Novel Fe‐modified CeO₂ Nanorod Catalyst for the Dimethyl Carbonate Formation from CO₂ and Methanol

Abstract

A series of Fe-modified CeO 2 catalysts with nanoparticle, nanorod, nanocube and nano-octahedron morphologies were synthesized and applied for direct synthesis of dimethyl carbonate (DMC) from CO 2 and methanol. The Fe-modification shows a remarkably promoting effect on the formation of DMC over Fe-modified CeO 2 nanorod. The DMC yield was improved from 0.202 to 2.568 mmol DMC per g cat by 2 %Fe-modification of CeO 2 nanorod. A synergistic effect among the moderate acidbasic sites, specific surface area and surface composition resulted from Fe-modification was proposed to be crucial to obtaining the high reactivity of DMC formation.

Ultrasonically assisted surface modified CeO2 nanospindle catalysts for conversion of CO2 and methanol to DMC

“…(g) Pressure (MPa) Temp. (°C) CeO 2 Hydrothermal – Spindle 0.1 5.0 140 1.38 [17] CeO 2 Precipitation – Spindle 1.0 8.0 140 13.84 [43] CeO 2 Hydrothermal – Rod 0.2 3.0 160 0.20 [44] CeO 2 Solvothermal Thermal reduction under H 2 Wire 0.2 5.0 120 16.85 [35] CuO/CeO 2 Hydrothermal Impregnation Rod 0.5 3.0 140 0.60 [70] CeO 2 Precipitation – Spindle 0.1 4.5 140 14.44 This work CeO 2 -B Precipitation Chemical redox etching Spindle 0.1 4.5 140 17.90 This work CeO 2 -B-CuO Precipitation Chemical redox etching & Impregnation Spindle 0.1 4.5 140 16.47 This work <...…”

“…However, due to thermodynamic limitations as shown, CO 2 + 2CH 3 OH → (CH 3 O) 2 CO + H 2 O (ΔG° = 26 kJ.mol −1 ), the conversion reaction requires energy input and the DMC yield is relatively low [33] , [34] , [35] . Hence, various metal oxide catalysts, for instance, K 2 CO 3 [36] , [37] , ZrO 2 [38] , [39] , TiO 2 [40] , [41] and CeO 2 [19] , [42] , [43] , [44] , have been used to increase the reaction rate and DMC formation.…”

Boat‐, Cuboid‐, and Dumbbell‐Shaped Hierarchical Morphology of Cerium (IV) Hydroxidophosphate Materials for Oxidative Coupling Reaction

“…The X-ray diffraction pattern (Figure S3) specified the presence of two phases in the CHP-6 materials, i. e. Ce(OH)PO 4 and CeO 2 ; because this obtained XRD pattern matches the JCPDS 96-723-2934 for orthorhombic Ce(OH)PO 4 phase and JCPDS 96-900-9009 for cubic CeO 2 . [25] This wide-angle XRD analysis evidently specifies that the as-synthesized materials are highly crystalline in nature.…”

Efficient Visible‐Light‐Assisted Synthesis of Dimethyl Carbonate from CO2 and Methanol by Ce–Metal Organic Framework‐Derived CeO2 Nanoparticles

“…[14] Luo et al reported that CeO 2 nanoparticle performance for the synthesis of DMC from CO 2 and methanol reached up to 1.6 mmol g À1 , exceeding the activity of nanorods, nanocubes, and nano-octahedrons. [15] It was proved that the Lewis acid-base sites on the catalyst surface were intimately connected with the formation of DMC. For instances, Xie and co-workers demonstrated that controlled vacancy clusters on the CeO 2 surfaces construct Lewis acid-base pairs to effectively enhance CO 2 /CH 3 OH activation and formation of key intermediates of methoxy carbonate species for the synthesis of DMC.…”