst provides strong and stable basic sites, enabling the depolymerization of 10 g PET with 0.1 g catalyst in 20 mL ethylene glycol (EG) at 185 °C for 2.25 h, achieving 88 ± 3 % PET conversion and 85 ± 3 % BHET yield. In addition, this work demonstrates high PET conversion and BHET yield under relatively mild conditions using a low amount of EG.

化学回收为聚对苯二甲酸乙二醇酯（PET）的闭环回收提供了一条途径，其中消费后的PET通过糖酶解解聚成双（2-羟乙基）对苯二甲酸乙二醇酯（BHET），随后可以再聚合产生再生PET （rPET）。在此，我们开发了一种使用MgO/Y2O3的多相催化方法，这是首次报道使用Y2O3进行聚酯解聚以促进PET的糖酵解。催化剂提供了强大和稳定的基本网站,使解聚10 g宠物0.1 g催化剂在20 毫升乙二醇(EG)在185°C 2.25 h,实现88年 ±  %宠物转换和85 ± 3 % BHET产量。此外，本研究表明，在相对温和的条件下，使用少量EG， PET转化率和bet收率较高。

引用次数: 0

On the origin of methane in the RWGS: Insights into selectivity on Mo2C catalysts 甲烷在RWGS中的来源：对Mo2C催化剂选择性的认识

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2026-02-05 Epub Date: 2025-11-30 DOI: 10.1016/j.apcata.2025.120735

Wijnand Marquart, Michael Claeys, Nico Fischer

The reverse water-gas shift (RWGS) reaction is thermodynamically limited due to its endothermic nature in terms of CO₂ conversion. While higher reaction temperatures and increased H₂/CO₂ feed ratios can enhance CO₂ conversion, a more efficient approach involves reaction intensification via the removal of the by-product (H₂O), shifting the equilibrium per Le Chatelier’s principle. Ex situ H₂O removal, combined with recycling of unreacted gases leads to CO-enriched feeds, which in turn promotes methanation, especially at lower temperatures. In this study, the origin of CH₄ formation was investigated under both conventional and CO-enriched RWGS feed conditions using (isotopically labelled) transient, breakthrough, experiments over a Mo₂C catalysts, known for its high RWGS activity. In CO-free feeds, methanation is highly suppressed, even under elevated pressure. In contrast, a CO enriched feed significantly enhanced CH₄ formation, particularly during reaction initiation. Using isotopically labelled C¹³O₂, two key insights were revealed: (1) CH₄ is primarily formed via adsorbed *CO species (either adsorbed from the gas phase or via CO₂ dissociation), and (2) in the presence of an extra reducing agent in the feed (CO), the activity of the catalysts is improved by facilitating the removal of surface *O species. These findings underscore the importance of improving the hydrogenation (or *O removal) capacity of Mo₂C catalysts to boost performance under both conventional and intensified RWGS conditions.

逆水气转换反应（RWGS）由于其吸热性质，在CO2转化方面受到热力学限制。虽然提高反应温度和增加H2/CO2进料比可以提高CO2转化率，但更有效的方法是通过去除副产物（H2O）来强化反应，根据勒夏特列原理改变平衡。脱除H2O，结合未反应气体的回收，产生co富集的饲料，这反过来促进甲烷化，特别是在较低温度下。在本研究中，利用（同位素标记的）瞬态突破实验，研究了在常规和co富集的RWGS进气条件下CH4形成的来源。在无co饲料中，甲烷化被高度抑制，即使在高压下也是如此。相反，富含CO的饲料显著提高了CH4的形成，特别是在反应开始阶段。使用同位素标记的C13O2，揭示了两个关键的见解：(1)CH4主要通过吸附的*CO形成（从气相吸附或通过CO2解离）；(2)在进料中存在额外的还原剂（CO）时，催化剂的活性通过促进表面*O的去除而提高。这些发现强调了提高Mo2C催化剂的加氢（或去除*O）能力对于提高常规和强化RWGS条件下性能的重要性。

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引用次数: 0

Bimetallic ZnCo anchoring of Pt species in CTAB-modified silicalite-1 (S-1) zeolite for propane dehydrogenation ctab改性硅石-1 （S-1）分子筛中Pt的双金属锌钴锚定作用

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2026-02-05 Epub Date: 2025-12-10 DOI: 10.1016/j.apcata.2025.120720

Jie Zhou , Yuan Tao , Xiaohui He , Hongbing Ji

Constructing stable Pt-based catalysts for propane dehydrogenation (PDH) under harsh conditions remains a critical challenge due to the sintering and the migration of Pt species, and coke deposition, all of which contribute to the deactivation of catalysts. Herein, we report a novel catalyst with bimetallic ZnCo anchoring of Pt species encapsulated in CTAB-modified silicalite-1 (S-1) zeolite. This catalyst demonstrates exceptional PDH performance, maintaining a low deactivation rate constant of 0.0014 h⁻¹ after 115 h of operation at 550℃ under a pure propane stream. It achieves a stable propylene space-time yield (STY) of 35.6 mol

g_{Pt}^{- 1} h^{- 1}

, with a propane conversion of 25.6 % and a propene selectivity exceeding 98.0 %. The introduction of ZnCo bimetallic species promotes electron transfer, effectively inhibiting Pt sintering and regulating electronic structure of Pt species. Meanwhile, the incorporation of the soft template CTAB adjusts the structure of the channel of S-1 zeolite and contributes to the improvement of the catalyst durability. This synergistic design strategy offers a promising pathway for the development of robust and efficient PDH catalysts suited for industrial applications.

在恶劣条件下构建稳定的Pt基丙烷脱氢（PDH）催化剂仍然是一个关键的挑战，因为Pt的烧结和迁移以及焦炭的沉积都会导致催化剂失活。本文报道了一种新型催化剂，该催化剂将双金属zn - co锚定的Pt包裹在ctab修饰的硅-1 （S-1）沸石中。该催化剂表现出优异的PDH性能，在550℃纯丙烷流下运行115 h后，保持了0.0014 h−1的低失活速率常数。丙烯空时产率（STY）为35.6 mol gPt−1h−1，丙烯转化率为25.6%，丙烯选择性超过98.0%。ZnCo双金属组分的引入促进了电子转移，有效抑制了Pt烧结，调节了Pt组分的电子结构。同时，软模板CTAB的加入调整了S-1分子筛的通道结构，有助于提高催化剂的耐久性。这种协同设计策略为开发适合工业应用的稳健高效的PDH催化剂提供了一条有希望的途径。

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引用次数: 0

Catalytic performance of Ru(0) nanoparticles supported on K-OMS-2 in transfer hydrogenation reactions K-OMS-2负载Ru(0)纳米颗粒在转移加氢反应中的催化性能

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2026-02-05 Epub Date: 2026-01-02 DOI: 10.1016/j.apcata.2026.120769

Fatma Kizil , Halil İbrahim Önal , Khadichakhan Rafikova , Filiz Koyuncu , Nurgul Satybaldi̇yeva , Akbota Aronkyzy Aronova , Bagadat Selenova , Feyyaz Durap , Murat Aydemir

Transfer hydrogenation-mediated reduction of ketones to yield secondary alcohols, which leads to the production of commercially important fine chemicals, is more favorable compared to conventional hydrogenation reactions. This research explores the effects of different Ru(0) nanoparticle loadings synthesized by treating a cryptomelane-type manganese oxide framework (K-OMS-2), which were characterized by advanced analytical methods including FT-IR, XRD, XPS, BET, SEM-EDX, and HR-TEM-EDX. The catalytic activity of Ru(0)@K-OMS-2 nanocatalyst was investigated in the transfer hydrogenation reaction of ketones. According to the catalytic results, Ru(0)@K-OMS-2 (3.0 %) catalyst containing 3 wt% Ru showed higher efficiency, high selectivity and high conversion (97 %) in transfer hydrogenation compared to other catalysts prepared in this study.

与传统的加氢反应相比，转移加氢介导的酮还原反应产生仲醇，从而生产具有重要商业价值的精细化学品。本研究探讨了通过处理隐黑烷型氧化锰骨架（K-OMS-2）合成的不同Ru(0)纳米颗粒的影响，并通过FT-IR、XRD、XPS、BET、SEM-EDX和HR-TEM-EDX等先进分析方法对其进行了表征。研究了Ru(0)@K-OMS-2纳米催化剂在酮类转移加氢反应中的催化活性。催化结果表明，含有3 wt% Ru的Ru(0)@K-OMS-2（3.0 %）催化剂与本研究制备的其他催化剂相比，具有更高的转移加氢效率、高选择性和高转化率（97 %）。

引用次数: 0

Production of aromatics from furfural and ethanol over zeolite catalysts: Reaction and deactivation mechanisms, effect of acidity and zeolite structures 糠醛和乙醇在沸石催化剂上生产芳烃：反应和失活机理，酸度和沸石结构的影响

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2026-02-05 Epub Date: 2025-11-25 DOI: 10.1016/j.apcata.2025.120718

Francesco Sandri , Jennifer Cueto , Christoph Schmidt , Anssi Peuronen , Pia Damlin , Teija Tirri , Kari Eränen , Mika Lastusaari , Narendra Kumar , David P. Serrano , Päivi Mäki-Arvela , Dmitry Yu. Murzin

The production of aromatics, specifically benzene, toluene and xylenes (BTX), from bio-derived feedstock such as ethanol and furfural can be achieved by zeolite catalysts. However, the formation of coke strongly limits this reaction leading to catalyst deactivation. In-depth understanding of the relationship between the catalyst characteristics and the mechanism of carbon deposit is needed to improve potential applicability of this novel approach for BTX production. Evaluation of the catalytic activity of β and ZSM-5 zeolites in the aromatization of ethanol and furfural, coupled with the characterization of the spent catalysts, gave important insights on the structure and features that are required to increase the aromatics formation. With these investigations it was possible to determine the location of the catalytic sites that are active in the aromatization reaction, defining at the same time the mechanism of deactivation by coke formation. These findings give important advances for the future design of efficient catalysts for the aromatics production.

用沸石催化剂可以从乙醇和糠醛等生物原料中生产芳烃，特别是苯、甲苯和二甲苯（BTX）。然而，焦炭的形成强烈地限制了这种反应，导致催化剂失活。需要深入了解催化剂特性与积碳机理之间的关系，以提高该新方法在BTX生产中的潜在适用性。对β和ZSM-5沸石在乙醇和糠醛芳构化反应中的催化活性进行了评价，并对废催化剂进行了表征，对提高芳构化反应所需的结构和特征有了重要的认识。通过这些研究，可以确定在芳构化反应中活跃的催化位点的位置，同时确定由焦炭形成的失活机制。这些发现为未来设计高效的芳烃生产催化剂提供了重要的进展。

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引用次数: 0

Effect of conductive polypyrrole on CuOx nanowire arrays for nitrate electroreduction to ammonia 导电聚吡咯对CuOx纳米线阵列硝酸电还原制氨的影响

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2026-02-05 Epub Date: 2025-12-04 DOI: 10.1016/j.apcata.2025.120742

Aijing Ma , Yuni Dewi Susanti , Xueqian Li , Dan Liu , Bhekie B. Mamba , Alex T. Kuvarega , Jianzhou Gui

Electrochemical nitrate reduction to ammonia (NRA) is recognized as a promising approach to address nitrate (NO₃^-) pollution while yielding high-value ammonia. However, the lack of efficient electrocatalysts has severely limited the development of this technology. In this study, conductive polypyrrole (PPy) modulated CuO_x nanowire arrays (CuO_x@PPy/CF) were elaborately designed, and the effect of PPy on NRA activity has been systematically investigated. The optimal CuO_x@PPy/CF-B2 electrocatalyst performed significantly better than the unmodified CuO_x/CF. It exhibited 96.52 % NO₃^- conversion, 99.76 % NH₄⁺ Faradaic efficiency, 93.28 % NH₄⁺ selectivity, and an NH₄⁺ yield of 0.249 mmol‧h⁻¹ ‧cm⁻². A series of characterizations confirmed that the porous PPy coating accelerated electron transfer and modulated the surface chemical microenvironment via promoting electrostatic adsorption of NO₃^- and accumulating hydrogenated species, thereby facilitating ammonia formation. Moreover, in situ ATR-FTIR spectroscopy identified reaction intermediates, enabling the proposal of a plausible reaction pathway. This work underscores the potential of conductive polymer-modified catalysts for advancing efficient nitrate electroreduction technology.

电化学硝酸还原制氨（NRA）被认为是解决硝态氮（NO3-）污染同时产生高价值氨的一种有前途的方法。然而，高效电催化剂的缺乏严重限制了该技术的发展。本研究精心设计了导电聚吡咯（PPy）调制的CuOx纳米线阵列（CuOx@PPy/CF），并系统研究了PPy对NRA活性的影响。优化后的CuOx@PPy/CF- b2电催化剂性能明显优于未改性的CuOx/CF。它的NO3-转化率为96.52 %，NH4+法拉第效率为99.76 %，NH4+选择性为93.28 %，NH4+产率为0.249 mmol·h⁻¹ ·cm−2。一系列表征证实了多孔PPy涂层通过促进NO3-的静电吸附和氢化物质的积累来加速电子转移和调节表面化学微环境，从而促进氨的形成。此外，原位ATR-FTIR光谱鉴定了反应中间体，从而提出了一个合理的反应途径。这项工作强调了导电聚合物改性催化剂在推进高效硝酸电还原技术方面的潜力。

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引用次数: 0

Limitations of proton-conducting materials as supports for Pt-catalyzed ethane dehydrogenation in membrane reactors 质子导电材料作为膜反应器中pt催化乙烷脱氢载体的局限性

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2026-02-05 Epub Date: 2025-12-14 DOI: 10.1016/j.apcata.2025.120749

Jord P. Haven, Leon Lefferts, Jimmy A. Faria Albanese

Olefin formation via non-oxidative dehydrogenation of light alkanes is limited by thermodynamic equilibrium. A possible strategy to increase olefin yields aims at removing H₂ from the reaction zone using ceramic proton-conducting membranes. An attractive proposition is to deposit the catalyst directly onto the proton-conducting material to optimize hydrogen transport. To test this concept a Pt dehydrogenation catalyst was deposited onto lanthanum tungstate (LWO) and barium zirconium cerium yttrium (BZCY) oxides, which are prototypical materials in proton-conducting ceramics. The performance of Pt/LWO and Pt/BZCY was compared to a conventional Pt/ZnAl₂O₄ dehydrogenation catalyst in the non-oxidative dehydrogenation of ethane. The ethylene selectivity on Pt/LWO and Pt/BZCY was much lower than for Pt/ZnAl₂O₄, at the cost of a higher methane selectivity. Methane formation is possibly boosted by C-C cleavage on Lewis acid sites of the LWO and BZCY supports. These acid sites originate from the presence of oxygen vacancies in LWO and BZCY. Additionally, Pt/LWO deactivated rapidly in dry atmospheres, due to Pt sintering. This sintering, however, was suppressed when cofeeding steam. The presence of steam, unfortunately, further decreased ethylene selectivity for Pt/LWO. The Pt/BZCY system was comparably stable relative to Pt/LWO, which was attributed to relatively strong interactions between Pt and the Ba in the support. Implementing proton-conducting materials, like LWO and BZCY, as catalyst supports requires significant improvements to compete with the conventional Pt/ZnAl₂O₄ catalyst. Addressing this issue will be key to enable large-scale implementation of proton ceramic catalytic membrane reactors for alkane dehydrogenation.

轻烷烃非氧化脱氢生成烯烃受到热力学平衡的限制。提高烯烃产量的一个可能的策略是利用陶瓷质子传导膜从反应区去除H2。一个有吸引力的建议是将催化剂直接沉积在质子导电材料上，以优化氢的传输。为了验证这一概念，将Pt脱氢催化剂沉积在钨酸镧（LWO）和钡锆铈钇（BZCY）氧化物上，这是质子导电陶瓷的原型材料。研究了Pt/LWO和Pt/BZCY在乙烷非氧化脱氢反应中的性能，并与常规Pt/ZnAl2O4脱氢催化剂进行了比较。Pt/LWO和Pt/BZCY的乙烯选择性比Pt/ZnAl2O4低得多，代价是甲烷选择性更高。甲烷的形成可能是由LWO和BZCY载体的Lewis酸位点上的C-C裂解促进的。这些酸位来源于LWO和BZCY中氧空位的存在。此外，由于Pt烧结，Pt/LWO在干燥气氛中迅速失活。然而，当共进蒸汽时，这种烧结被抑制。不幸的是，蒸汽的存在进一步降低了Pt/LWO的乙烯选择性。相对于Pt/LWO， Pt/BZCY体系相对稳定，这是由于Pt与支架中Ba之间的相互作用相对较强。实现质子导电材料，如LWO和BZCY，作为催化剂支撑需要显著改进，以与传统的Pt/ZnAl2O4催化剂竞争。解决这一问题将是大规模实施质子陶瓷催化膜反应器进行烷烃脱氢的关键。

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引用次数: 0

Sustainable chemical recycling of PET via methanolysis over engineered hydroxyapatite nanorod catalysts 工程羟基磷灰石纳米棒催化剂甲醇分解PET的可持续化学回收

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2026-02-05 Epub Date: 2025-12-16 DOI: 10.1016/j.apcata.2025.120751

Yu Yang , Qingmei Ge , Nan Jiang , Hongxiu Zhao , Yin-Hui Huang , Hang Cong , Song Yang , Wenfeng Zhao

The disposal of waste plastics, particularly polyethylene terephthalate (PET), is a growing environmental issue, with PET accounting for a significant portion of global plastic waste. This work presents an efficient catalytic strategy for upcycling PET to high-value dimethyl terephthalate (DMT) using engineered hydroxyapatite (HAP) as a solid catalyst. HAP was prepared and characterized under different calcination conditions, resulting in rod-like porous structures with mesoporous features. The HAP catalyst calcined at 700 °C exhibited excellent catalytic activity for the methanolysis of PET, achieving 100 % PET conversion and more than 90 % DMT yield at 180 °C within 2 h. Notably, HAP showed good reusability, maintaining its catalytic performance over at least four cycles without significant deactivation. The mechanism of the HAP-catalyzed methanolysis of PET was studied via SEM and ³¹P solid-state NMR, revealing its role in promoting ester bond cleavage through both Lewis and Brønsted acid sites. This approach provides an efficient pathway for PET recycling, offering a sustainable solution to the growing problem of plastic waste.

废塑料的处理，特别是聚对苯二甲酸乙二醇酯（PET），是一个日益严重的环境问题，PET占全球塑料废物的很大一部分。本研究提出了一种利用工程羟基磷灰石（HAP）作为固体催化剂将PET升级为高价值对苯二甲酸二甲酯（DMT）的有效催化策略。在不同的煅烧条件下制备了HAP并对其进行了表征，得到了具有介孔特征的棒状多孔结构。在700℃下煅烧的HAP催化剂对PET的甲醇分解表现出优异的催化活性，在180℃下，2 h内PET转化率达到100% %，DMT产率达到90% %以上。值得注意的是，HAP表现出良好的可重复使用性，在至少四个循环中保持其催化性能而没有明显的失活。通过SEM和31P固体核磁共振研究了hap催化PET甲醇分解的机理，揭示了其通过Lewis和Brønsted酸位点促进酯键裂解的作用。这种方法为PET回收提供了有效途径，为日益严重的塑料废物问题提供了可持续的解决方案。

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引用次数: 0

Preface to the special issue in honor of Prof. Luca Lietti on his 65th birthday 为纪念卢卡·利蒂教授65岁生日而出版的特刊序言

IF 4.8 2区化学 Q2 CHEMISTRY, PHYSICAL

Applied Catalysis A: General

Pub Date : 2026-02-05 Epub Date: 2025-12-17 DOI: 10.1016/j.apcata.2025.120753

Alessandra Beretta , Gianpiero Groppi , Matteo Maestri , Isabella Nova , Enrico Tronconi , Carlo Giorgio Visconti

引用次数: 0

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