Low Reaction Barrier Research Articles

Determining Reaction Paths by Evaluating Kinetic Isotopic Effects with Density Functional Theory: Example of Methane Thermogenesis

This study demonstrates the determination of reaction pathways by evaluating the carbon kinetic isotopic effect and interpreting isotopic fractionations based on quantum chemical calculations. The reaction under investigation is methane thermogenesis from the decomposition of kerogen, which is a geochemical reaction under temperatures below 150 °C and lasts for tens of millions of years. Investigating its mechanism requires theoretical simulations because lab experiments at practical time-lengths require elevated temperatures, which introduce unwanted side reactions. Density functional theory and kinetic simulations were conducted on isotopic fractionations with the use of two possible pathways (free-radical versus carbonium), and the results were compared to field data sets. Different molecular sizes of kerogen were investigated to account for the hindrance of translation and rotation in modeling a reactant in the solid phase. Both pathways have low reaction barriers, implying that the reaction rates are limited by the concentration of active species (hydrated protons and free radicals). The results support the carbonium pathway and rule out the free-radical pathway as the 13CH4 from the latter would be 30‰ more depleted than the observed data. Additionally, simulations were conducted on hydrocarbon isotope fractionation of the carbonium pathway with consideration of hydrogen exchange between methane and water, successively reproducing the observed abundances of deuterium-containing isotopologues (13CH3D, 13CH3D, and 12CH2D2).

Insights into the Three-Component Coupling Reactions of Aldehydes, Alkynes, and Amines Catalyzed by N-heterocyclic Carbene Silver: A DFT Study

Density functional theory (DFT) was used to investigate the three-component coupling reactions of aldehydes, alkynes, and amines (A3 coupling) using N-heterocyclic carbene silver as the catalyst. This study reveals that the addition reaction between the catalyst N-heterocyclic carbene silver and phenylacetylene (PAE) forms Ag_PAE. Subsequently, one hydrogen atom of the Ag_PAE migrates to the nitrogen atom of the Amine. Thereafter, the amine aldehyde condensation reaction generates a molecule of water and an imine ion with (Path one) or without (Path two) another amine catalyst. Path one has a lower reaction barrier than Path two. Subsequently, the imine ion reacts with silver phenylacetylide to generate the A3 coupling reaction product propargylamine (PPA). Furthermore, the triple bond and −N3 group in PPA undergo a cycloaddition reaction and generate the final product (PR). The entire reaction is strongly exothermic, and, therefore, the reaction is easy to conduct. Moreover, conceptual density functional theory calculations confirm the reaction mechanism. Investigating the mechanism of these reactions will be helpful for understanding and developing new synthesis strategies for similar functional compounds.

First-Principles Examination of Multiple Criteria of Organic Solvent Oxidative Stability in Batteries

Oxidative instability of the liquid electrolyte at or near battery cathode oxide surfaces has significant detrimental effects on batteries. Organic solvent molecules are often the fuel and precursors of such degradation processes, releasing electrons and protons that react with cathode oxides and electrolyte anions. These reactions contribute to cathode–electrolyte interphase (CEI) film formation, transition-metal ion dissolution, and phase transformation of the surface regions of the cathode. Here we apply density functional theory calculations to examine four criteria of oxidative stability (oxidation potential, hydrogen removal energies, and initial reactivity on two types of oxide facets) using four different solvent/additive molecules (ethylene carbonate, fluoroethylene carbonate, 1,3-dioxolane, and dimethyl ether). The ranking of molecular stability differs with each criterion. Surprisingly, the all-oxygen-terminated basal planes of layered oxides exhibit lower reaction barriers than spinel surface facets with exposed transition-metal cations, especially for ether solvents; the calculations also suggest basal planes contribute to the dissolution of transition-metal ions. The structure–degradation relation complexity underscores the challenge of understanding the function of the CEI but also offers a guide to future degradation-mitigation strategies including facet engineering. Our predictions and models help establish a framework for future studies relevant to high-voltage conditions.

Free-standing nanowires growing on ginkgo biloba as high areal capacity Li-ion battery anode at high and low temperatures

The low cost and special structure of biomass materials enable them to be applicable for many energy-storage systems. Here, we develop NiCo2O4 nanowires growing on carbonized ginkgo biloba to form free-standing anodes of Li-ion battery. The porous NiCo2O4 nanowires have a high capacity, and they are able to accommodate the expansion of volume in cycling. Low surface reaction barrier of the NiCo2O4/ginkgo biloba anode is confirmed by galvanostatic intermittent titration technique analysis. The NiCo2O4/ginkgo biloba anode displays recoverable rate-performance and good stability when cycling at different current densities, which remains 2.6 mAh cm−2 after 350 cycles at room temperature. The Coulombic efficiency is about 99 % under −10 °C at 1 mA cm−2, and the capacity remains 1.28 mAh cm−2 after cycling 200 times. Capacity keeps 1.83 mA cm−2 under 45 °C, exhibiting a good Li-storage performance. The NiCo2O4/ginkgo biloba anode displays a better cycling performance than NiCo2O4/nickel foam and NiCo2O4/carbon cloth. The cost-effective synthesis strategy provides extensible applications for metal oxide/ginkgo biloba-based composites. Growing other binary metal oxides on the carbonized ginkgo biloba is also achievable such as ZnCo2O4, indicating the developed composite system is promising for preparing other free-standing energy-storage composites.

Revealing the Superior Electrocatalytic Performance of 2D Monolayer WSe2 Transition Metal Dichalcogenide for Efficient H2 Evolution Reaction

AbstractH2 evolution reaction (HER) requires an electrocatalyst to reduce the reaction barriers for the efficient production of H2. 2D transition metal dichalcogenides (2D TMDs) have emerged as a pinnacle group of materials for many potential applications, including HER. In this work, a pristine 2D monolayer WSe2 TMD is computationally designed using the first principle‐based hybrid density functional theory (DFT) to investigate its structural, electronic properties and the electrocatalytic performance for HER. The possible Volmer‐Heyrovsky and Volmer‐Tafel reaction mechanisms for HER at the W‐edge of the active site of WSe2 are studied by using a nonperiodic finite molecular cluster model W10Se21. The study shows that the pristine 2D monolayer WSe2 follows either the Volmer‐Heyrovsky or the Volmer‐Tafel reaction mechanisms with a single‐digit low reaction barrier about 6.11, 8.41 and 6.61 kcal mol−1 during the solvent phase calculations of H•‐migration, Heyrovsky and Tafel transition (TS) states, respectively. The lower reaction barriers, high turnover frequency (TOF) ≈ 4.24 × 106 s−1 and 8.86 × 107 s−1 during the Heyrovsky and Tafel reaction steps and the low Tafel slope 29.58 mV dec−1 confirm that the pristine 2D monolayer WSe2 might be a promising alternative to platinum group metals (PGM) based electrocatalyst.

Screening Carbon-Boron Frustrated Lewis Pairs for Small-Molecule Activation including N2 , O2 , CO, CO2 , CS2 , H2 O and CH4 : A Computational Study.

Dinitrogen (N2 ) activation is particularly challenging under ambient conditions because of its large highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gap (10.8 eV) and high bond dissociation energy (945 kJ mol-1 ) of the N≡N triple bond, attracting considerable attention from both experimental and theoretical chemists. However, most effort has focused on metallic systems. In contrast, nitrogen activation by frustrated Lewis pairs (FLPs) has been initiated recently via theoretical calculations. Here we perform density functional theory (DFT) calculations to screen a series of experimentally viable FLPs for small-molecule activation including N2 , O2 , CO, CO2 , CS2 , H2 O and CH4 . In addition, aromaticity is found to play an important role in most of these small-molecule activation. The particularly thermodynamic stabilities of the activation products and low reaction barriers could be a step forward for the development of FLP towards small-molecule activation including N2 , inviting experimental chemists' verification.

Electrocatalytic study of the hydrogen evolution reaction on MoS2/BP and MoSSe/BP in acidic media.

Molecular hydrogen (H2) production by the electrochemical hydrogen evolution reaction (HER) is being actively explored for non-precious metal-based electrocatalysts that are earth-abundant and low cost like MoS2. Although it is acid-stable, its applicability is limited by catalytically inactive basal planes, poor electrical transport and inefficient charge transfer at the interface. Therefore, the present work examines its bilayer van der Waals heterostructure (vdW HTS). The second constituent monolayer boron phosphide (BP) is advantageous as an electrode material owing to its chemical stability in both oxygen and water environments. Here, we have performed first-principles based calculations under the framework of density functional theory (DFT) for the HER in an electrochemical double layer model with the BP monolayer, MoS2/BP and MoSSe/BP vdW HTSs. The climbing image nudged elastic band method (CI-NEB) has been employed to determine the minimum energy pathways for Tafel and Heyrovsky reactions. The calculations reveal that the Tafel reaction shows no reaction barrier. Thereafter, for the Heyrovsky reaction, we obtained a low reaction barrier in the vdW HTSs as compared to that in the BP monolayer. Subsequently, we have observed no significant difference in the reaction profile of MoS2/BP and MoSSe/BP vdW HTSs in the case of 2 × 2 supercell configuration. However, in the case of 3 × 3 and 4 × 4 configurations, MoSSe/BP shows a feasible Heyrovsky reaction with no reaction barrier. The coverages with 1/4H+ concentration (conc.) deduced high coverage with low conc. and low coverage with high conc. to be apt for the HER via the Heyrovsky reaction path. Finally, on observing the activation barrier of the Heyrovsky pathway along with that of second H adsorption at the surface, the Heyrovsky path is expected to be favoured.

Density Functional Theory Analysis of the Copolymerization of Cyclopropenone with Ethylene Using a Palladium Catalyst

Density functional theory has been used to elucidate the mechanism of Pd copolymerization of cyclopropenone with ethylene. The results reveal that introducing ethylene and cyclopropenone to Pd catalyst is thermodynamically feasible and generates the α,β-unsaturated ketone unit (UnitA). Cis-mode insertion and Path A1a are the most favorable reaction routes for ethylene and cyclopropenone, respectively. Moreover, cyclopropenone decomposition can generate CO in situ without a catalyst or with a Pd catalyst. The Pd-catalyzed decomposition of cyclopropenone exhibits a lower reaction barrier (22.7 kcal/mol) than its direct decomposition. Our study demonstrates that incorporating CO into the Pd catalyst can generate the isolated ketone unit (UnitB). CO is formed first; thereafter, UnitB is generated. Therefore, the total energy barrier of UnitB generation, accounting for the CO barrier, is 22.7 kcal/mol, which is slightly lower than that of UnitA generation (24.0 kcal/mol). Additionally, the possibility of copolymerizing ethylene, cyclopropenone, and allyl acetate (AAc) has been investigated. The free energy and global reactivity index analyses indicate that the cyclopropenone introduction reaction is more favorable than the AAc insertion, which is consistent with the experimental results. Investigating the copolymerization mechanism will help to develop of a functionalization strategy for polyethylene polymers.

Synthesis of Sterically Encumbered Thiourea S-Oxides through Direct Thiourea Oxidation.

Thiourea S-oxides can be viewed as formal analogs of the currently unknown diamino-substituted Criegee intermediates (urea O-oxides). However, the preparation of such S-oxides is rather challenging, and the direct oxidation of thioureas typically only leads to formation of desulfurized products. Employing the accurate revDSD-PBEP86-D4 double hybrid density functional, it was found that the peracid mediated oxidation of thiourea S-oxides exhibits a lower reaction barrier than the oxidation of the corresponding thiourea itself in contrast to most other ordinary thioketones. The undesired overoxidation reactivity, which is associated with strong π-donation from the thiourea's nitrogen atoms, can be partially suppressed by introduction of bulky substituents and the utilization of protic solvents. In this regard, we managed to prepare two sterically encumbered thiourea S-oxides in isolated yields of 35-40 %. The S-oxides are stable in the solid state and in alcoholic solutions at room temperature for extended periods of time, but swiftly decompose in aprotic solvents by disproportionation. A dimesityl-substituted thiourea S-oxide complexed with residual mCBA could be characterized by means of X-ray crystallography, confirming the importance of hydrogen bonding in the stabilization of the amino-substituted C=S+ -O- moiety.

Unexpected Redispersion Effect of Au Nanoclusters for Enormous Enhancement of Electrocatalytic Stability and Activity

AbstractThe irreconcilable conflict between stability and excellent electrocatalytic activity of Au nanoclusters greatly limits their application. Extensive efforts are devoted to fabricating various substrates to immobilize Au nanoclusters while it is still challenging to maintain its electrocatalytic activities for long term tasks due to the highly reactive environments that the Au nanoclusters encounter in electrocatalytic reactions. Herein, an unexpected “redispersion effect” is discovered when Au25 nanoclusters are loaded on the nanocomposites of black phosphorus and N‐doped graphene (AuCs/BP‐NG), forming the sandwich configuration with the enhanced stability. The size of Au nanoclusters reduce from 1.56 ± 0.5 to 1.04 ± 0.2 nm, leading to improved catalytic ability. Such redispersion effect yields a super‐high electrocatalytic performance of the AuCs/BP‐NG toward Cr(VI) sensing that the detection sensitivity achieved 0.414 µA ppb−1, which is two orders of magnitude higher than the state‐of‐the‐art value. Compared with BP‐NG and Au nanoparticles (AuNPs) loaded on BP‐NG (AuNPs/BP‐NG), the lowest reaction barrier in the rate‐determining steps of H2CrO4 reduction is observed. The findings provide an opportunity to develop a superior electrocatalyst in the community of energy and environment‐related electrocatalysis.

Experimental and Theoretical Evidence for Relativistic Catalytic Activity in C-H Activation of N-Phenylbenzamide Using a Cationic Iridium Complex.

This study elucidates that relativistic effect plays a key role in catalytic C-H activation using a cationic Ir complex. Experiments show that the cationic Ir(I)-diphosphine catalyst can be used for the deuterium substitution of N-phenylbenzamide, whereas a cationic Rh(I)-diphosphine catalyst is scarcely effective. Density functional theory calculations, including the relativistic effect, demonstrate a large difference in the reaction energy diagrams for the C-H activation of N-phenylbenzamide between the cationic Ir and Rh catalysts. In particular, the relatively low reaction barrier and considerably stabilized product obtained for the Ir catalysts are rationalized by strong Ir-C and Ir-H interactions, which originate from the relativistic self-consistent d-orbital expansion of Ir.

In-situ growing nanowires on biomass corn pods as free-standing electrodes with low surface reaction barrier for Li-, Al-, and Na-ion batteries

Biomass materials have received extensive attention for energy-storage due to low cost and specific structures. Here, a cost-effective carbonaceous material is prepared from biomass corn pod which is commonly considered as a waste, then CuCo2O4 nanowires are in-situ grown on the surface to form a three-dimensional free-standing electrode for several types of secondary batteries. The porous nanowires accommodate the volumetric change, which is beneficial for the stability; and low surface reaction barrier of the composite is verified by using galvanostatic intermittent titration technique (GITT) analysis. When using as a Li-ion battery anode, the CuCo2O4 nanowires/corn pod displays a capacity of 887 mAh/g after 250 cycles at 0.2 A/g, and the Coulombic efficiency exceeds 99.7 %. Under −10 °C and 45 °C, the capacities remain 726 and 700 mAh/g after 120 cycles, respectively. High rate-performance is achievable after three rounds of measurements. The low-cost free-standing electrode is also suitable for different battery types, displaying high performances as Al-ion battery cathode and Na-ion battery anode, which indicate a potential for engineering high-valuable energy-storage systems.

SrTiO3/Ti3C2Tx Schottky heterojunction as a promising high-efficiency photocatalyst for H2 evolution

Exploring low-cost, high-efficiency, and stable photocatalysts is still a significant challenge. SrTiO3, one of the appealing photocatalysts, can meet most of the screening criteria except for its efficiency, which is restricted by its poor absorption of visible light and its prompt photogenerated carrier recombination. Recently, a two-dimensional transition metal carbide Ti3C2Tx (2D MXene) has been found to serve as a co-catalyst due to its excellent metallic conductivity, hydrophilic property, large specific surface area, abundance of active sites, and low reaction barrier to hydrogen production. In this work, SrTiO3 nanoparticles are rationally integrated with Ti3C2Tx nanosheets via a simple hydrothermal process. The hydrogen production rate can achieve up to 3.43 mmol g−1 h−1 in the hybridization of SrTiO3-3 wt. % Ti3C2Tx, which is almost six times that of SrTiO3 alone. This remarkable enhancement arises predominantly from the Schottky contact between SrTiO3 and Ti3C2Tx, which can effectively suppress the recombination of photogenerated carriers and accelerate their separation. In addition, such enhancement benefits from the hydrogen evolution capacity of Ti3C2Tx. This work opens an excellent prospect for constructing highly active, low-cost, and stable photocatalysts with 2D MXene and finding potential applications of 2D MXene in energy conversion fields.

Fe@χ3-borophene as a promising catalyst for CO oxidation reaction: A first-principles study.

A novel single-atom catalyst of Fe adsorbed on χ3-borophene has been proposed as a potential catalyst for CO oxidation reaction (COOR). Quantitative pictures have been provided of both the stability of Fe@χ3-borophene and various kinetic reaction pathways using first-principles calculations. Strong adsorption energy of -3.19 eV and large diffusion potential of 3.51 eV indicates that Fe@χ3-borophene is highly stable. By exploring reaction mechanisms for COOR, both Eley-Ridel (E-R) and trimolecule E-R (TER) were identified as possible reaction paths. Low reaction barriers with 0.49 eV of E-R and 0.57 eV of TER suggest that Fe@χ3-borophene is a very promising catalyst for COOR. Charge transfer between the χ3-borophene and CO, O2 and CO2 gas molecules plays a key role in lowering the energy barrier during the reactions. Our results propose that Fe@χ3-borophene can be a good candidate of single-atom catalyst for COOR with both high stability and catalytic activity.

Coupling Dual-phased nickel selenides with N-doped carbon enables efficient urea electrocatalytic oxidation

Electrochemical urea oxidation reaction (UOR) is urgently in demand for diverse energy conversion and storage device coupled with pollution treatment because of its favorable thermodynamic potential (0.37 V vs RHE) and wide distribution nature of urea, but simultaneously gravely limited by the sluggish reaction dynamics and poisoning of catalyst. Herein, dual-phased Ni0.85Se/NiSe2 coupling with N doped carbon (Ni0.85Se/NiSe2@NC-2) in situ is prepared by a solvothermal-selenization pathway. Benefiting from the collective promotion of the dual-phased composition and the NC support, Ni0.85Se/NiSe2@NC provides abundant active sites, enhanced electrical conductivity. It delivers a current density of 252 mA cm−2 at 1.6 V vs RHE with a small Tafel slop of 64.4 mV dec-1 and gets a lower reaction barrier. Moreover, it requires a cell voltage of 1.46 V to approach 50 mA cm−2, about 250 mV less than that of water electrolysis, confirming the less energy consumption. Notably, the N doped carbon protects Ni0.85Se/NiSe2 nanocrystals from aggregation leading to a faster CO2 desorption from Ni sites, which endow the Ni0.85Se/NiSe2@NC-2 a much better working stability. The direct urea hydrogen peroxide fuel cell (DUHPFC) achieves a maximum power density of 9.09 mW cm−2 at 20 °C. This work extends highly efficient dual-phased structure loading in NC catalysts system for urea-assisted energy conversion.

Defected tungsten disulfide decorated CdS nanorods with covalent heterointerfaces for boosted photocatalytic H2 generation

Owing to their intrinsic and pronounced charge carrier transport when facing the formidable challenge of inhibiting severe surface charge recombination, one-dimensional (1D) CdS nanostructures are promising for advancing high-yield hydrogen production. We herein demonstrate an efficient strategy of boosting interfacial carrier separation by heterostructuring 1D CdS with defective WS2. This process yields solid covalent interfaces for high flux carrier transfer that differ distinctively from those reported structures with physical contacts. As a nonnoble cocatalyst, WS2 can accept photogenerated electrons from CdS, and the sulfur vacancies existing at its edges can effectively trap electrons as active sites for H2 evolution. Moreover, due to its strong negative property, the H+ from the aqueous solution can gather around WS2. WS2 possesses a lower reaction barrier than CdS, which expedites the kinetic process for the reaction. The optimized sample exhibits a high photocatalytic H2 evolution rate of 183.4 µmol/h (10 mg photocatalyst), which is as far as we know among the top in the records for CdS-based photocatalysts. We believe this present work will be inspiring in addressing the interfacial charge carrier transfer by constructing covalent heterointerfaces.

Theoretical investigation on the sensing mechanism of a fluorescent probe 3TBN for cyanide anion detection

In this study, we performed the theoretical simulations to investigate the sensing mechanism of a fluorescent probe 3TBN for cyanide anion (CN–) detection. This calculation details the interaction mechanism between 3TBN and CN– and the excited state properties for the probe 3TBN with addition of CN–. CN– attacks the CC bond of 3TBN, and induced the nucleophilic addition reaction. The Gibbs-free-energy profile demonstrates that the nucleophilic addition reaction is exothermic and has a low reaction barrier (19.0 kcal/mol), which are responsible for the rapid response speed of the probe 3TBN to the CN–. The larger binding energy and the strong interaction between 3TBN and CN– compared to other anions (F-, HCO3–, HSO3-, etc.) indicates that 3TBN has a high selectivity for CN–. The calculated spectrum of probe 3TBN and product 3TBN-CN are in reasonably good agreement with the experimental observations. The sensing mechanism of the probe 3TBN is attributed to the local excitation and the restraining of the intramolecular charge transfer (ICT) process.

Two routes to hydrogen evolution for a Co-polypyridyl complex with two open sites

Cobalt polypyridyl complexes efficiently catalyze hydrogen evolution in aqueous media and exhibit high stability under reducing conditions. Their stability and activity can be tuned through electronic and steric considerations, but the rationalization of these effects requires detailed mechanistic understanding. As an example, tetradentate ligands with two non-permanently occupied coordination sites show higher activity with these sites in cis compared to trans configuration. Here reaction mechanisms of the Co-polypyridyl complex [CoII(bpma)Cl2] (bpma = bipyridinylmethyl-pyridinylmethyl-methyl-amine) have been studied using hybrid density-functional theory. This complex has two exchangeable cis sites, and provides a flexible ligand environment with both pyridyl and amine coordination. Two main pathways with low barriers are found. One pathway, which includes both open sites, is hydrogen evolution from a CoII-H intermediate with a water ligand as the proton donor. In the second pathway H–H bond formation occurs between the hydride and the protonated bpma ligand, with one open site acting as a spectator. The two pathways have similar barriers at higher pH, while the latter becomes more dominant at lower pH. The calculations consider a large number of interconnected variables; protonation sites, isomers, spin multiplicities, and the identities of the open binding sites, as well as their combinations, thus exploring many simultaneous dimensions within each pathway. The results highlight the effects of having two open cis-coordination sites and how their relative binding affinities change during the reaction pathway. They also illustrate why CoII-H intermediates are more active than CoIII-H ones, and why pyridyl protonation gives lower reaction barriers than amine protonation.

Kinetics study of the OH + SiH4 hydrogen abstraction reaction: A theoretical analysis

AbstractThe temperature dependence of the rate constants and the kinetics isotope effects of the OH + SiH4 hydrogen abstraction reaction were theoretically studied. Three different kinetics approaches were used in this study: variational transition state theory with multidimensional tunneling (VTST/MT) corrections, quasi‐classical trajectory (QCT) calculations, and ring polymer molecular dynamics (RPMD). These studies were performed on a global analytical potential energy surface based on explicitly correlated high level ab initio calculations developed in the present work. While the experimental rate constants are practically independent with temperature, the VTST/MT results show a pronounced dependence, the QCT partially corrects this behavior, and RPMD rates are in better agreement with experiment. In this case, in the experimental common temperature range, 300–600 K, the T‐expression for the RPMD rate constants is: k(T) = 6.40 × 10−13.T0.52exp(−0.10/T). The kinetics isotope effects, H/D, are small in this temperature range, revealing the small importance of tunneling effects in this very exothermic and low barrier reaction. Different factors, such as anharmonicity, the zero‐point violation problem or limitations of the surface, without ruling out experimental uncertainties, were analyzed to explain the discrepancies.

Crystal plane effects of CeO2 on supported cobalt and its catalytic performance for Fischer-Tropsch synthesis

The exposing planes of carrier play an essential role in determining the exposing planes and catalytic performance of supported metal catalysts. In this work, Co3O4 nanoparticles were supported on the CeO2 nanorods, nanocubes, and nanopolyhedrons, with dominantly exposing CeO2 (110), (100), and (111) planes, respectively. High resolution transmission electron microscope graphs clearly confirmed that CeO2 has obvious crystal selection effects on supported cobalt, the corresponding supported Co3O4 dominantly exposed (220), (111), and (311) planes, respectively, and the reduced Co dominantly exposed (10–11), (0001), and (111) planes, respectively. Their catalytic behaviors for Fischer–Tropsch synthesis (FTS) were studied in detail, and the optimal catalytic performance was obtained over the cobalt catalyst supported on CeO2 nanorods, mainly due to its exposed Co (10–11) plane with low reaction barrier (-0.83 eV) after reduction. The laser Raman spectra, X-ray photoemission spectroscopy, temperature-programmed reduction, and in situ CO Fourier transform infrared spectroscopy further confirmed the effects of carriers with exposing different planes on the supported cobalt catalysts, explaining the reason for the significantly differences in FTS catalytic performance.