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Chinese Journal of Catalysis
2020, Vol. 41, No. 9
Online: 18 September 2020

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Cover: Wan and coworkers in their Article on pages 1337–1347 reported that the experimentally measurable surface d charge at the Pd sites in the AuPd nanoalloy had a linear relationship with the activation entropy (ΔS^0*) and catalytic activity (TOF_Pd) for the hydrogenation of quinoline.

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Table of Contents for VOL.41 No.9 2020, 41 (9):  0-0.  Abstract ( 13 )   PDF (1209KB) ( 16 )

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Selective hydrogenolysis of glycerol to 1,3-propanediol over Pt-W based catalysts Jia Wang, Man Yang, Aiqin Wang 2020, 41 (9):  1311-1319.  DOI: 10.1016/S1872-2067(20)63586-0 Abstract ( 199 )   [Full Text(HTML)] () PDF (771KB) ( 370 )   The selective hydrogenolysis of glycerol to 1,3-propanediol (1,3-PDO) is an attractive reaction due to the high demand for valorization of huge excess amounts of glycerol supply as well as the important application of 1,3-PDO in polyester industry. Nevertheless, the formation of 1,3-PDO is thermodynamically less favorable than 1,2-PDO, which necessitates the development of efficient catalysts to manipulate the reaction kinetics towards the 1,3-PDO formation. Among others, Pt-W based catalysts have shown promising activities and selectivities of 1,3-PDO although the reaction mechanism is not well addressed at the molecular level. In this short review, we have compared the performances of different Pt-W based catalysts and discussed the key factors influencing the activity and selectivity. Three possible reaction mechanisms have been discussed in terms of the synergy between Pt and WOx and the origin of acid sites. Finally, the long-term stability of the Pt-W catalysts has been discussed. We hope this review will provide useful information for the development of more efficient catalysts for this important reaction.

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Structural sensitivity of heterogeneous catalysts for sustainable chemical synthesis of gluconic acid from glucose Wenjuan Yan, Dongpei Zhang, Yu Sun, Ziqi Zhou, Yihang Du, Yiyao Du, Yushan Li, Mengyuan Liu, Yuming Zhang, Jian Shen, Xin Jin 2020, 41 (9):  1320-1336.  DOI: 10.1016/S1872-2067(20)63590-2 Abstract ( 258 )   [Full Text(HTML)] () PDF (1635KB) ( 384 )   Gluconic acid and its derivatives have been widely used in the food and pharmaceutical industries. Conventional processes that involve the conversion of glucose into gluconic acid via fermentation present several technological shortcomings as they involve energy-intensive wastewater treatment and complex enzyme separation. Greener oxidation processes over heterogeneous metal catalysts have attracted increasing attention worldwide. Au-, Pt- and Pd-based heterogeneous catalysts have been extensively used for the chemical oxidation of glucose to gluconic acid. Bimetallic catalysts synthesized by adding either noble or inexpensive metals have also presented excellent performance for the oxidations of glucose. In particular, particle size, which has been recognized as the most important factor that affect catalytic performances, could be rationally tuned by changing the types of support and ligand as well as the synthesis conditions. In this perspective review, we summarize and critically discuss the recent advances in the structural design of mono- and bimetallic catalysts for the oxidation of glucose in aqueous media. Furthermore, the challenges of developing catalysts for the green synthesis of gluconic acid have been highlighted. This review provides alternative insights for designing effective catalytic materials for the catalytic oxidation of bio-derived oxygenates over heterogeneous catalysts.

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Measurable surface d charge of Pd as a descriptor for the selective hydrogenation activity of quinoline Shunlin Li, Lili Wang, Mengmeng Wu, Yafei Sun, Xiaojuan Zhu, Ying Wan 2020, 41 (9):  1337-1347.  DOI: 10.1016/S1872-2067(20)63580-X Abstract ( 48 )   [Full Text(HTML)] () PDF (1333KB) ( 287 )   Supporting Information AuPd nanoalloys with tunable Pd concentrations have been synthesized and used as model catalysts. They have been directly imaged by high-angle annular dark-field scanning transmission electron microscopy and investigated by thorough analyses of their extended X-ray absorption fine structure, X-ray absorption near-edge structure, X-ray diffraction and X-ray photoelectron spectroscopy measurements. The bimetallic nanoparticles are embedded in a carbonaceous matrix and have almost an identical structure at the atomic level and the same electronic properties as AuPd bulk alloys with the same compositions. The d-electron increase at surface Pd sites is determined by the Pd concentration of the alloy. Similarly, their activation entropy and catalytic activity for the hydrogenation of quinoline is related to the Pd concentration, with Au50Pd50 the most active of the alloys investigated. An almost 11 times higher activity was achieved compared to a pure Pd catalyst. The experimentally measurable surface d charge at the Pd sites in the AuPd was found to linearly correlate with the activation entropy and catalytic activity for the hydrogenation of quinoline. The alloy structure is stable, showing negligible metal segregation, dissolution-redeposition and aggregation during the hydrogenation process which involves strong adsorption.

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Copper-ceria solid solution with improved catalytic activity for hydrogenation of CO2 to CH3OH Bin Yang, Wei Deng, Limin Guo, Tatsumi Ishihara 2020, 41 (9):  1348-1359.  DOI: 10.1016/S1872-2067(20)63605-1 Abstract ( 235 )   [Full Text(HTML)] () PDF (1695KB) ( 415 )   Supporting Information A copper-ceria solid solution and ceria-supported copper catalysts were prepared and used for the catalytic hydrogenation of CO2 to CH3OH. According to site-specific classification and quantitative analyses (X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, H2 temperature-programmed reduction, and CO adsorption), the interfaces of the prepared catalysts were classified as Cu incorporated into ceria (Cu-Ov-Cex), dispersed CuO (D-CuO-CeO2), and bulk CuO (B-CuO-CeO2) over the CeO2 surface. These results, together with those of activity tests, showed that the Cu-Ov-Cex species was closely related to the CO2 hydrogenation activity and resulted in a much higher turnover frequency of CH3OH production than that observed with the D-CuO-CeO2 and B-CuO-CeO2 species. Thus, the copper-ceria solid solution exhibited improved activity due to the higher Cu-Ov-Cex fraction.

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Structures and reactivities of the CeO2/Pt(111) reverse catalyst: A DFT+U study Zhu-Yuan Zheng, Dong Wang, Yi Zhang, Fan Yang, Xue-Qing Gong 2020, 41 (9):  1360-1368.  DOI: 10.1016/S1872-2067(20)63564-1 Abstract ( 70 )   [Full Text(HTML)] () PDF (712KB) ( 170 )   Supporting Information For heterogeneous catalysts, the build-up of interface contacts can influence markedly their activities. Being different from the conventional supported metal/oxide catalysts, the reverse type of oxide/metal structures, e.g. the ceria/Pt composite, have emerged as novel catalytic materials in many fields. However, it remains challenging to determine the optimal interface structure and/or the metal-oxide synergistic effect that can boost catalytic activities. In this work, we conducted density functional theory calculations with on-site Coulomb interaction correction to determine the optimal structures and investigate the physical as well as catalytic properties of various CeO2/Pt(111) composites containing CeO2(111) monolayer, bilayer, and trilayer at Pt(111). We found that the interaction strength between CeO2(111) and Pt(111) substrate first reduces as the ceria slab grows from monolayer to bilayer, and then largely gets converged when the trilayer occurs. Such trend was well rationalized by analyzing the number and distances of O-Pt bonds at the interface. Calculated Bader charges uncovered the significant charge redistribution occurring around the interface, whereas the net electron transfer across the interface is non-significant and decreases as ceria thickness increases. Moreover, comparative calculations on oxygen vacancy formation energies clarified that oxygen removal can be promoted on the CeO2/Pt(111) composites, especially at the interface. We finally employed CO oxidation as a model reaction to probe the surface reactivity, and determined an intrinsic activity order of monolayer CeO2(111) > monolayer CeO2(111)/Pt(111) > regular CeO2(111). More importantly, we emphasized the significant role of the moderate ceria-Pt interaction at the interface that endows the CeO2/Pt reverse catalyst both good thermostability and high catalytic activity. The monolayer CeO2(111)/Pt(111) composite was theoretically predicted highly efficient for catalyzing CO oxidation.

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Multi sites vs single site for catalytic combustion of methane over Co3O4(110): A first-principles kinetic Monte Carlo study Wende Hu, Zheng-Jiang Shao, Xiao-Ming Cao, P. Hu 2020, 41 (9):  1369-1377.  DOI: 10.1016/S1872-2067(20)63563-X Abstract ( 51 )   [Full Text(HTML)] () PDF (1030KB) ( 329 )   Single-atom catalysts have been applied in many processes recently. The difference of their kinetic behavior compared to the traditional heterogeneous catalysts has not been extensively discussed yet. Herein a complete catalytic cycle of CH4 combustion assuming to be confined at isolated single sites of the Co3O4(110) surface is computationally compared with that on multi sites. The macroscopic kinetic behaviors of CH4 combustion on Co3O4(110) is systematically and quantitatively compared between those on the single site and multi sites utilizing kinetic Monte Carlo simulations upon the energetic information from the PBE + U calculation and statistic mechanics. The key factors governing the kinetics of CH4 combustion are disclosed for both the catalytic cycles respectively following the single-site and multi-site mechanisms. It is found that cooperation of multi active sites can promote the activity of complete CH4 combustions substantially in comparison to separated single-site catalyst whereas the confinement of active sites could regulate the selectivity of CH4 oxidation. The quantitative understanding of catalytic mechanism paves the way to improve the activity and selectivity for CH4 oxidation.

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In-situ route for the graphitized carbon/TiO2 composite photocatalysts with enhanced removal efficiency to emerging phenolic pollutants Yunqing Liu, Peiyu Xia, Lingyu Li, Xinyue Wang, Jiaqi Meng, Yuxin Yang, Yihang Guo 2020, 41 (9):  1378-1392.  DOI: 10.1016/S1872-2067(20)63565-3 Abstract ( 48 )   [Full Text(HTML)] () PDF (1470KB) ( 212 )   Supporting Information TiO2 is the most photoactive material because of its superstrong photooxidizing ability, and TiO2 photocatalysis has been widely applied in sustainable water treatment and environmental remediation. However, poor sunlight or visible-light harvesting efficiency and fast recombination rate of the photogenerated charge carriers severely limit the practical applications of TiO2. To overcome these problems, the present work demonstrates a facile in-situ co-condensation method combined with hydrothermal treatment to prepare a series of graphitized carbon/TiO2 composite photocatalysts, and anatase TiO2 phase and p-p-conjugated polycyclic aromatic carbon structure are created simultaneously. As-prepared TiO2/C composites exhibit remarkably high visible-light photocatalytic activity in the degradation of aqueous emerging phenolic pollutants, acetaminophen (APAP) and methylparaben (MPB), and apparent rate constant of the TiO2/C composite with carbon doping level of 10.3% for APAP and MPB removal is 7.6 and 2.8 times higher than that of bare TiO2, and 6.2 and 2.6 times higher than that of Degussa P25 TiO2. Based on the results of photoelectrochemical experiments, indirect chemical probe measurements, and ESR spectroscopy, it is verified that doping TiO2 with graphitized carbon is responsible for this enhanced photocatalytic activity, which renders the improved visible-light harvesting ability, the accelerated separation of the photogenerated charge carriers, and enlarged BET surface areas. Through analyzing the intermediates yielded in the photodegradation process, the pathway of visible-light photocatalytic degradation of APAP and MPB over the TiO2/C composite is proposed.

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Copper-indium bimetallic catalysts for the selective electrochemical reduction of carbon dioxide Jiaqi Shao, Yi Wang, Dunfeng Gao, Ke Ye, Qi Wang, Guoxiong Wang 2020, 41 (9):  1393-1400.  DOI: 10.1016/S1872-2067(20)63577-X Abstract ( 144 )   [Full Text(HTML)] () PDF (1123KB) ( 487 )   Supporting Information Copper-indium bimetallic catalysts with a dendritic structure are fabricated by a two-step electrodeposition method using a hydrogen evolution template for the CO2electroreduction reaction (CO2RR). The dendritic Cu-In-30 catalyst electrodeposited for 30 min shows the highest specific surface area and exposes the most active sites, resulting in improved CO2RR activity. The dendritic Cu-In-30 catalyst exhibits distinctly higher formate partial current density (42.0 mA cm-2) and Faradaic efficiency (87.4%) than those of the In-30 catalyst without the dendritic structure (the formate partial current density and Faradaic efficiency are 4.6 mA cm-2and 57.0%, respectively) at -0.85 V vs. reversible hydrogen electrode, ascribed to the increased specific surface area. The Cu-In-30 catalyst can maintain stable performance for 12 h during the CO2RR. In addition, the intrinsic current density of Cu-In-30 with the dendritic structure (4.8 mA cm-2) is much higher than that of In-30 without the dendritic structure (2.1 mA cm-2), indicating that the dendritic structure promotes the CO2RR, possibly due to additional coordination unsaturated atoms.

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Acid-catalyzed chemoselective C- and O-prenylation of cyclic 1,3-diketones Ying Li, Yan-Cheng Hu, Ding-Wei Ji, Wei-Song Zhang, Gu-Cheng He, Yu-Feng Cong, Qing-An Chen 2020, 41 (9):  1401-1409.  DOI: 10.1016/S1872-2067(20)63575-6 Abstract ( 62 )   [Full Text(HTML)] () PDF (741KB) ( 136 )   The chemoselective C- and O-prenylation of cyclic 1,3-diketones was achieved by tuning the prenyl source and catalyst. In the presence of the solid acid Nafion, the coupling of 1,3-cyclohexanediones with isoprene gave C-prenylated 5-chromenones. Alternatively, using prenol as the substrate with the Lewis acid AlCl3 as the catalyst resulted in the exclusive O-prenylation of 1,3-cyclohexanediones. Notably, the resulting products could easily undergo aromatization to deliver prenylated resorcinols that are otherwise difficult to prepare. Our methodology is highly selective, atom-economical, operationally simple, easily scalable, and has potential applications throughout organic synthesis.

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A reconstruction strategy for the synthesis of Cu-SAPO-34 with excellent NH3-SCR catalytic performance and hydrothermal stability Lijing Sun, Miao Yang, Yi Cao, Peng Tian, Pengfei Wu, Lei Cao, Shutao Xu, Shu Zeng, Zhongmin Liu 2020, 41 (9):  1410-1420.  DOI: 10.1016/S1872-2067(20)63583-5 Abstract ( 58 )   [Full Text(HTML)] () PDF (1185KB) ( 230 )   Supporting Information A reconstruction strategy has been developed to synthesize Cu-SAPO-34 with a wide crystallization phase region, high solid yield, and tunable Si and Cu contents. Cu-rich SAPO-34 was prepared from a Cu-amine complex, which acted as a precursor and Cu source for the reconstruction synthesis. The role of the Cu-amine complex as a template was restricted, which allowed easier control over the Cu and Si contents than in the previously reported "one-pot" synthesis method. Characterization of the material revealed that the Si(4Al) coordination environment dominates the synthesized Cu-SAPO-34 catalysts. High-temperature hydrothermal treatment increased the isolated Cu2+ content slightly, and the acid sites in the low-silica catalyst are more resistant to hydrothermal treatment than those of the existing catalysts. The obtained materials, especially the low-silica Cu-SAPO-34 sample, exhibit excellent catalytic activity and hydrothermal stability for the selective catalytic reduction of NOx by NH3 (NH3-SCR). In addition, the influence of the catalyst acidity on the NH3-SCR reaction was also investigated and is discussed. The high synthetic efficiency and outstanding catalytic performance make Cu-SAPO-34 synthesized by the reconstruction method a promising catalyst for the NH3-SCR process.

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CdS/ZnS/ZnO ternary heterostructure nanofibers fabricated by electrospinning for excellent photocatalytic hydrogen evolution without co-catalyst Diankun Sun, Jian-Wen Shi, Dandan Ma, Yajun Zou, Guotai Sun, Siman Mao, Lvwei Sun, Yonghong Cheng 2020, 41 (9):  1421-1429.  DOI: 10.1016/S1872-2067(20)63576-8 Abstract ( 108 )   [Full Text(HTML)] () PDF (768KB) ( 349 )   Supporting Information In recent years, ternary heterostructures (HSs) composed of three semiconductors have attracted significant attention because of the effective separation and transfer of photogenerated electrons and holes in these materials. In this work, new ternary CdS/ZnS/ZnO (CZZ) HSs with one-dimensional (1D) nanofiber morphology have been successfully fabricated for the first time by a series of processes:electrospinning ZnO nanofibers, sulfurizing ZnO in situ to form ZnS/ZnO binary HSs, and depositing CdS quantum dots in situ on the ZnS/ZnO HSs. Benefiting from the efficient separation and transfer of photoinduced charge carriers, the optimized CZZ ternary HSs exhibit a hydrogen evolution rate of 51.45 mmol h-1 g-1 (quantum efficiency:26.88% at 420 nm) without any co-catalyst, which is 93.54 and 2.28 times higher than those exhibited by pristine ZnO and ZnS/ZnO binary HSs, respectively, under the same conditions. Furthermore, the rate of hydrogen evolution over the 1D CZZ nanofibers is significantly higher than that over 2D CZZ nanosheets (27.25 mmol h-1 g-1, in the presence of a Pt co-catalyst) prepared by the same sulfurization and deposition procedures. This can be ascribed to the significantly smaller geometric sizes of 1D nanofibers compared to those of 2D nanosheets, resulting in effectively suppressed recombination of photogenerated charge carriers and promotion of photocatalytic H2 evolution performance.

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Bi quantum dots implanted 2D C-doped BiOCl nanosheets: Enhanced visible light photocatalysis efficiency and reaction pathway Ye He, Jieyuan Li, Kanglu Li, Minglu Sun, Chaowei Yuan, Ruimin Chen, Jianping Sheng, Geng Leng, Fan Dong 2020, 41 (9):  1430-1438.  DOI: 10.1016/S1872-2067(20)63612-9 Abstract ( 110 )   [Full Text(HTML)] () PDF (684KB) ( 269 )   Supporting Information The simultaneous integration of heteroatom doping and surface plasmon resonance (SPR) modulation on semiconductor photocatalysts could be capable of improving visible light utilization and charge separation, achieving better solar light conversion and photocatalysis efficiency. For this purpose, we have designed a novel Bi quantum dots (QDs) implanted C-doped BiOCl photocatalyst (C/BOC/B) for NOx removal. The feasibility was firstly evaluated through density functional theory (DFT) calculations methods, which indicates that the enhanced photocatalytic performance could be expected owing to the synergistic effects of doped C heteroatoms and loaded Bi QDs. Then, the C/BOC/B was synthesized via a facile hydrothermal method and exhibited efficient and stable visible light photocatalytic NO removal. The results found that the doped C atoms can serve as electron guides to induce oriented charge transfer from Bi QDs to BiOCl, while the Bi QDs can act as light-capture and electron-donating sites. The reaction pathway and mechanism for NO conversion was unveiled by in situ Fourier-transform infrared spectroscopy combined with DFT calculation. The enhanced adsorption of reactants and intermediates could promote the overall reaction efficiency and selectivity in photocatalytic NO conversion. This work could provide a new perspective on the mechanistic understanding of the synergistic effects toward non-metal doping and SPR effects in semiconductor photocatalysts, and this presented technique could be extended for other semiconductor materials.