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• W4309947231 abstract "Open AccessCCS ChemistryRESEARCH ARTICLES22 Dec 2022Selective Hydrogenation of Phenylacetylene by Carbon Monoxide and Water Xuetao Qin†, Ruiqi Zhang†, Ming Xu, Yao Xu, Lirong Zheng, Chengyu Li, Shixiang Yu, Jie Yan, Jinglin Xie, Genghuang Wu, Junfeng Rong, Meng Wang and Ding Ma Xuetao Qin† College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 †X. Qin and R. Zhang contributed equally to this work.Google Scholar More articles by this author , Ruiqi Zhang† College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 †X. Qin and R. Zhang contributed equally to this work.Google Scholar More articles by this author , Ming Xu College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029 Google Scholar More articles by this author , Yao Xu College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 Google Scholar More articles by this author , Lirong Zheng Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049 Google Scholar More articles by this author , Chengyu Li College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 Google Scholar More articles by this author , Shixiang Yu College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 Google Scholar More articles by this author , Jie Yan College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 Google Scholar More articles by this author , Jinglin Xie College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 Google Scholar More articles by this author , Genghuang Wu Research Institute of Petroleum Processing, SINOPEC, Beijing 100083 Google Scholar More articles by this author , Junfeng Rong *Corresponding authors: E-mail Address: [email protected] E-mail Address: [email protected] E-mail Address: [email protected] Research Institute of Petroleum Processing, SINOPEC, Beijing 100083 Google Scholar More articles by this author , Meng Wang *Corresponding authors: E-mail Address: [email protected] E-mail Address: [email protected] E-mail Address: [email protected] College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 Google Scholar More articles by this author and Ding Ma *Corresponding authors: E-mail Address: [email protected] E-mail Address: [email protected] E-mail Address: [email protected] College of Chemistry and Molecular Engineering, Peking University, Beijing 100871 Google Scholar More articles by this author https://doi.org/10.31635/ccschem.022.202202402 SectionsSupplemental MaterialAboutAbstractPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail Catalytic selective hydrogenation of alkynes to the corresponding alkenes is an important process in industrial production. Modulating the selective hydrogenation of alkynes to the alkenes requires ingenuity since alkenes can easily be converted into the corresponding alkanes under reductive conditions. Applying different reductive reagents to prevent the direct usage of H2 can avoid difficulties in hydrogen storage and transportation. Herein, we demonstrate a tandem process to hydrogenate phenylacetylene by CO and H2O via the coupling of the low-temperature water-gas shift reaction and selective hydrogenation of phenylacetylene utilizing the α-MoC catalyst. The reductive reagent, CO, not only produces H2 from H2O to drive the reaction forward, but it also regulates the selectivity of styrene by preventing further hydrogenation. Download figure Download PowerPoint Introduction The production of fine chemicals and the polymerization industry both place a great deal of importance on the catalytic selective hydrogenation of alkynes to the corresponding alkenes. Styrene can be utilized as a monomer for synthetic resin and rubber in addition to being a key raw material in the production of polystyrene.1 The extraction of styrene from cracked petroleum is one of the most promising processes for producing styrene. However, the extraction procedure leaves behind phenylacetylene, which will eventually become richer,2,3 and the styrene polymerization process becomes poisoned by the presence of phenylacetylene.4 Therefore, the removal of any remaining acetylene through selective hydrogenation prior to styrene polymerization is crucial. But excessive hydrogenation to ethylbenzene of acetylene and styrene during the hydrogenation process may be unavoidably result. Therefore, the creation of a catalytic system with high selectivity and activity for the selective hydrogenation of phenylacetylene is critical. Molecular hydrogen is not the only choice to process the reaction, especially when the selectivity for hydrogenation reactions can be regulated with different hydrogen donors.5–9 In the meantime, the alternatives, for example, alcohols, polyol, and CO and H2O, for the synthesis of valuable chemicals—a promising route for hydrogen utilization—can avoid problems with the transportation and storage of hydrogen.6,10–16 Hydrogenation can occur directly via hydrogen transfer6 or proceed with H2 generated in situ via dehydrogenation5 or the water-gas shift (WGS) reaction15,17 under reaction conditions. Except for several examples from homogeneous catalysis,18,19 hydrogenation by CO and H2O has been found to show a special advantage in different heterogeneous catalytic systems including hydroformylation,14 reduction of aromatic nitro compounds15,20 and CO hydrogenation,17 which modulate the liner-to-branch ratio of aldehyde products, achieves rapid conversion of aromatic nitro compounds, and converts CO and H2O directly into liquid fuels, respectively. For selective hydrogenation of alkynes, complex catalyst structures were fabricated, or toxic additives were added to increase the selectivity.21–27 Since the toxic effect of CO and the usage of in situ-generated H2 from WGS15,17 have been investigated for different hydrogenation processes, we propose a novel system by applying CO and H2O as reactants to combine the WGS reaction for the H2 supply and the selectivity control of alkyne hydrogenation with the presence of CO. Transition metal carbides have shown similar or even better catalytic activities than noble metals in hydrogenation reactions,28 and the strong dissociative adsorption of CO and water on metal carbides10,11,29 inspires us to combine the WGS reaction and hydrogenation of phenylacetylene directly. Thus, instead of using conventional catalysts like the noble metals (e.g., Pd, Au, and Pt),5,21,22,25,27,30 molybdenum carbide (MoC) was chosen because it has noble metal-like properties31 and exhibits strong antitoxicity and excellent WGS reactivity,10,11,32 which is beneficial for us to realize the tandem of the WGS reaction and the selective hydrogenation of phenylacetylene. Herein, we report the tandem process of low-temperature WGS reaction and selective hydrogenation of phenylacetylene using an α-MoC catalyst. With this strategy, not only the storage and transportation problems of hydrogen are avoided, but the selectivity of styrene can also be regulated. Therefore, this coupling route presents a promising method for the preparation of alkenes during the selective hydrogenation of phenylacetylene and its derivatives without the use of noble metal catalysts. Experimental Details Chemicals and materials Ammonium paramolybdate ((NH4)6Mo7O24·4H2O) and cyclohexane were purchased from Sinopharm Chemical Reagent Co., Ltd. (Haidian, Beijing, China). Phenylacetylene, styrene, and 4-ethynyltoluene were purchased from Shanghai Macklin Biochemical Co., Ltd. (Pudong New Area, Shanghai, China). 4-Fluorophenylacetylene and 3-aminophenylacetylene were purchased from Energy Chemical (Pudong New Area, Shanghai, China). 4-Methoxyphenylacetylene and 1-Octyne were purchased from Aladdin (Fengxian, Shanghai, China). 1-Phenyl-1-propyne was purchased from 9ding Chemistry (Fengxian, Shanghai, China). 3-Chloro-1-ethynylbenzene was purchased from Shanghai Yuanye Bio-Technology Co., Ltd. (Songjiang, Shanghai, China). Gas: ammonia gas, 15% CH4/85% H2, 0.5%O2 in Ar, 20% CH4/80% H2, 96% CO/4% Ar, 90% H2/10% Ar, Ar were purchased from Haikeyuanchang Gas Co., Ltd. (Haidian, Beijing, China). Preparation of the α-MoC catalyst MoO3 was prepared first via calcination of (NH4)2Mo7O24·4H2O (>99.0%, Sinopharm Chemical Reagent Co., Ltd., Haidian, Beijing, China) in stagnant air at 773 K for 4 h. These MoO3 powders were heated to 973 K (10 K/min) in flowing NH3 (160 mL/min; prepurified gas) and held at 973 K for 2 h, and then they were treated in flowing 20% CH4/H2 (125 mL/min; prepurified gas), at the same temperature for 2 h to obtain pure-phase α-MoC. Catalysts were passivated in flowing 0.5% O2/Ar (60 mL/min) at ambient temperature for 12 h before exposure to air. Catalyst characterization X-ray diffraction (XRD) experiments were carried out on an X’Pert3 Powder diffractometer (PANalytical B.V. Eindhoven, Noord-Brabant, Netherlands) with Cu Kα radiation (Condition: 40 kV and 100 mA; Scan rate: 5° min−1) and a 2θ angle ranging from 5° to 80°. The crystal structure of components was identified based on Joint Committee on Powder Diffraction Standards (JCPDS) standard cards. X-ray absorption spectroscopy (XAS) were measured in transmission mode at the Mo K-edge (20,000 eV) using the 1W1B beamline at the Beijing Synchrotron Radiation Facility (BSRF), Institute of High Energy Physics (IHEP), Chinese Academy of Sciences (CAS). Mo foil and MoO3 (Aldrich, Pudong New Area, Shanghai, China) were used as references. The chemical state of Mo atoms exposed on α-MoC catalysts was determined using an Axis ultra imaging photoelectron spectrometer (Kratos Analytical, Manchester, Greater Manchester, Britain). These samples were transferred into the chamber of the X-ray photoelectron spectroscopy (XPS) spectrometer under argon protection for measurements. The (scanning) transmission electron microscopy ((S)TEM) imaging and energy-dispersive X-ray spectroscopy mapping of α-MoC catalysts was conducted on a field emission FEI Tecnai F20 (FEI Company, Hillsboro, Oregon, America) microscope equipped with a high-angle annular dark field (HAADF) detector and an Oxford X-MaxN TSR silicon drift detector. The operating voltage of the microscope was 200 kV. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) were carried out to further monitor the CO effect on reactive molecules and products with CO or without CO for the reaction over the α-MoC catalyst. The temperature-programmed desorption (TPD) experiments for the phenylacetylene or styrene with CO or without CO were conducted in a fixed-bed reactor with a quartz lining under the atmosphere. Then TPD was operated at the programmed rising temperature of 5 K/min. The temperature-programmed surface reaction (TPSR) experiments for the phenylacetylene hydrogenation with CO or without CO were conducted in a fixed-bed reactor with a quartz lining under atmospheric pressure. Then TPSR was operated at the programmed rising temperature for 5 K/min with H2 (H2: Ar=10: 90; 30 mL/min) or H2 and CO (H2: CO: Ar=10: 20: 70; 30 mL/min). A mass detector (OMNI Star™ GSD 350) was used to analyze the TPD and TPSR signal of m/z = 28 (CO), 91 (EB), 102 (PA), and 104 (ST). Catalyst evaluation Phenylacetylene hydrogenation coupled with the WGS reaction was carried out in a 150 mL stainless-steel autoclave. One mmol phenylacetylene (>99%, Macklin, Pudong New Area, Shanghai, China) and 30 mL solvent (water and cyclohexane) previously deaerated by argon flow for 30 min, together with a certain amount of α-MoC catalysts (50–100 mg), were loaded into the autoclave. The autoclave was sealed and purged by 96% CO/4% Ar three times, pressurized with CO/Ar to the desired values (0.1–2 MPa), and then heated to the reaction temperature (stirring speed at 800 rpm to ensure the removal of mass transfer effects during the reaction). The concentration of phenylacetylene and reaction products were analyzed using a gas chromatograph (Agilent 7820A) equipped with a flame ionization detector and an Agilent HP-INNOWWax column in which decahydronaphthalene was used as an external calibration agent for quantifying phenylacetylene conversions and product selectivities. The chemical identity of the products was confirmed by a mass selective detector (Agilent 5975) after separation by gas chromatography (Agilent 7820A). The carbon balance was typically above 95%, and the product selectivities were reported here on a carbon basis. Results and Discussion Catalyst structure The α-MoC catalyst was manufactured by programmed-temperature nitriding and carbonization of MoO3 powders. Synthesis details of the α-MoC catalyst have been reported previously.29 Transmission electron microscopy (TEM) characterization showed that the catalyst had the porous appearance with highly textured nanocrystals of 2–10 nm in size, and Mo and C atoms were uniformly distributed in the bulk phase (Figure 1a,b and Supporting Information Figure S1). The crystalline phase was confirmed by XRD measurement (Figure 1c). The XRD pattern of the synthesized α-MoC catalyst exhibited peaks at 37.0°, 42.6°, 62.4°, and 74.4° within the 2θ range of 20°–80°, agreeing with that predicted theoretically.29 In particular, the Mo atoms in the α-MoC phase have positive charges, as measured by both XPS and X-ray absorption near-edge structure (XANES) spectroscopy (Figure 1d,e), while the extended X-ray-absorption fine-structure and wavelet transform (WT) analysis showed that such Mo centers in α-MoC had Mo-C interactions (Figure 1f and Supporting Information Figure S2). Figure 1 | Characterization results of catalyst. (a) TEM images of the fresh α-MoC catalyst (denoted as α-MoC-fresh). (b) Selected area electron diffraction pattern of the α-MoC-fresh catalyst. (c) XRD of the α-MoC-fresh catalyst. (d) XPS spectra of O 1s, Mo 3p, C 1s, and Mo 3d regions of the α-MoC-fresh catalyst. (e) Mo K-edge XANES results of Mo foil, MoO3 and α-MoC-fresh. (f) The k2-weighted Fourier transform spectra and WT analysis of the α-MoC-fresh catalyst. Download figure Download PowerPoint Catalytic performance We first tested the α-MoC catalyst in a batch reactor to explore how they perform in the WGS reaction (step I) and the hydrogenation of phenylacetylene by H2 (step II) (Figure 2a). The WGS reaction easily occurred with the 10.3% conversion of CO and generated an extensive amount of H2 (∼5 mmol) for the further hydrogenation reaction at 120 °C in 6 h (Reaction 1, Figure 2b). For the hydrogenation of phenylacetylene (1 mmol) by pure H2, the phenylacetylene was fully converted in 6 h, and the selectivity to styrene was only 52% because it was over-hydrogenated into ethylbenzene (Reaction 2, Figure 2b). By switching the gas atmosphere to CO, the hydrogen production from the WGS reaction was close to the system without the feeding of phenylacetylene. In the meantime, 100% conversion of phenylacetylene was achieved as well in 6 h, but the selectivity of styrene was 91% (Reaction 4, Figure 2b). The selectivity was much higher than the reaction in H2. It seems that the CO not only produced H2 with H2O but also modulated the selectivity of styrene. By adding CO to H2 for the hydrogenation process without using water as the solvent to prohibit the H2 generation from CO and H2O (Reaction 3, Figure 2b), the modulation effect was demonstrated. Compared to the process under pure H2 (52%), the selectivity of styrene (77%) was enhanced when the full conversion was achieved under the same reaction temperature and time. To further confirm this, styrene was fed as the reactant with CO under the same conditions compared to Reaction 4, and we discovered that styrene was almost unreactive and ethylbenzene was not detected even though an extensive amount of H2 was produced as usual (conversion <0.5%, Reaction 5 in Figure 2b and Supporting Information Table S2). Figure 2 | Catalytic performance of the α-MoC catalyst. (a) Scheme of the tandem process for selective hydrogenation of phenylacetylene combining WGS reaction (step I) and hydrogenation reaction (step II). (b) Catalytic performance of the α-MoC catalyst with different reactants. (c) Catalytic performance of phenylacetylene hydrogenation with CO and H2O on the α-MoC catalyst with different reaction time. (d) Catalytic stability of the α-MoC catalyst. Typical reaction conditions: 1 mmol substrate (PA or ST), 30 mL solvent (water/cyclohexane = 25/5), α-MoC (100 mg), 1 MPa reaction gas at room temperature (RT) (H2, H2 + CO, or CO), 120 °C, reaction time is 6 h for (b) and (d). * solvent was pure cyclohexane. Phenylacetylene and styrene are denoted as PA and ST respectively. Download figure Download PowerPoint Then, we simultaneously examined the hydrogenation reaction of phenylacetylene with different reaction times. The transformation of CO and phenylacetylene both increased gradually with the reaction time. The conversion of CO rapidly reached 3.0% in the first 30 min, generating enough H2 (∼2 mmol) for the hydrogenation of phenylacetylene, and the excess amount of H2 was formed in the following 24 h (H2: phenylacetylene ∼15 at 24 h). Even so, the high selectivity of styrene was maintained not only during the first 6 h when the conversion of phenylacetylene rose from 0% to 100%, but also during the prolonged reaction time from 6 to 24 h (Figure 2c and Supporting Information Table S3). This demonstrates that the ability of the α-MoC catalyst to control the selectivity of phenylacetylene hydrogenation under WGS reaction conditions is an inherent feature rather than being subject to kinetic control. To evaluate the stability of the α-MoC catalyst, we carried out five experimental cycles. This showed the good stability on reactivity and selectivity of the α-MoC catalyst for the hydrogenation of phenylacetylene under WGS conditions (Figure 2d and Supporting Information Table S4). And the structure of the catalyst remained stable after one and five cycles according to quasi in situ XRD, TEM, XPS, and XAS ( Supporting Information Figures S6–S14). To investigate the modulation effect of CO for the selective hydrogenation reaction, the adsorption properties of reactant (phenylacetylene) and product (styrene) on α-MoC were studied using in situ DRIFTS and TPD. For the DRIFTS analysis, the desorption processes of phenylacetylene and styrene were monitored by prolonging the time by switching to an inert gas atmosphere (Ar) after the preadsorption with or without the presence of CO at 120 °C ( Supporting Information Figures S16–S22). By selecting the stretching vibrations at 3330 cm−1 [v(≡C–H) stretching vibrations of phenylacetylene], 2171 cm−1 (gas phase CO), and 1490 cm−1 [v(C=C) stretching vibrations of styrene] for the analysis for phenylacetylene, CO, and styrene, respectively, and setting their intensities prior to the desorption to be 100% (Figure 3a,b), we could semiquantitatively analyze the desorption behaviors of the chemicals under reaction temperature (120 °C). The rapid decrement of CO from 100% to 0% was assigned to the quick replacement of gaseous components. The desorption plots of phenylacetylene were not affected by whether CO was present or absent during the adsorption (Figure 3a). The relatively slower decrement compared to CO could be explained by the physisorbed species while the remaining proportion (∼30%) was assigned to the chemisorbed phenylacetylene at 120 °C. The adsorption of styrene in the absence of CO was close to phenylacetylene that showed physisorbed and chemisorbed species as well (Figure 3b). This indicates that both phenylacetylene and styrene can easily be adsorbed on α-MoC, and they both can be hydrogenated with pure H2 which might lead to poor selectivity of styrene for the hydrogenation. But the chemisorption was blocked by CO because the gaseous and physisorbed styrene could be fully purged in 30 min (Figure 3b). The prohibition of styrene adsorption from CO explains the failure of styrene hydrogenation with CO and H2O (Reaction 5, Figure 2a) and the modulation of the selectivity of styrene during phenylacetylene hydrogenation. Figure 3 | Analysis of the adsorption of phenylacetylene and styrene on α-MoC with/without CO. The decrements of the IR bands of phenylacetylene (a) or styrene (b) from in situ DRIFT spectra during the purging processes under Ar at 120 °C after the adsorption with/without the presence of CO. The bands were 3330 and 1490 cm−1 for phenylacetylene and styrene respectively ( Supporting Information Figures S15–S18). The temperature-programmed desorption-mass spectra (TPD-MS) analysis of phenylacetylene (c) or styrene (d) after the adsorption with/without the presence of CO. Phenylacetylene and styrene were monitored by the signals from m/z = 102 and 104 respectively. The gaseous CO (IR band at 2171 cm−1 or MS signal from m/z = 28) was monitored as well when it was cofed during the adsorption. Download figure Download PowerPoint The adsorption behaviors of phenylacetylene and styrene were confirmed via TPD investigations after the preadsorption processes with or without CO. In the case of phenylacetylene, desorption peaks of phenylacetylene were observed regardless of the presence of CO or not (Figure 3c). This is consistent with the infrared (IR) results that the chemisorption of phenylacetylene could not be affected by CO. But when CO was present during the adsorption process of styrene, no signal from styrene desorption was observed (Figure 3d). Then, we speculated that styrene was rapidly desorbed from the surface of α-MoC when it was formed from the hydrogenation of phenylacetylene in the presence of CO. To confirm the hypothesis that could explain the vital role of CO in reaction selectivity, we carried out TPSR experiments under H2 or H2/CO (H2∶CO = 1∶10) to investigate the hydrogenation of preadsorbed phenylacetylene. Ethylbenzene was the dominant product from 50 to 150 °C in pure H2, and the desorption of phenylacetylene or styrene was not detected, suggesting that styrene generated from phenylacetylene hydrogenation can keep being hydrogenated to create ethylbenzene on the α-MoC surface (Figure 4a). However, when CO was present with H2 (Figure 4b), desorption of styrene was obtained from 90 to 210 °C as the major product while desorption of phenylacetylene and formation of ethylbenzene were observed with much less signal under the lower temperature. We suspected that CO could weaken the chemisorption of phenylacetylene and lead to desorption before it could be hydrogenated at a lower temperature (<90 °C). And the active sites on α-MoC might be ununiform such that a few of them would show high activity and would not be affected by CO. Thus, ethylbenzene desorption was observed at a relatively lower temperature (∼90 °C) during the TPSR analysis, and ethylbenzene was always obtained from the reactions with nonnegligible selectivities (∼7%) under various conditions in the presence of CO (Figure 2 and Supporting Information Figures S3–S5 and Tables S1–S7). Figure 4 | TPSR analysis under H2 (a) or H2/CO (b) of α-MoC after the adsorption of phenylacetylene. Phenylacetylene, styrene, and ethylbenzene are denoted as PA, ST, and EB, respectively. Download figure Download PowerPoint The α-MoC catalyst also showed good activity and selectivity for the selective hydrogenation reactions of different alkynes under the condition of water as a hydrogen source by adding CO. Either electron-donating groups, electron-withdrawing groups, or straight-chain alkynes can be successfully transformed (conversions >92%) under the reaction conditions (Table 1). All alkynes showed high alkene selectivity (>73%), although phenylpropyne required 150 °C to achieve high conversions. Therefore, α-MoC catalysts can be used in a wide range of selective hydrogenation processes of alkynes. Table 1 | Reaction Results of Substrate Exploration over the α-MoC Catalyst Entry Substrate Temperature (°C) Conv. & Select. (%) Entry Substrate Temperature (°C) Conv. & Select. (%) 1 120 >99/91 5 120 >99/89 2 150 92/90 6 120 >99/86 3 120 >99/92 7 120 >99/96 4 120 >99/89 8 120 93/73 Reaction conditions: 100 mg α-MoC, 1 mmol Substrate, 1 MPa 96% CO/4% Ar, 6 h. Conclusions We demonstrated that selective hydrogenation of phenylacetylene and different alkynes could be accomplished through a straightforward approach, coupling with the low-temperature WGS reaction process on the α-MoC catalyst. Meanwhile, in situ DRIFTS and temperature-programmed (TP) experiments indicated that CO obviously contributes to excellent selectivity by weakening the adsorption of styrene. As a result, this coupling pathway provides a viable strategy for preparing alkenes without using noble metal catalysts or molecular hydrogen during the hydrogenation of alkynes. Supporting Information Supporting Information is available and includes methods, Figures S1–S22, Tables S1–S7, and references. Acknowledgments This work received financial support from the Natural Science Foundation of China (grant nos. 21725301, 21932002, and 21821004), the National Key R&D Program of China (grant no. 2021YFA1501102), and China Petrochemical Corporation (grant no. 420043-10). The authors are thankful for the support of the BSRF during the X-ray absorption spectroscopy (XAS) measurements at the beamline 1W1B. References 1. 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Google Scholar Previous articleNext article FiguresReferencesRelatedDetails Issue AssignmentVolume 0Issue 0Page: 1-8Supporting Information Copyright & Permissions© 2022 Chinese Chemical SocietyKeywordsmodulating selectivity by COselective hydrogenation of phenylacetyleneα-MoC catalystwater-gas shift reactionAcknowledgmentsThis work received financial support from the Natural Science Foundation of China (grant nos. 21725301, 21932002, and 21821004), the National Key R&D Program of China (grant no. 2021YFA1501102), and China Petrochemical Corporation (grant no. 420043-10). The authors are thankful for the support of the BSRF during the X-ray absorption spectroscopy (XAS) measurements at the beamline 1W1B. Downloaded 128 times PDF downloadLoading ..." @default.
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