Catalysts For Fischer-Tropsch Synthesis Research Articles

Determination of the conditions of technologically optimized reduction of high-performance Fischer–Tropsch synthesis catalysts

Determination of the conditions of technologically optimized reduction of high-performance Fischer–Tropsch synthesis catalysts

Tuning the strong metal support interaction of the Fischer-Tropsch synthesis silica-coated cobalt-based nano-catalyst

The catalyst is crucial in enhancing productivity within the Fischer-Tropsch synthesis (FTS). The metal support interaction (MSI) plays a pivotal role in the FTS catalyst performance, impacting activity, stability, and selectivity. he configuration and composition of the catalyst dramatically impact MSI, with a strong MSI (SMSI) specified for the core-shell structure. In this study, two methods consisting of chemical treatment of etching and adding a promoter (Ru) for tuning the SMSI of the FTS catalyst are presented, and their footprints on the catalysts’ performance are screened by utilizing various characterization tests, molecular dynamic simulation, and catalytic tests. It is recognized that the silica interfacial perimeter acts as a barrier that restricts the charge transfer and boosts the SMSI in the silica-coated catalyst. Conversely, the etched catalyst exhibits a moderate MSI, contributing to increased reducibility, stability, and activity. Furthermore, the Ru-doped etched catalyst represents the optimum MSI, resulting in the highest overall performance.

Life cycle assessment of iron-biomass supported catalyst for Fischer Tropsch synthesis.

The iron-based biomass-supported catalyst has been used for Fischer-Tropsch synthesis (FTS). However, there is no study regarding the life cycle assessment (LCA) of biomass-supported iron catalysts published in the literature. This study discusses a biomass-supported iron catalyst's LCA for the conversion of syngas into a liquid fuel product. The waste biomass is one of the source of activated carbon (AC), and it has been used as a support for the catalyst. The FTS reactions are carried out in the fixed-bed reactor at low or high temperatures. The use of promoters in the preparation of catalysts usually enhances C5+ production. In this study, the collection of precise data from on-site laboratory conditions is of utmost importance to ensure the credibility and validity of the study's outcomes. The environmental impact assessment modeling was carried out using the OpenLCA 1.10.3 software. The LCA results reveals that the synthesis process of iron-based biomass supported catalyst yields a total impact score in terms of global warming potential (GWP) of 1.235E + 01kg CO2 equivalent. Within this process, the AC stage contributes 52% to the overall GWP, while the preparation stage for the catalyst precursor contributes 48%. The comprehensive evaluation of the iron-based biomass supported catalyst's impact score in terms of human toxicity reveals a total score of 1.98E-02kg 1,4-dichlorobenzene (1,4-DB) equivalent.

Physical Grinding of Prefabricated Co3O4 and MCM-22 Zeolite for Fischer-Tropsch Synthesis: Impact of Pretreatment Procedure on the Dispersion and Catalytic Performance.

To improve the mess-specific activity of Co supported on zeolite catalysts in Fischer-Tropsch (FT) synthesis, the Co-MCM-22 catalyst was prepared by simply grinding the MCM-22 with nanosized Co3O4 prefabricated by the thermal decomposition of the Co(II)-glycine complex. It is found that this novel strategy is effective for improving the mess-specific activity of Co catalysts in FT synthesis compared to the impregnation method. Moreover, the ion exchange and calcination sequence of MCM-22 has a significant influence on the dispersion, particle size distribution, and reduction degree of Co. The Co-MCM-22 prepared by the physical grinding of prefabricated Co3O4 and H+-type MCM-22 without a further calcination process exhibits a moderate interaction between Co3O4 and MCM-22, which results in the higher reduction degree, higher dispersion, and higher mess-specific activity of Co. Thus, the newly developed method is more controllable and promising for the synthesis of metal-supported catalysts.

Synergism of surface Co-rich activated carbon-supported bimetallic Co:Fe catalysts for Fischer-Tropsch synthesis

ABSTRACT The present study explores the remarkable potential of activated carbon-supported cobalt-rich bimetallic catalysts (Co:Fe) in Fischer-Tropsch (FT) synthesis. The H2/CO ratio of the syngas was maintained at 1 to simulate biomass gasification. The temperature, pressure, and GHSV were maintained at 240°C, 20 bar, and 20 mL g.cat−1 min−1, respectively. Totally five combinations of mono- and bimetallic catalysts were synthesized by sequential impregnation of Fe followed by Co, offering a novel and facile approach. The characterization studies revealed the Co-rich surface of the bimetallic catalysts with Co3O4 as an active metal species. The FT activity tests revealed the superior performance of the bimetallic catalysts than their monometallic counterparts. The selectivity to C5+ compounds increased with increase in Co content while the CO conversion increased up to 5% Fe content and then decreased further. The maximum CO conversion (67.4%) and C5+ yield (47.6%) were observed for 15Co5Fe/AC. The study provides a unique perspective on the advancement of C5+ fuel production in Fischer-Tropsch synthesis, achieved through the synergy of FTS-active cobalt and WGS-active iron.

ZSM‐5‐Promoted Co‐Based Light‐Assisted Thermocatalytic Fischer–Tropsch Synthesis Catalyst for Production of Liquid Fuel

Light‐assisted thermocatalytic Fischer–Tropsch synthesis (FTS) provides a more efficient and sustainable approach to synthesizing high‐value chemicals compared to the thermal‐driven FTS. However, producing liquid fuel via cobalt‐based light‐assisted thermocatalytic FTS catalyst poses a challenge since photogenerated electrons increase CO conversion simultaneously with a significant reduction in the selectivity of C5+ product. Herein, a cobalt‐based light‐assisted thermocatalytic FTS catalyst containing ZSM‐5 molecular sieve promoter is prepared by a unique wet chemical reduction method, and the constructed 15%Co/Ta3N5‐ZSM‐5 catalyst exhibits nearly 90% C5+ product selectivity and 63% CO conversion under photothermal condition. Further characterization indicates that the simultaneous increase in the number of active sites and the density of acidic sites in the catalyst is crucial to achieve a simultaneous increase in CO conversion and C5+ product selectivity, which enables the catalyst to produce liquid fuel via light‐assisted thermocatalytic FTS reaction. This work provides an approach to introduce solar energy into the process of liquid fuel production, which can improve the sustainability of the liquid fuel production process.

Importance of zeolite in multifunctional catalysts for syngas conversion

Conversion of syngas into valuable fuels and chemicals has been studied for about 100 years since the discovery of Fischer–Tropsch synthesis (FTS) for conversion of syngas to fuels. Generally, the products in conventional FTS adhere to the Anderson–Schultz–Flory model, which has restricted selectivity to the target products. Other highly demanded compounds such as valuable aromatics and oxygenates, could not be directly obtained from the conventional FTS. According to recent findings, the cascade reactions including isomerization, cracking, and aromatization can optimize the product selectivity, when the zeolite is added to FTS catalysts. Additionally, by offering a confined environment for the C–O bond formation, zeolite makes a substantial contribution to the conversion of syngas into oxygenates. In this review, we primarily focus on the role of zeolites in FTS processes and how it regulates the reaction pathways. The structure–performance interplay of zeolites was particularly discussed, which might be helpful to guide the rational design of zeolites in the development of more effective catalysts.

Impact of Co impregnation on 3D printed alumina supports for Fischer-Tropsch synthesis

3D printing of catalyst has made a significant headway the past decade. Very often metal species on 3D printed supports are being used in catalysis. However, there is no standardized method of impregnation of 3D printed structures. In this work, the impact of the step in the production process where the impregnation is done was studied. Cobalt on alumina catalyst structures were synthesized using direct ink writing (DIW), characterized and tested in Fischer-Tropsch synthesis. Three different impregnation methods were tested (A) incipient wetness impregnation of the structure after printing (B) adding the metal salt precursor to the printing recipe and (C) impregnation of the alumina powder before printing. The catalysts exhibited significant differences in final properties, including pore volume in the fibers of the structure, cobalt nanoparticle size and metal-support interaction. When using the catalysts in Fischer-Tropsch synthesis, the activity of the catalyst impregnated after printing, was more than double the one with the metal salt in the print paste. The difference in conversion showed a clear correlation with the reducibility of the metal species measured with H2-TPR.

Boosting Fischer–Tropsch Synthesis via Tuning of N Dopants in TiO2@CN-Supported Ru Catalysts

Nitrogen (N)-doped carbon materials as metal catalyst supports have attracted significant attention, but the effect of N dopants on catalytic performance remains unclear, especially for complex reaction processes such as Fischer–Tropsch synthesis (FTS). Herein, we engineered ruthenium (Ru) FTS catalysts supported on N-doped carbon overlayers on TiO2 nanoparticles. By regulating the carbonization temperatures, we successfully controlled the types and contents of N dopants to identify their impacts on metal–support interactions (MSI). Our findings revealed that N dopants establish a favorable surface environment for electron transfer from the support to the Ru species. Moreover, pyridinic N demonstrates the highest electron-donating ability, followed by pyrrolic N and graphitic N. In addition to realizing excellent catalytic stability, strengthening the interaction between Ru sites and N dopants increases the Ru0/Ruδ+ ratios to enlarge the active site numbers and surface electron density of Ru species to enhance the strength of adsorbed CO. Consequently, it improves the catalyst’s overall performance, encompassing intrinsic and apparent activities, as well as its ability for carbon chain growth. Accordingly, the as-synthesized Ru/TiO2@CN-700 catalyst with abundant pyridine N dopants exhibits a superhigh C5+ time yield of 219.4 molCO/(molRu·h) and C5+ selectivity of 85.5%.

Effects of Co3C formation on the catalytic performance for Fischer-Tropsch synthesis over Co/SiO2 catalysts

Cobalt carbides demonstrate higher selectivity towards light olefins and alcohols in the Fischer-Tropsch synthesis (FTS). In this study, we present an investigation of a series of supported cobalt catalysts that were carburized with CO for different time. The presence of Co3CCo, Co and Co2CCo phases in these catalysts was confirmed through Transmission Electron Microscopy (TEM). The Co/SiO2-RC-0.5 h catalyst with both Co3C and Co structure exhibits the highest CO conversion for the FTS reaction. By utilizing the chemisorption techniques, we studied the structure-performance relationships between the phase and activity, and confirmed that Co3C has the highest intrinsic activity, which is beneficial for CO activation. This study provides further insight into the positive effects of Co3C on the FTS reaction and guides us in the rational design of high active Co-based FTS catalysts.

Eco-friendly solid-state synthesis of Na-promoted Mn-Fe/ZrO2 catalyst for Fischer-Tropsch synthesis

The advancement of large-scale and environmentally-friendly solid-state synthesis methods is of paramount importance for the production of precipitated catalysts, notably Fe-based catalysts utilized in Fischer-Tropsch synthesis (FTS). In this study, we present an innovative solvent-independent, wastewater-free solid-state approach for the synthesis of highly efficient Fe/ZrO2 catalysts, elucidating the mechanisms of promotion within this specific methodology. The prepared catalysts underwent rigorous evaluation under industrially-relevant FTS conditions (230–270 °C, 20 bar, and WHSV = 5400 mL/(gcat⋅h)). A comprehensive suite of characterization techniques was employed to establish the intricate interplay between catalytic activity and structural attributes. We meticulously examined the impact of Na as an alkali promoter and the role of transition metals (Cu and Mn) in enhancing FTS catalytic performance. The catalytic outcomes obtained clearly demonstrate the pivotal role of the synergistic interaction between Mn and Na within the Na-Mn-Fe/ZrO2 catalyst system in driving the FTS reaction. This synergism significantly enhances FTS performance, yielding an impressive CO conversion rate (89.91 %) while maintaining low selectivity to CH4 (7.75 %). The incorporation of Mn and Na into the catalyst matrix enhances the dispersion of Fe2O3, thereby improving the reducibility of Mn/Fe oxides and elevating the electron density on the catalyst surface. These factors facilitate the formation of active Hägg iron carbide (χ-Fe5C2), stimulating chain propagation and ultimately leading to the generation of valuable C5+ hydrocarbon products, which underscores its potential as an optimal candidate for future industrial applications in Fe-based Fischer-Tropsch synthesis.

Atomic-scale understanding of the impact of CoO phase in cobalt-catalyzed Fischer-Tropsch synthesis: A combined computational and experimental study

In cobalt-catalyzed Fischer-Tropsch synthesis (FTS), the active metallic cobalt phase always suffers from oxidation under FTS reaction conditions, leading to the coexistence of metallic cobalt and cobalt oxide (CoO) phases. However, there still exist contradictory views on the impact of CoO phase in FTS. Some researchers proposed that the oxidation of metallic Co to CoO causes the deactivation of cobalt-based FTS catalysts, while some held the view that CoO phase could act as the potential active phase in FTS. In this study, by combining theoretical calculations and experiments, we systematically investigated the fundamental FTS reactions including CO adsorption and activation, C-C coupling, and CxHy hydrogenation on CoO phase, and compared them with those on metallic cobalt phase, aiming at identifying the exact role of CoO, understanding how CoO influences the activity and selectivity, and unraveling the intrinsic mechanism that determines the catalytic behaviors of CoO phase in FTS. The results reveal that the CoO(200) crystal facet is the dominantly exposed surface structure for CoO phase under FTS reaction conditions. The d-band center of CoO(200) surface shifts downward in comparison with that of active metallic Co surface, which causes difficulties in adsorbing and activating CO and gives rise to high energy barriers for the dissociation of C-O bond. This determines the inactive nature of CoO phase in FTS reaction. As for the product selectivity, the CoO(200) surface restricts the C-C chain growth due to its higher barriers for C-C coupling, facile desorption ability for light olefins, and lower energy barrier for CH4 formation compared with metallic cobalt, and consequently leads to the loss of selectivity to C5+ hydrocarbons and enhancement of selectivity to light olefins and undesired methane. Moreover, a strong linear relationship between the experimental observed selectivity change and the DFT-calculated energy difference of CoO and metallic cobalt phases was found, validating the DFT-calculated results. This study provides a comprehensive understanding of the nature and intrinsic catalytic behaviors of CoO phase in cobalt-catalyzed FTS.

Morphological effect of MnO2 promoter on iron-based Fischer-Tropsch synthesis catalysts

In this work, flower-like spherical, sea urchin-like and tubular MnO2 are prepared via hydrothermal synthesis and used as promoters of iron-based Fischer-Tropsch synthesis (FTS) catalysts to investigate their morphological effects. It is found that the different morphology of MnO2 exhibits observably distinct promotion functions on iron-based FTS catalysts. Tubular MnO2 contains moderate amount of surface oxygen vacancies accompany with weak Fe-Mn electronical interaction, as a result, tubular MnO2 promotes the formation of long-chain hydrocarbon and olefins, and restrains the generation of CH4. Flower-like spherical MnO2 presents negative roles in the CO conversion and formation of long-chain hydrocarbon, due to its insufficient oxygen vacancies and moderate Fe-Mn electronical interaction. With the most abundance of oxygen vacancies and strongest Fe-Mn interaction, sea urchin-like MnO2 modified catalysts exhibits the highest initial CO conversion, but deactivates rapidly. Besides, the sea urchin-like MnO2 enhances the formation of long-chain paraffins. This work presents new insights of the promotion roles of Mn additive, which is beneficial for the rational design of efficient iron-based FTS catalysts.

Enhancing the stability of a cobalt-based Fischer–Tropsch synthesis catalyst using g-C3N4-coated SBA-15 as support

BackgroundThe design and synthesis of catalysts with high stability, activity and selectivity in Fischer–Tropsch synthesis (FTS) have been attracting extensive research attention. Maintaining high catalytic stability and activity is the best strategy for improving the catalyst efficiency and economic benefits. MethodsIn this study, graphitic carbon nitride (g-C3N4)-coated SBA-15 was utilised as a support material to prepare cobalt-based FTS catalysts. The catalysts coated with g-C3N4 were studied via TEM, XPS, XRD, H2-TPR, TG, N2 adsorption–desorption, and tested in a fixed-bed reactor. Significant findingsThe catalysts coated with g-C3N4 were considerably more stable than the Co/SBA-15 catalyst without g-C3N4 coating during a 100 h test period. Furthermore, the CO-conversion performance of the Co/SBA-15 catalyst decreased continuously. Notably, the activity of the Co/SBA-15@0.5C3N4 catalyst with a low g-C3N4 loading was higher than that of the Co/SBA-15@1C3N4 catalyst with a relatively high g-C3N4 loading. g-C3N4 can significantly strengthen the interaction between the cobalt species and the support, thereby increasing the catalyst stability. Therefore, a highly stable catalyst with good activity can be achieved by employing a small amount of g-C3N4 for surface modification. The results highlight the effectiveness of the proposed strategy for preparing highly stable, cobalt-based catalysts with good activity.

A novel machine learning framework for designing high-performance catalysts for production of clean liquid fuels through Fischer-Tropsch synthesis

Fischer-Tropsch synthesis (FTS) attracts great interest as a sustainable route for production of sustainable transportation fuels. Catalyst design and operational conditions tune the selectivity of FTS to liquid fuels, which can be predicted with machine learning models (ML). Herein, a comprehensive dataset including 27 key input features related to the catalyst structure (with the focus on carbon supports), preparation, activation, and FTS operating conditions were investigated to predict the CO conversion and C5+ selectivity using three ML algorithms. Feature engineering and selection were implemented to identify the significant catalyst formulation descriptors. Principal component analysis was used to explore the information space and decrease the dimension of the dataset before ML prediction. In addition to the well-known effects of the operational conditions on FTS, roles of physico-chemical properties of the carbon materials were also extensively analyzed. Random forest (RF) including 4 principal components, indicated the highest accuracy for prediction of the CO conversion and C5+ selectivity with R2 of 0.91 and 0.97, respectively. The proposed framework can provide a reliable strategy in designing efficient carbon supported catalysts for FTS and guide experiments by identifying the key descriptors in the catalyst formulation and operating conditions to enhance the selectivity of liquid fuels.

Compositional Evolution of Individual CoNPs on Co/TiO2 during CO and Syngas Treatment Resolved through Soft XAS/X-PEEM.

The nanoparticle (NP) redox state is an important parameter in the performance of cobalt-based Fischer-Tropsch synthesis (FTS) catalysts. Here, the compositional evolution of individual CoNPs (6-24 nm) in terms of the oxide vs metallic state was investigated in situ during CO/syngas treatment using spatially resolved X-ray absorption spectroscopy (XAS)/X-ray photoemission electron microscopy (X-PEEM). It was observed that in the presence of CO, smaller CoNPs (i.e., ≤12 nm in size) remained in the metallic state, whereas NPs ≥ 15 nm became partially oxidized, suggesting that the latter were more readily able to dissociate CO. In contrast, in the presence of syngas, the oxide content of NPs ≥ 15 nm reduced, while it increased in quantity in the smaller NPs; this reoxidation that occurs primarily at the surface proved to be temporary, reforming the reduced state during subsequent UHV annealing. O K-edge measurements revealed that a key parameter mitigating the redox behavior of the CoNPs were proximate oxygen vacancies (Ovac). These results demonstrate the differences in the reducibility and the reactivity of Co NP size on a Co/TiO2 catalyst and the effect Ovac have on these properties, therefore yielding a better understanding of the physicochemical properties of this popular choice of FTS catalysts.

The role of Zr as promoter in the CoZr catalysts for Fischer-Tropsch synthesis

It is reported that Zirconium (Zr) is an effective promoter of cobalt-based catalysts for Fisher-Tropsch synthesis (FTS). Numerous studies have been conducted to explore the nature of the promotion. However, many of these studies focus on oxide-supported cobalt-based catalysts, in which the support effects may have partially enhanced or masked the influences of Zr. In the present work, CoZr catalysts without oxide support have been prepared across a wide range of Zr/Co molar ratio from 0.04 to 0.33 to investigate the nature of the Zr promotion. Comparing with the nano-Co3O4, the promoted catalysts exhibit excellent performance. The reaction temperature required to convert the same amount of syngas on the same amount of cobalt has decreased by about 40 °C. The selectivity of C5+ has increased from 70∼81% to over 85% at the same CO conversion, and even higher than 90% on the CoZr catalysts with high Zr/Co ratio. Evidences from multiple techniques, including in situ XPS, CO-DRIFTs, CO-TPD, NH3-TPD, Py-IR, HRTEM, Raman and XRD, shows that Zr tends to occupy the coordinately unsaturated sites of nano-Co3O4. After reduction, Zr enters the lattice of Co metal, leading to the lattice expansion. Benefitting from the Zr induced structural changes of the Co metal, CO adsorption and dissociation on the CoZr catalysts have been enhanced. Besides, due to the strong interaction between Co and Zr, the growth of the Co metal crystal during H2 reduction and O atoms adsorption on the reduced catalysts surface are inhibited significantly, which make more Co atoms available during FTS reaction. As a result, the catalytic performances are improved obviously.

Study fischer-tropsch synthesis

This work was to evaluate the catalytic properties Ru/Cobalt/SBA-15 catalyst for Fischer-Tropsch synthesis (FTS). The molecular sieve SBA-15 synthesized by hydrothermal method with rice husk ashes (RHA) and with tetraethyl orthosilicate (TEOS). The Ru promoted Co/SBA-15 catalyst was prepared by wet impregnation method and was characterized by X-ray diffraction, X-ray energy dispersion spectrophotometer, N2 adsorption-desorption, temperature-programmed reduction and transmission electron microscopy. The Fischer-Tropsch synthesis using the catalysts were carried out to evaluate the catalysts activities and its effect on FTS product distribution. The synthesis was carried out in a slurry reactor operating at 513 K, 20 atm, CO : H2 molar ratio of 1 : 2. X-ray diffraction showed that the calcined cobalt catalyst did not modify the structure of SBA-15, proving that Co was present under the form of Co3O4 in the catalyst. The addition of cobalt in SBA-15 decreased the specific superficial area of the molecular sieve. By RTP results was found the ranges of temperature reduction typical of iron oxides phases. Fischer-Tropsch synthesis activity and C5+hydrocarbon selectivity increased with the addition of Ru. The increases in activity and selectivity were attributed to the increased number of active sites resulting from higher reducibility and the synergetic effect of Ru and Co. The most interesting fact to be pointed out is that the use of this catalytic system for the catalyst prepared with alternative source of silica and cheap (rice hull ash) showed high selectivity in liquid products, that is, in hydrocarbons with C5+ (88.2% w/w ), higher than the catalyst prepared with conventional silica source.

Support effects on Ru-based catalysts for Fischer-Tropsch synthesis to olefins

The effects of supports (CeO2, ZrO2, MnO2, SiO2 and active carbon) on the structure and catalytic performance of Ru-based catalysts for Fischer-Tropsch synthesis to olefins (FTO) were investigated. It was found that the intrinsic characteristics of supports and the metal-support interaction (MSI) would greatly influence the catalytic performance. The catalytic activity followed the order: Ru/SiO2 > Ru/ZrO2 > Ru/MnO2 > Ru/AC > Ru/CeO2. As far as olefins selectivity was concerned, both Ru/SiO2 and Ru/MnO2 possessed high selectivity to olefins (>70%), while olefins selectivity for Ru/ZrO2 was the lowest (29.9%). Ru/SiO2 exhibited the appropriate Ru nanoparticles size (~ 5 nm) with highest activity due to the relatively low MSI between Ru and SiO2. Both Ru/AC and Ru/MnO2 presented low CO conversion with Ru nanoparticles size of 1–3 nm. Stronger olefins secondary hydrogenation capacity led to the significantly decreased olefins selectivity for Ru/AC and Ru/ZrO2. In addition, partial Ru species might be encapsulated by reducible CeO2 layer for Ru/CeO2 due to strong MSI effects, leading to the lowest activity.

Hydrophobic Fe‐Based Catalyst Derived from Prussian Blue for Enhanced Photothermal Conversion of Syngas to Light Olefins

AbstractAlthough there are many promising works in the field of Fischer–Tropsch synthesis (FTS), it is still a huge challenge to achieve the rational design of FTS catalysts for excellent selectivity toward light olefins with a high olefins/paraffins ratio (o/p ratio). Herein, a hydrophobic core–shell Fe‐based FTS catalyst is developed by calcination and hydrophobic modification of polyvinylpyrrolidone (PVP)‐decorated Prussian blue (PB, Fe4[Fe(CN)6]3) precursor. The hydrophobic modification is achieved by using trimethylchlorosilane (TMCS) as the hydrophobic agent. Under light irradiation and near ambient pressure (0.18 MPa), compared with the catalyst without the hydrophobic surface to mainly convert CO to valueless CO2, the optimal catalyst delivers excellent selectivity of 48.0% for value‐added light olefins (C2–4 = ) with a high o/p ratio of 10.1 but low selectivity for CO2 at a CO conversion of 22.6%. The excellent FTS performance can be attributed to that the hydrophobic surface of the catalyst regulates the chemical reaction pathway, which promotes the CO hydrogenation but suppresses the conversion of CO to CO2. The study demonstrates that a rationally designed functional surface of a catalyst can govern the reaction pathway along value‐added solar‐to‐chemicals conversion.