Influence of the Time Scale on the Reaction Mechanism of CO Oxidation over a Au/TiO2 Catalyst

Knowledge of the reaction mechanism is key for rational catalyst improvement. Traditionally mechanistic studies focus on structure and the reaction conditions like temperature, pH, pressure, etc., whereas the time dimension is often overlooked. Here, we demonstrate the influence of time on the mechanism of a catalytic reaction. A dual catalytic mechanism was identified for the CO oxidation over Au/TiO₂ by time-resolved infrared spectroscopy coupled with modulation excitation spectroscopy. During the first seconds, CO on the gold particles is the only reactive species. As the reaction proceeds, the redox properties of TiO₂ dominate the catalytic activity through electronic metal-support interaction (EMSI). CO induces the reduction and reconstruction of TiO₂ whereas oxygen leads to its oxidation. The activity of the catalyst follows the spectroscopic signature of the EMSI. These findings demonstrate the power of studying short-time kinetics for mechanistic studies.     

Selective Oxidative Dehydrogenation of Ethane and Propane over Copper-Containing Mordenite: Insights into Reaction Mechanism and Product Protection

Copper(II)-containing mordenite (CuMOR) is capable of activation of C−H bonds in C₁-C₃ alkanes, albeit there are remarkable differences between the functionalization of ethane and propane compared to methane. The reaction of ethane and propane with CuMOR results in the formation of ethylene and propylene, while the reaction of methane predominantly yields methanol and dimethyl ether. By combining in situ FTIR and MAS NMR spectroscopies as well as time-resolved Cu K-edge X-ray absorption spectroscopy, the reaction mechanism was derived, which differs significantly for each alkane. The formation of ethylene and propylene proceeds via oxidative dehydrogenation of the corresponding alkanes with selectivity above 95 % for ethane and above 85 % for propane. The formation of stable π-complexes of olefins with Cu^I sites, formed upon reduction of Cu^II-oxo species, protects olefins from further oxidation and/or oligomerization. This is different from methane, the activation of which proceeds via oxidative hydroxylation leading to the formation of surface methoxy species bonded to the zeolite framework. Our findings constitute one of the major steps in the direct conversion of alkanes to important commodities and open a novel research direction aiming at the selective synthesis of olefins.     

Surface Chemistry and Catalytic Reactivity of Borocarbonitride in Oxidative Dehydrogenation of Propane

Borocarbonitride (BCN) materials are newly developed oxidative dehydrogenation catalysts that can efficiently convert alkanes to alkenes. However, BCN materials tend to form bulky B₂O₃ due to over-oxidation at the high reaction temperature, resulting in significant deactivation. Here, we report a series of super stable BCN nanosheets for the oxidative dehydrogenation of propane (ODHP) reaction. The catalytic performance of the BCN nanosheets can be easily regulated by changing the guanine dosage. The control experiment and structural characterization indicate that the introduction of a suitable amount of carbon could prevent the formation of excessive B₂O₃ from BCN materials and maintain the 2D skeleton at a high temperature of 520 °C. The best-performing catalyst BCN exhibits 81.9 % selectivity towards olefins with a stable propane conversion of 35.8 %, and the propene productivity reaches 16.2 mmol h⁻¹ g⁻¹, which is much better than hexagonal BN (h-BN) catalysts. Density functional theory calculation results show that the presence of dispersed rather than aggregated carbon atoms can significantly affect the electronic microenvironment of h-BN, thereby boosting the catalytic activity of BCN.     

Boosting CO2 Hydrogenation to Formate over Edge-Sulfur Vacancies of Molybdenum Disulfide

Synthesis of formate from hydrogenation of carbon dioxide (CO₂) is an atom-economic reaction but is confronted with challenges in developing high-performance non-precious metal catalysts for application of the process. Herein, we report a highly durable edge-rich molybdenum disulfide (MoS₂) catalyst for CO₂ hydrogenation to formate at 200 °C, which delivers a high selectivity of over 99 % with a superior turnover frequency of 780.7 h⁻¹ surpassing those of previously reported non-precious metal catalysts. Multiple experimental characterization techniques combined with theoretical calculations reveal that sulfur vacancies at MoS₂ edges are the active sites and the selective production of formate is enabled via a completely new water-mediated hydrogenation mechanism, in which surface OH* and H* species in dynamic equilibrium with water serve as moderate hydrogenating agents for CO₂ with residual O* reduced by hydrogen. This study provides a new route for developing low-cost high-performance catalysts for CO₂ hydrogenation to formate.     

Cr/NaZSM-5催化剂上CO2氧化丙烷脱氢反应

以亚微米级NaZSM-5为载体合成了一系列负载型Cr催化剂, 采用氮气吸附、 XRD、 UV-Vis和H2-TPR对Cr/NaZSM-5催化剂的结构和织构性质进行了表征, 并评价了催化剂在CO2气氛下的丙烷脱氢性能. 硅铝摩尔比为60, Cr质量分数为3%的催化剂具有最高的反应活性, 于550 ℃反应10 min和8 h后的丙烷转化率分别为48.3%和30.1%, 丙烯选择性则分别为86.0%和91.8%. 催化剂中的Cr6+含量和反应初活性具有良好的对应关系, 表明高Cr6+含量对催化剂表现出高的丙烷脱氢活性是至关重要的. CO2气氛下的丙烯产率明显比氮气气氛下的高, 这是由于CO2气氛下催化剂表面有较多量的Cr6+, 并且CO2可通过逆水煤气变换反应除去脱氢反应生成的氢.     

丙烷氧化脱氢催化剂V2O5/MPO4(M=Al, Zr, Ca)的研究

制备了3种磷酸盐(MPO     

乙烷氧化脱氢制乙烯反应中制备方法及助剂对镍基催化剂性能的影响

采用不同方法制备了镍基催化剂,并考察了乙烷氧化脱氢制乙烯(ODE)的反应活性,结果表明,在3种不同制备方法的催化剂上,ODE反应的活性及产物选择性存在明显差异,浸渍法制备的催化剂性能最佳.在相同的条件下,以共浸渍法引入CeO2助剂后,N iO/-γA l2O3催化剂上的低温选择氧化活性显著提高,而目的产物C2H4的选择性变化不大.XRD,还原TG和XPS对催化剂进行表征的结果显示:反应的活性物相可能是易于还原的高度分散于催化剂表面的微晶N iO和表面尖晶石N iA l2O4物相;高分散的微晶N iO,类似于纯N iO,有利于ODE反应低温选择氧化生成目的产物C2H4,而易还原的表面尖晶石N iA l2O4物相的存在则可能是在高温下获得高选择氧化活性和选择性的主要原因之一.     

Probing the Nature of Zinc in Copper-Zinc-Zirconium Catalysts by Operando Spectroscopies for CO2 Hydrogenation to Methanol

Active Zn species in Cu-based methanol synthesis catalysts have not been clearly identified yet due to their complex nature and dynamic structural changes during reactions. Herein, atomically dispersed Zn on ZrO₂ support is established in Cu-based catalysts by separating Zn and Zr components from Cu (Cu−ZnZr) via the double-nozzle flame spray pyrolysis (DFSP) method. It exhibits superiority in methanol selectivity and yield compared to those with Cu−ZnO interface and isolated ZnO nanoparticles. Operando X-ray absorption spectroscopy (XAS) reveals that the atomically dispersed Zn species are induced during the reaction due to the strengthened Zn−Zr interaction. They can suppress formate decomposition to CO and decrease the H₂ dissociation energy, shifting the reaction to methanol production. This work enlightens the rational design of unique Zn species by regulating coordination environments and offers a new perspective for exploring complex interactions in multi-component catalysts.     

丙烷氧化脱氢催化剂V2O5/MPO4(M=Al,Zr,Ca)的研究

制备了3种磷酸盐(MPO₄,M=Al,Zr,Ca)载体,并在其上负载0.6%～6.0%的V₂O_5.活性评价结果表明,负载型V₂O₅/MPO₄催化剂在丙烷氧化脱氢反应中具有良好的催化性能.丙烯选择性按V₂O₅/Ca₃(PO₄)₂>V₂O₅/Zr₃(PO₄)₄>V₂O₅/AlPO₄顺序降低,这与载体的碱性强弱顺序变化一致.载体的性质和钒的负载量影响催化剂的氧化还原性能.ESR结果表明,V⁴⁺离子能可逆存在于催化剂中,暗示V⁵⁺/V⁴⁺氧化还原偶参与了氧化还原反应.     

Inside Cover: Ligand Assisted Thermal Atomization of Palladium Clusters: An Inspiring Approach for the Rational Design of Atomically Dispersed Metal Catalysts (Angew. Chem. Int. Ed. 16/2023)

The transformation from metal nanocluster catalysts to metal single-atom catalysts is an important procedure in the rational design of atomically dispersed metal catalysts (ADCs). However, the conversion methods often involve high annealing temperature as well as reducing atmosphere. Herein, we reported a continuous and convenient approach to transfer Pd nanocluster into Pd single-atom in a ligand assisted annealing procedure, by which means we reduced its activating temperature low to 400 °C. Using ex-situ microscopy and spectroscopy, we comprehensively monitored the structural evolution of Pd species though the whole atomization process. Theoretical calculation revealed that the structural instability caused by remaining Cl ligands was the main reason for this low-temperature transformation. The present atomization strategy and mechanistic knowledge for the conversion from cluster to atomic dispersion provides guidelines for the rational design of ADCs.     

乙烷氧化脱氢制乙烯CeO2-NiO/A2O3催化剂上氧物种的研究

在镍基催化剂上进行了乙烷氧化脱氢制乙烯的研究.结果表明,浸渍法制备的催化剂性能最佳.以浸渍法引入CeO2后,催化剂的低温反应活性显著提高.采用O2-TPD-MS、TPR和XPS等表征技术对催化剂进行了表征,结果显示:在ODE反应中,在低温下起主导作用的是"非化学计量氧"(O2-、O-和O22-);在高温下起主导作用的是晶格氧;CeO2的添加减弱了NiO与载体-γAl2O3间的强相互作用,提高了镍物种在载体上的分散度,高分散于催化剂表面的微晶NiO的量明显增加,此物种有利于催化剂的低温活性;影响了催化剂表面氧物种的分布,表面的晶格氧的相对浓度提高了,非化学计量氧的相对浓度降低了.     

氧化铈的氧化还原性能对VOx/CeO2催化剂催化氯苯氧化性能的影响

分别采用尿素、氨水和碳酸钠作沉淀剂制备了三种具有不同氧化还原性能的氧化铈载体,并考察了这三种氧化铈载体负载氧化钒催化剂催化氧化消除氯苯的性能.三种氧化钒催化剂在300℃下对氯苯氧化的转换频率依次为4.9,1.6和0.8h-1.该结果表明氧化铈载体的氧化还原性质影响着负载氧化钒催化剂催化氧化消除氯苯的活性,V-O-Ce键中的氧物种在该催化氧化反应中起着重要作用.     

Effect of the pH on the absorption spectrum of the isolated D1-D2-cytochrome b559 complex of photosystem II

The effect of pH on the Q_y absorption band has been studied in the isolated D1-D2-cytochrome b559 complex. The pH treatments are done on an ion-exchange chromatographic column. The absorption spectra at 77 K of the complex treated with acidic pH show irreversible loss of absorbance at both the blue and the red sides of the Q_y absorption band, with minima at 664.5 and 683.5 nm, respectively. These absorption changes are not accompanied by modifications in the Q_x absorption region characteristic of pheophytin pigments. Furthermore, the pigment composition of the D1-D2-cytochrome b559 complex remains unchanged after this treatment. The effects of basic pH are similar to those of acidic pH, but somewhat more pronounced. These results suggest that chlorophyll pigments absorbing at 664.5 and 683.5 nm are located on or close to the surface of the complex. Freezing/thawing cycle treatment first affects the band absorbing at 683.6 nm, indicating that it corresponds to the chlorophyll most exposed to the medium in the D1-D2-cytochrome b559 complex. At pH <5 a small reversible change at 672.5 nm is measured that correlates with a reversible change at 542 nm, indicating that inactive pheophytin a will absorb at this wavelength.     

镧对V2O5/γ-Al2O3催化剂在异丁烷脱氢中活性的影响

V2O5／γ-Al2O3是用于异丁烷脱氢的新型催化剂，引入适量的镧不仅可改善活性组分的分散度，提高催化脱氢活性，而且还增强了催化剂的抗积炭能力，通过FTIR，BET，TG，TPR和TEM等手段研究了镧对催化剂性能的影响。     

The Active Oxygen Species for Oxidative Coupling of Methane over CeO_2/BaF_2 Catalyst by in Situ Confocal Microprobe Raman Spectroscopy

ＴｈｅＡｃｔｉｖｅＯｘｙｇｅｎＳｐｅｃｉｅｓｆｏｒＯｘｉｄａｔｉｖｅＣｏｕｐｌｉｎｇｏｆＭｅｔｈａｎｅｏｖｅｒＣｅＯ２／ＢａＦ２ＣａｔａｌｙｓｔｂｙｉｎＳｉｔｕＣｏｎｆｏｃａｌＭｉｃｒｏｐｒｏｂｅＲａｍａｎＳｐｅｃｔｒｏｓｃｏｐｙ＊＊Ｓｕｐｐｏｒｔｅ...     

Ce助剂对V/SiO2催化CO2氧化乙苯脱氢性能的影响

通过N₂吸附、X射线衍射(XRD)、X射线光电子能谱(XPS)、H₂程序升温还原(H₂-TPR)、CO₂程序升温脱附(CO₂-TPD)和热重分析(TGA)等多种表征手段和催化反应性能评价,研究了铈助剂的添加对V/SiO₂催化CO₂氧化乙苯脱氢性能的影响. 结果表明,Ce助剂不仅提高了催化剂活性组分分散性和氧化还原性能,抑制了钒物种的深度还原,而且增强了催化剂碱性和CO₂吸附能力,减缓了积炭生成,从而显著提高了V-Ce/SiO₂对CO₂氧化乙苯脱氢反应的催化活性和稳定性. 在本实验中,V(0.8)-Ce(0.25)/SiO₂催化剂表现出最佳的催化性能,苯乙烯(ST)收率可达55.6%,选择性为98.5%,反应12 h 后,催化剂活性基本不变,与惰性N₂气氛比较,CO₂明显促进了乙苯脱氢反应,归因于CO₂能保持催化剂表面钒物种的高价态.     

Na-W-Mn/SiO_2催化剂活化甲烷的研究 Ⅰ.活性中心的结构

制备了不同 Na、W、Mn组分的 Na- W- Mn/ Si O2 催化剂 ,并进行了甲烷氧化偶联反应催化性能的评价和XPS、XRD、L RS表征 .研究结果表明 ,Na不但有强的表面富集能力 ,而且可以使 Mn向表面发生迁移 .首次发现 Na2 W2 O7也是活化甲烷的活性相 .活化甲烷的活性中心是 Na- O- Mn和 Na- O- W结构单元 ,且 Na- O-Mn主要存在于催化剂的表面 ,Na- O- W则分布在距催化剂表面较深的部位     

Dehydrogenation of cyclohexane over Pt/SiO2?AlPO4 catalysts, I. Influence of the catalyst particle size

The influence of Pt loading on the metal dispersity and catalytic activity of Pt catalysts on SiO₂−AlPO₄ in the dehydrogenation of cyclohexane to benzene has been analyzed. Kinetic parameters and apparent reaction rate constants were determined by the Bassett-Habgood equation. Thermodynamic parameters for the reaction were determined.     

Kinetics of the Oxidative Dehydrogenation of Isobutane over Cr2O3/La2(CO3)3

The oxidative dehydrogenation (ODH) of isobutane over Cr2O3/La2(CO3)3 has been investi-gated in a low-pressure Knudsen cell reactor, under conditions where the kinetics of the primary reactionsteps can be accurately determined. By heating the catalyst at a constant rate from 150-300 ℃, temper-ature fluctuations due to non-equilibrium adsorption are minimized. The evolved gas profiles show thatODH to isobutene and water is a primary reaction pathway, while carbon dioxide, which forms from thecatalyst during reaction, is the only other product. This CO2 evolution may enhance the activity of thecatalyst. Isobutene formation proceeds with the participation of lattice oxygen from the Cr2O3/La2(CO3)3catalyst. The intrinsic Arrhenius rate constant for the ODH of isobutane isk(s-1) = 1011.5±2.2exp{-((55 ± 5) - △Hads kJmol-1)/RT}The small pre-exponential factor is expected for a concerted mechanism and for such a catalyst with asmall surface area and limited porosity.     

Kinetics of the Oxidative Dehydrogenation of Isobutance over Cr2o3／La2（CO3）3

The oxidative dehydrogenation (ODH) of isobutane over Cr2O3/La2(CO3)3 has been investi- gated in a low-pressure Knudsen cell reactor, under conditions where the kinetics of the primary reaction steps can be accurately determined. By heating the catalyst at a constant rate from 150-300oC, temper- ature uctuations due to non-equilibrium adsorption are minimized. The evolved gas profiles show that ODH to isobutene and water is a primary reaction pathway, while carbon dioxide, which forms from the catalyst during reaction, is the only other product. This CO2 evolution may enhance the activity of the catalyst. Isobutene formation proceeds with the participation of lattice oxygen from the Cr2O3/La2(CO3)3 catalyst. The small pre-exponential factor is expected for a concerted mechanism and for such a catalyst with a small surface area and limited porosity.