Reaction kinetics and phase behavior in the chemoselective hydrogenation of 3‐nitrostyrene over Co‐N‐C single‐atom catalyst in compressed CO_(2)

Single‐atom catalysts(SACs)have demonstrated excellent performances in chemoselective hydrogenation reactions.However,the employment of precious metals and/or organic solvents compromises their sustainability.Herein,we for the first time report the chemoselective hydrogenation of 3‐nitrostyrene over noble‐metal‐free Co‐N‐C SAC in green solvent—compressed CO2.An interesting inverted V‐curve relation is observed between the catalytic activity and CO2 pressure,where the conversion of 3‐nitrostyrene reaches the maximum of 100%at 5.0 MPa CO2(total pressure of 8.1 MPa).Meanwhile,the selectivities to 3‐vinylaniline at all pressures remain high(>99%).Phase behavior studies reveal that,in sharp contrast with the single phase which is formed at total pressure above 10.8 MPa,bi‐phase composed of CO2/H_(2)gas‐rich phase and CO2‐expanded substrate liquid phase forms at total pressure of 8.1 MPa,which dramatically changes the reaction kinetics of the catalytic system.The reaction order with respect to H_(2)pressure decreases from~0.5 to zero at total pressure of 8.1 MPa,suggesting the dissolved CO2 in 3‐nitrostyrene greatly promotes the dissolution of H_(2)in the substrate,which is responsible for the high catalytic activity at the peak of the inverted V‐curve.

Construction of bifunctional single-atom catalysts on the optimized β-Mo_(2)C surface for highly selective hydrogenation of CO_(2) into ethanol

Green and economical CO_(2)utilization is significant for CO_(2)emission reduction and energy development.Here,the 1D Mo_(2)C nanowires with dominant(101)crystal surfaces were modified by the deposition of atomic functional components Rh and K.While unmodifiedβMo_(2)C could only convert CO_(2)to methanol,the designed catalyst of K_(0.2)Rh_(0.2)/β-Mo_(2)C exhibited up to 72.1%of ethanol selectivity at 150℃.It was observed that the atomically dispersed Rh could form the bifunctional active centres with the active carrierβMo_(2)C with the synergistic effects to achieve highly specific controlled C–C coupling.By promoting the CO_(2)adsorption and activation,the introduction of an alkali metal(K)mainly regulated the balanced performance of the two active centres,which in turn improved the hydrogenation selectivity.Overall,the controlled modification ofβMo_(2)C provides a new design strategy for the highly efficient,lowtemperature hydrogenation of CO_(2)to ethanol with single-atom catalysts,which provides an excellent example for the rational design of the complex catalysts.

Enhanced stability of highly-dispersed copper catalyst supported by hierarchically porous carbon for long term selective hydrogenation

Copper based catalysts have high potential for the substituent of noble-metal based catalysts as their high selectivity and moderate activity for selective hydrogenation reaction;however,achieving further high catalytic stability is very difficult.In this work,the carbonization process of Cu-based organic frameworks was explored for the synthesis of highly-dispersed Cu supported by hierarchically porous carbon with high catalytic performance for selective hydrogenation of 1,3-butadiene.The porous hierarchy of carbon support and the dispersion of copper nanoparticles can be precisely tuned by controlling the carbonization process.The resultant catalyst carbonized at 600°C exhibits a rather low reaction temperature at 75°C for 100%butadiene conversion with 100%selectivity to butenes,due to its reasonable porous hierarchy and highly-dispersed copper sites.More importantly,unprecedentedly stability of the corresponding Cu catalyst was firstly observed for selective 1,3-butadiene hydrogenation,with both 100%butadiene conversion and 100%butenes selectivity over 120 h of reaction at 75°C.This study verifies that a simply control the carbonization process of metal organic frameworks can be an effective way to obtain Cu-based catalysts with superior catalytic performance for selective hydrogenation reaction.

Control of reactive dividing wall column for selective hydrogenation and separation of C3 stream

In our previous work, the reactive dividing wall column(RDWC) was proposed and proved to be effective for selective hydrogenation and separation of C3 stream. In the present paper, the dynamics and control of the proposed RDWC are investigated. Four control structures including composition and temperature controls are proposed. The feed forward controllers are employed in the four control strategies to shorten the dynamic response time, reduce the maximum deviations and offer an immediate adjustment. The control structures are compared by applying them into the RDWC system with 20% disturbances in both the feed flow rate and the feed compositions, and the results are discussed.

In Situ IR Spectroscopic Study on the Hydrogenation of 1,3-Butadiene on Fresh Mo_2C/γ-Al_2O_3 Catalyst

The surface species formed from the adsorption of 1,3-butadiene and 1,3-butadiene hydrogenation over the fresh Mo2C/γ-Al2O3 catalyst was studied by in situ IR spectroscopy. It is found that 1,3-butadiene adsorption on the Mo2C/γ-Al2O3 catalyst mainly forms π-adsorbed butadiene(πs and πd) and σ-bonded surface species. These species are adsorbed mainly on the surface Moδ+(0<δ<2) sites as evidenced by co-adsorption of 1,3-butadiene and CO on the fresh Mo2C/γ-Al2O3 catalyst. The IR spectrometric analysis show that hydrogenation of 1,3-butadiene over fresh Mo2C/γ-Al2O3 catalyst produces mainly butane coupled with a small portion of butene. The selectivity of butene during the hydrogenation of 1,3-butadiene over fresh Mo2C/γ-Al2O3 catalyst might be explained by the adsorption mode of adsorbed 1,3-butadiene. Additionally, the active sites of the fresh Mo2C/γ-Al2O3 catalyst may be covered by coke during the hydrogenation reaction of 1,3-butadiene. The treatment with hydrogen at 673 K cannot remove the coke deposits from the surface of the Mo2C/γ-Al2O3 catalyst.

Selective C3-alkenylation of oxindole with aldehydes using heterogeneous CeO2 catalyst

We report herein that a commercially available CeO2 is an active and reusable catalyst for the C3-selective alkenylation of oxindole with aldehydes under solvent-free conditions. This catalytic method is generally applicable to different aromatic and aliphatic aldehydes, giving 3-alkyledene-oxindoles in high yields(87%–99%) and high stereoselectivities(79%–93% to E-isomers). This is the first example of the catalytic synthesis of 3-alkenyl-oxindoles from oxindole and various aliphatic aldehydes. The Lewis acid-base interaction between Lewis acid sites on CeO2 and benzaldehyde was studied by in situ IR. The structure-activity relationship study using CeO2 catalysts with different sizes suggests that defect-free CeO2 surface is the active site for this reaction.

Studies on the Hydrogenation of Acetonitrile over Fresh Mo_2C/γ-Al_2O_3 Catalyst by In-situ IR Spectroscopy

The adsorption of acetonitrile, the co-adsorption of acetonitrile with CO, and hydrogenation of acetonitrile on fresh Mo2C/γ-Al2O3 catalyst were studied by in situ IR spectroscopy. It was found out that CH3CN exhibited strong interaction with the fresh Mo2C/γ-Al2O3 catalyst and was adsorbed mainly on Moδ+ sites of fresh Mo2C/γ-Al2O3 catalyst. Moreover, CH3CN could affect the shifting of IR spectra for CO adsorption towards a lower wave number. The IR spectroscopic study on acetonitrile hydrogenation showed that CH3CN could be easily hydrogenated in the presence of H2 on the Mo2C/γ-Al2O3 catalyst. Furthermore, it was observed that CH3 CN could be selectively hydrogenated to imines on fresh Mo2C/γ-Al2O3 catalyst. Additionally, the active sites of fresh Mo2C/γ-Al2O3 catalyst might be covered with coke during the hydrogenation reaction of acetonitrile. The treatment of catalyst with hydrogen at 673 K could not completely remove coke deposits on the surface of the Mo2C/γ-Al2O3 catalyst.

Selective adsorption of thiocyanate anions on Ag-modified g-C_3N_4 for enhanced photocatalytic hydrogen evolution

Silver‐modified semiconductor photocatalysts typically exhibit enhanced photocatalytic activitytoward the degradation of organic substances.In comparison,their hydrogen‐evolution rates arerelatively low owing to poor interfacial catalytic reactions to producing hydrogen.In the presentstudy,thiocyanate anions(SCN–)as interfacial catalytic active sites were selectively adsorbed ontothe Ag surface of g‐C3N4/Ag photocatalyst to promote interfacial H2‐evolution reactions.The thiocyanate‐modified g‐C3N4/Ag(g‐C3N4/Ag‐SCN)photocatalysts were synthesized via photodepositionof metallic Ag on g‐C3N4and subsequent selective adsorption of SCN– ions on the Ag surface by animpregnation method.The resulting g‐C3N4/Ag‐SCN photocatalysts exhibited considerably higherphotocatalytic H2‐evolution activity than the g‐C3N4,g‐C3N4/Ag,and g‐C3N4/SCN photocatalysts.Furthermore,the g‐C3N4/Ag‐SCN photocatalyst displayed the highest H2‐evolution rate(3.9μmolh?1)when the concentration of the SCN– ions was adjusted to0.3mmol L?1.The H2‐evolution rateobtained was higher than those of g‐C3N4(0.15μmol h?1)and g‐C3N4/Ag(0.71μmol h?1).Consideringthe enhanced performance of g‐C3N4/Ag upon minimal addition of SCN– ions,a synergistic effectof metallic Ag and SCN– ions is proposed―the Ag nanoparticles act as an effective electron‐transfermediator for the steady capture and rapid transportation of photogenerated electrons,while theadsorbed SCN– ions serve as an interfacial active site to effectively absorb protons from solution andpromote rapid interfacial H2‐evolution reactions.Considering the present facile synthesis and itshigh efficacy,the present work may provide new insights into preparing high‐performance photocatalytic materials

Selective Oxidation of Toluene with Hydrogen Peroxide Catalyzed by V-Mo-based Catalyst

The selective catalytic oxidation of toluene with hydrogen peroxide over V-Mo-based catalysts under mild conditions was studied.The promotion effect of Mo on the catalysts was studied with V/Al2O3 and Mo/Al2O3 as reference samples.The catalysts were characterized by XRD,TPR,and XPS techniques.The results show that the addition of Mo to V/Al2O3 may change the distribution of V species on Al2O3 surface.Over V-Mo/Al2O3 catalyst,highly dispersed amorphous V species facilitates benzaldehyde formation,and crystalline V2O5 species increases the conversion of toluene but decreases the selectivity to benzaldehyde,while AlVMoO7 species favors both the conversion of toluene and the formation of cresols.The yield of benzaldehyde depends remarkably on the surface O/Al and Mo/V atomic ratios,and gets to a maximum value of 13.2% with a selectivity of 79.5% at an O/Al atomic ratio of 3.0 and Mo/V atomic ratio of 0.7.

高分散Ru/Si_(3)N_(4)催化剂的制备及其在CO_(2)加氢中的应用

氮化硅是一种良好的载体,具有较高的水热稳定性和机械稳定性,其表面的氨基基团能够较好地锚定金属,显著提高金属分散度。但是,商品氮化硅比表面积较低,对金属分散作用仍然有限。因此,以自制的高比表面积氮化硅(Si_(3)N_(4))为载体,通过浸渍法制备了不同Ru负载量(质量分数分别为0.5%、1.0%和2.0%)的催化剂(分别为0.5%Ru/Si_(3)N_(4)、1.0%Ru/Si_(3)N_(4)和2.0%Ru/Si_(3)N_(4)),并以商品氮化硅(Si_(3)N_(4)-C)为载体制备了2.0%Ru/Si_(3)N_(4)-C催化剂作为对照组。表征了催化剂的理化性质,测试了其在300℃、0.1 MPa下的CO_(2)加氢反应活性。结果显示,与Si_(3)N_(4)-C相比,Si_(3)N_(4)的比表面积较高(502 m^(2)/g),Si_(3)N_(4)作为载体显著提高了金属分散度,降低了金属粒径,催化剂暴露出更多的活性位点。0.5%Ru/Si_(3)N_(4)的金属粒径较小,展现出强的H_(2)吸附能力,H难以解吸,抑制了中间物种CO加氢生成CH_(4)。随着Ru负载量增加,金属粒径增大,催化剂的CH_(4)选择性更好。Ru/Si_(3)N_(4)系列催化剂中,2.0%Ru/Si_(3)N_(4)的CH_(4)选择性较高(98.8%)。空速为10000 m L/(g·h)时,0.5%Ru/Si_(3)N_(4)的CO选择性为88.2%。与2.0%Ru/Si_(3)N_(4)相比,2.0%Ru/Si_(3)N_(4)-C的金属粒径更大,活性位点较少,活性更低。2.0%Ru/Si_(3)N_(4)和2.0%Ru/Si_(3)N_(4)-C的CO_(2)转化率分别为53.1%和9.2%。Si_(3)N_(4)有效提高了金属分散度,提高了催化剂的CO_(2)加氢反应活性;通过调控Ru负载量控制催化剂金属粒径,可实现对产物CO或CH_(4)选择性的调控。

In situ construction of protonated g-C3N4/Ti3C2 MXene Schottky heterojunctions for efficient photocatalytic hydrogen production

Converting sustainable solar energy into hydrogen energy over semiconductor-based photocatalytic materials provides an alternative to fossil fuel consumption.However,efficient photocatalytic splitting of water to realize carbon-free hydrogen production remains a challenge.Heterojunction photocatalysts with well-defined dimensionality and perfectly matched interfaces are promising for achieving highly efficient solar-to-hydrogen conversion.Herein,we report the fabrication of a novel type of protonated graphitic carbon nitride(PCN)/Ti3C2 MXene heterojunctions with strong interfacial interactions.As expected,the two-dimensional(2D)PCN/2D Ti3C2 MXene interface heterojunction achieves a highly improved hydrogen evolution rate(2181μmol∙g‒1)in comparison with bulk g-C3N4(393μmol∙g‒1)and protonated g-C3N4(816μmol∙g‒1).The charge-regulated surfaces of PCN and the accelerated charge transport at the face-to-face 2D/2D Schottky heterojunction interface are the major contributors to the excellent hydrogen evolution performance of the composite photocatalyst.

Metal-doped Mo2C(metal=Fe,Co,Ni,Cu)as catalysts on TiO2 for photocatalytic hydrogen evolution in neutral solution

The neutral hydrogen evolution reaction(HER)is vital in the chemical industry,and its efficiency depends on the interior character of the catalyst.Herein,work function(WF)engineering is introduced via 3d metal(Fe,Co,Ni,and Cu)doping for modulating the Fermi energy level of Mo2C.The defective energy level facilitates the free water molecule adsorption and,subsequently,promotes the neutral HER efficiency.Specifically,at a current density of 10 mA/cm2,Cu-Mo2C exhibits the best HER performance with an overpotential of 78 mV,followed by Ni-Mo2C,Co-Mo2C,Fe-Mo2C,and bare Mo2C with 90,95,100,and 173 mV,respectively,and the corresponding Tafel slope values are 40,43,42,56,and 102 mV/dec.The modified WF can also lead to an enhanced photocatalytic efficiency owing to the lowered Schottky barrier and excellent carrier transition across the electrocatalyst–solution interface.When coupling the metal-doped Mo2C samples with TiO2,enhanced photocatalytic neutral HER rates are obtained in comparison to the case with bare TiO2.Typically,the HER rates are 521,404,275,224,147,and 112μmol/h for Cu,Ni,Co,Fe,bare Mo2C,and bare TiO2,respectively.Time-resolved photoluminescence spectroscopy(TRPS)and ultrafast transient absorption(TA)measurements are carried out to confirm the recombination and migration of the photogenerated carriers.The fittedτvalues from the TRPS curves are 22.6,20.5,10.1,4.7,4.0,2.5,and 1.9 ns for TiO2,TiO2-Mo2C,TiO2-Fe-Mo2C,TiO2-Fe-Mo2C,TiO2-Fe-Mo2C,TiO2-Fe-Mo2C,and TiO2-Pt,respectively.Additionally,the fittedτvalues from the TA results are 31,73,and 105 ps for the TiO2-Mo2C,TiO2-Cu-Mo2C,and TiO2-Pt samples,respectively.This work provides in-depth insights into the WF modulation of an electrocatalyst for improving the HER performance.

Probing into Surface Sites of Fresh Mo_2N/Al_2O_3,Mo_2C/Al_2O_3 and MoP/Al_2O_3 Catalysts by CO Adsorption and In Situ FT-IR Spectroscopy

The surface nature of fresh Mo2N/Al2O3, Mo2C/Al2O3 and/MoP/Al2O3 catalysts, which were synthesized directly in the IR cell to avoid passivation, were characterized by in situ IR spectroscopy with CO as a probe molecule. CO adsorbed on fresh catalysts showed characteristic IR bands at 2045 cm-1 for Mo2N/Al2O3 catalyst, 2054 cm-1 for MozC/Al2O3 catalyst and 2037 cm-1 for MoP/Al2O3 catalyst, respectively. A strong band at 2200 cm-1 for Mo2N/Al2O3 catalyst, which could be ascribed to NCO species formed when CO reacted upon surface active nitrogen atoms, and a weak band at 2196 cm-1 for Mo2C/Al2O3 catalyst, which could be attributed to CCO species, were also detected. CO adsorbed on fresh Mo2N/Al2O3 catalyst, Mo2C/Al2O3 catalyst and MoP/Al2O3 catalyst, showed strong molecular adsorption, just like noble metals. Our experimental results are bolstered by direct IR evidence demonstrating the similarity in surface electronic property between the fresh Mo2N/Al2O3, Mo2C/Al2O3 and MoP/Al2O3 catalysts and noble metals.

FT-IR Spectroscopic Investigation of Co-adsorption of Acetonitrile and CO on Fresh Mo_2C/Al_2O_3 Catalyst

The adsorption of acetonitrile and its co-adsorption with CO on fresh Mo_2C/Al_2O_3 catalyst have been studied by insitu FT-IR spectroscopy.Linearly adsorbed CH_3CN and CH_3CH_2NH_2 were formed after CH_3CN adsorption on the Mo_2C/ Al_2O_3 catalyst.The appearance of a strong band at 1578 cm^(-1) indicates that CH_3CN was reactive with hydrogen on the Mo_2C/Al_2O_3 catalyst.

Silica-Grafted Ionic Liquids as Recyclable Catalysts for the Synthesis of 3,4-Dihydropyrano[c]chromenes and Pyra-no[2,3-c]pyrazoles

Silica-grafted N-propyl-imidazolium hydrogen sulfate ([Sipim]HSO4) is employed as a recyclable heterogeneous ionic liquid catalyst for the synthesis of 3,4-dihydropyrano[c]-chromenes by the reaction of aromatic aldehydes, malononitrile and 4-hydroxycoumarin at 100°C under solvent-free conditions. Also, heterogeneous ionic liquid catalyst was used for the synthesis of pyrano[2,3-c]-pyrazoles by the reaction of aromatic aldehydes, malononitrile and 3-methyl-l-phenyl-5-pyrazolone at 110°C under solvent-free conditions. The heterogeneous ionic liquid showed much the same efficiency when used in consecutive reaction runs.

Atomic Dispersion of Rh on Interconnected Mo_(2)C Nanosheet Network Intimately Embedded in 3D Ni_(x)MoO_(y) Nanorod Arrays for pH-Universal Hydrogen Evolution

Herein,a simple synthetic approach is employed for the atomic dispersion of Rh atoms(Rh SAs)over the surface of interconnected Mo_(2)C nanosheets intimately embedded in a three-dimensional Ni_(x)MoO_(y)nanorod arrays(Ni_(x)MoO_(y)NRs)framework;we found that the introduction of both isolated Rh SAs and Ni_(x)MoO_(y)NRs adjusts the electrocatalytic function of the host Mo_(2)C toward the direction of being an advanced and highly stable electrocatalyst for efficient hydrogen evolution at pH-universal conditions.As a result,the proposed catalyst outperforms most recently reported transition metal-based catalysts,and its performance even rivals that of commercial Pt/C,as demonstrated by its ultralow overpotentials of 31.7,109.7,and 95.4 mV at a current density of 10 mA cm^(-2),along with its small Tafel slopes of 42.4,51.2,and 46.8 mV dec^(-1)in acidic,neutral,and alkaline conditions,respectively.In addition,the catalyst shows remarkable long-term stability over all pH values with good maintenance of its catalytic activity and structural characteristics after continuous operation.

在ThO_2－SrCO_3／BaSO_4催化剂中甲烷氧化偶联反应的研究

研究了ＴｈＯ２－ＳｒＣＯ３／ＢａＳＯ４催化剂在甲烷氧化偶联反应中的催化作用，发现在ＳｒＣＯ３／ＢａＳＯ４中添加ＴｈＯ２可明显提高催化剂的活性，其Ｃ２选择性及Ｃ２收率可达６１．３１％和１８．１７％，而且经过３００ｈ的连续考察，活性稳定。用ＸＲＤ方法研究了３组份催化剂的物相组成，推测结构与催化性能的关系。用ＴＰＤ方法研究３组份催化剂的酸碱性与活性的关系。

Cu-Co/γ-Al_(2)O_(3)催化臭氧氧化深度处理维生素废水研究

为解决维生素C废水经二级生化处理后仍不能达到排放标准的问题,以γ-氧化铝为载体,采用化学浸渍法工艺制备出一种高效稳定的Cu-Co/γ-Al_(2)O_(3)催化剂,构成臭氧催化氧化体系。采用XRD、BET、SEM对催化剂进行表征,并探究不同条件下对维生素C废水深度处理效果的影响。结果表明,在反应初始溶液pH=9、臭氧浓度20 mg/L、臭氧流量1 L/min、催化剂投加量为16 g/L、过氧化氢投加量6 mL/L、在反应时间持续90 min的条件下,COD去除率、UV 254去除率、TOC去除率分别达到83.25%,92.14%,79.39%。EPR测试表明臭氧催化氧化体系遵从羟基自由基作用机理,Cu-Co/γ-Al_(2)O_(3)催化剂重复使用10次后,COD去除率、UV 254去除率、TOC去除率仍达到76.37%,86.15%和74.29%,且负载金属离子浸出维持在较低水平,表明该催化剂是一种优异稳定的非均相臭氧催化剂。

Ni改性Mo_(2)C/γ-Al_(2)O_(3)催化剂在逆水气变换反应中的应用

以掺杂Y型分子筛的γ-Al_(2)O_(3)为载体,七钼酸铵(AMT)、六次甲基四胺(HMT)为原料,Ni CO_(2)·2Ni(OH)_(2)·4H_(2)O为改性助剂,通过共浸渍和程序升温炭化法制备了Mo_(2)C/γ-Al_(2)O_(3)(MCAS)和Ni改性的Ni-Mo_(2)C/γ-Al_(2)O_(3)(MNCAS)催化剂。采用XRD、ICP、N;吸附-脱附、TEM和EDS对其进行了表征,考察了其在逆水气变换反应中的催化性能。结果表明,MNCAS催化剂出现了Ni_(3)Mo_(2)N的特征衍射峰,Ni的加入有效改善了Mo_(2)C的聚集现象,并且该催化剂具有良好的介孔结构。MCAS催化剂对逆水气反应有较高的催化活性,300℃时CO选择性为93.87%,MNCAS-8催化剂[n(AMT)∶n(HMT)=1∶8,Mo和Ni的理论负载量分别为30%和5%,实际负载量分别为28.52%和4.51%]倾向于将CO_(2)转化成CH_(4),在低温段CH_(4)选择性达到84.37%,生成的Ni_(3)Mo_(2)N有利于提高CH_(4)的选择性。

Pd／Al_2O_3催化剂物性对C_4馏份选择加氢性能的影响

考查了用浸渍法制备的Ｐｄ／Ａｌ２Ｏ３系列加氢催化剂的比表面、Ｐｄ含量、Ｐｄ在载体上的分散度及催化剂的孔径分布与Ｃ４馏份选择加氢反应性能的关系。采用微型催化反应器对Ｃ４馏份选择加氢的主要工艺条件进行了试验。结果表明，载体Ａｌ２Ｏ３在适当的温度下焙烧，使比表面约为１１０—１１５ｍ２／ｇ，控制Ｐｄ含量在０．１％—０．３％（ｍ），活性前身物ＰｄＣｌ２在４００—４５０℃分解８ｈ后用Ｈ２还原。制备成的催化剂，得到了较满意的Ｐｄ分散度和孔结构。在较佳的工艺条件（温度：３０—４０℃；压力：０．７—０．８ＭＰａ；Ｈ２／炔摩尔比：４—６；液体空速：１５ｈ－１）下，对上述催化剂进行评价，反应产物中总炔烃含量＜２０×１０－６，丁二烯损失＜３％。