Noble Metal Catalysts Research Articles

Indene as an alternative hydrogen carrier: Performance of supported noble metal catalysts for indene and indane hydrogenation

We propose in this article the use of indene, obtained from the light fraction of coal tar rectification, as a Liquid Organic Hydrogen Carrier (LOHC), with a thorough study of its hydrogenation. The hydrogenation process, conducted on noble metal catalysts (Pd, Pt, Rh, and Ru) supported by activated carbon or alumina, involves the rapid conversion of indene to indane, followed by the formation of cis- and trans-hydrindane. Carbon-supported catalysts exhibited faster reactions rates, with catalytic activities varying among metal phases, Rh and Ru being the most active. Indene was found to have an inhibitory effect on the hydrogenation reactions. While Ru catalysts enhance cracking, Rh catalysts are the most selective for total hydrogenation. The study highlights that Ru catalysts favour cracking reactions more than Rh. The proposed reaction mechanisms involve successive steps and follow a Langmuir-Hinshelwood type kinetics, confirming the inhibitory effect of indene.

Co Cluster-Modified Ni Nanoparticles with Superior Light-Driven Thermocatalytic CO2 Reduction by CH4

Excessive fossil burning causes energy shortages and contributes to the environmental crisis. Light-driven thermocatalytic CO2 reduction by methane (CRM) provides an effective strategy to conquer these two global challenges. Ni-based catalysts have been developed as candidates for CRM that are comparable to the noble metal catalysts. However, they are prone to deactivation due to the thermodynamically inevitable coking side reactions. Herein, we reported a novel Co-Ni/SiO2 nanocomposite of Co cluster-modified Ni nanoparticles, which greatly enhance the catalytic durability for light-driven thermocatalytic CRM. It exhibits high production rates of H2 (rH2) and CO (rCO, 22.8 and 26.7 mmol min−1 g−1, respectively), and very high light-to-fuel efficiency (ƞ) is achieved (26.8%). Co-Ni/SiO2 shows better catalytic durability than the referenced catalyst of Ni/SiO2. Based on the experimental results of TG-MS, TEM, and HRTEM, we revealed the origin of the significantly enhanced light-driven thermocatalytic activity and durability as well as the novel photoactivation. It was discovered that the focused irradiation markedly reduces the apparent activation energy of CO2 on the Co-Ni/SiO2 nanocomposite, thus significantly enhancing the light-driven thermocatalytic activity.

Manganese- and Iron-Catalyzed Carbonylation Reactions: A Personal Account

AbstractTransition-metal-catalyzed carbonylative transformations have been widely employed to convert CO gas into valuable carbonyl-containing molecules, mainly using noble metals (Pd, Rh, Ir, Ru) and more recently nickel and other catalysts. Although noble-metal catalysts have the advantage of reaction efficiency, their high-cost has led scientists to explore alternative procedures. Also under these backgrounds, we carried out some studies on nonexpensive metal-catalyzed carbonylative transformations. In this Account, we summarize the carbonylation reactions developed in our research group by using manganese and iron catalysis. These carbonylation reactions proceeded either via SET (single-electron transfer) or TET (two-electron transfer) mechanism.1 Introduction2 Manganese-Catalyzed Carbonylation of Alkyl Chlorides3 Manganese-Catalyzed Carbonylation of Alkyl Iodides4 Iron/Copper-Catalyzed Carbonylation of Alkyl Bromides5 Iron-Catalyzed Carbonylation of Alkyl Bromides6 Iron-Catalyzed Carbonylation of Alkyl-Boronic Pinacol7 Iron-Catalyzed Aminoalkylative Carbonylative Cyclization of Alkenes8 Conclusion and Outlook

Self‐Polycondensation Flux Synthesis of Ultrastable Olefin‐Linked Covalent Organic Frameworks for Electrocatalysis

AbstractCreating new functional materials that efficiently support noble metal catalysts is important and in high demand. Herein, we develop a self‐polycondensation flux synthesis strategy that can produce olefin‐linked covalent organic framework (COF) platforms with high crystallinity and porosity as the supports of Pd nanoparticles for electrocatalytic nitrogen reduction reaction (ENRR). A series of “two in one” monomers integrating aldehyde and methyl reactive groups are rationally designed to afford COFs with square‐shaped pores and ultrahigh chemical stability (e.g., strong acid or alkali environments for >1 month). Functionalizing Fluorine significantly boosts the hydrophobicity of fluoro‐functionalized COFs, which can inhibit the competing hydrogen evolution reaction (HER) and enhance ENRR performances. The COFs loading Pd nanoparticles show high NH3 production yields up to 90.0±2.6 μg ⋅ h−1 ⋅ mgcat.−1 and the faradaic efficiency of 44 % at −0.2 V versus reversible hydrogen electrode, the best comprehensive performance among all reported COFs. Meanwhile, the catalysts are easy to recover and recycle, as demonstrated by their use for 15 cycles and 17 hours, with good performance retention. This work not only provides a new synthesis strategy for olefin‐linked COFs, but also paves a new avenue for the design of highly efficient ENRR catalysts.

One-Pot, Solvent Free Synthesis of 2,5-Furandicarboxylic Acid from Deep Eutectic Mixtures of Sugars as Mediated by Bifunctional Catalyst.

Currently one-pot conversion of sugars to 2,5-furandicarboxylic acid (FDCA) is of significant interest due to the attainability of sugars as a feedstock and the enormous potential of FDCA as a bioplastic monomer. However, it remains challenging to construct efficient catalysts for this process. In this study, Co3O4 species were anchored to a sulfonated covalent organic framework thus affording a bifunctional catalyst (Co3O4@COF-SO3H). The sulfonic acid sites dehydrate sugars to 5-hydroxymethylfurfural (HMF), which is next oxidized to FDCA as catalyzed by the Co3O4 species. Such a process was applied in the conversion of various binary and ternary deep eutectic mixtures involving choline chloride and sugars without additional solvent. The maximum FDCA yield of 84 % was obtained using glucose-fructose eutectic mixture as the substrates. Moreover, the catalyst was recyclable and stable under the applied reaction conditions. Our process eliminates the employment of organic solvents and expensive noble metal catalysts, resulting in green and economic biomass conversions.

Non-Noble Metal Catalysts for Electrooxidation of 5-Hydroxymethylfurfural.

2,5-Furandicarboxylic acid (FDCA) is a class of valuable biomass-based platform compounds. The creation of FDCA involves the catalytic oxidation of 5-hydroxymethylfurfural (HMF). As a novel catalytic method, electrocatalysis has been utilized in the 5-hydroxymethylfurfural oxidation reaction (HMFOR). Common noble metal catalysts show catalytic activity, which is limited by price and reaction conditions. Non-noble metal catalyst is known for its environmental friendliness, affordability and high efficiency. The development of energy efficient non-noble metal catalysts plays a crucial role in enhancing the HMFOR process. It can greatly upgrade the demand of industrial production, and has important research significance for electrocatalytic oxidation of HMF. In this paper, the reaction mechanism of HMF undergoes electrocatalytic oxidation to produce FDCA are elaborately summarized. There are two reaction pathways and two oxidation mechanisms of HMFOR discussed deeply. In addition, the speculation on the response of the electrode potential to HMFOR is presented in this paper. The main non-noble metal electrocatalysts currently used are classified and summarized by targeting metal element species. Finally, the paper focus on the mechanistic effects of non-noble metal catalysts in the reaction, and provide the present prospects and challenges in the electrocatalytic oxidation reaction of HMF.

Modified Si Oxidation Behavior by Ultrathin Ni Catalyst Enabling Oxidant-Less Metal-Assisted Chemical Etching.

Metal-assisted chemical etching (MACE), a wet-based anisotropic etching process for semiconductors, has emerged as an alternative to plasma-based etching. However, using noble metal catalysts in MACE limits the implementation of complementary metal-oxide-semiconductor (CMOS) processes. This study explores Si etching using an ultrathin Ni catalyst as a novel approach for MACE. The thickness of the Ni catalyst emerges as a critical parameter, with 1 nm of Ni proving to be the optimal thickness to achieve smooth and deep etching. Unlike conventional MACE methods, the ultrathin Ni catalyst enables Si etching without strong oxidants. Wafer-scale Si etching demonstrates the versatility of the ultrathin Ni catalyst in producing various microstructures. It is found that the ultrathin Ni/Si interfacial state plays a crucial role in influencing the Si reactivity, lowering the barrier for Si oxidation. CMOS-compatible and cost-efficient ultrathin Ni makes MACE a promising alternative for semiconductor nanofabrication. This study pioneers MACE using an ultrathin non-noble metal catalyst, offering valuable insights for researchers in this field.

Photoredox Catalyzed Tandem Denitrogenative [4 + 2] Annulation of 1,2,3-Benzotriazin-4(3H)-ones with Terminal Olefins.

The dihydroisoquinolones skeleton is ubiquitous in natural products and biological molecules. Reported strategies for constructing dihydroisoquinolones usually require noble metal catalysts or stoichiometric oxidants, which limit their wide applications. Herein, we developed a photoredox catalyzed tandem denitrogenative [4 + 2] annulation reaction of 1,2,3-benzotriazin-4(3H)-ones with terminal olefins. A variety of dihydroisoquinolones can be accessed in moderate to excellent yield. This protocol features high atom-economy, mild reaction conditions, and is external oxidant-free, enabling the synthesis of various substituted dihydroisoquinolones.

Recent Advancements in Fe-Based Catalysts for the Efficient Reduction of NOx by CO.

The technology of CO selective catalytic reduction of NOx (CO-SCR) showcases the potential to simultaneously eliminate CO and NOx from industrial flue gas and automobile exhaust, making it a promising denitrification method. The development of cost-effective catalysts is crucial for the widespread implementation of this technology. Transition metal catalysts are more economically viable than noble metal catalysts. Among these, Fe emerges as a prominent choice due to its abundant availability and cost-effectiveness, exhibiting excellent catalytic performance at moderate reaction temperatures. However, a significant challenge lies in achieving high catalytic activity at low temperatures, particularly in the presence of O2, SO2, and H2O, which are prevalent in specific industrial flue gas streams. This review examines the use of Fe-based catalysts in the CO-SCR reaction and elucidates their catalytic mechanism. Furthermore, it also discusses various strategies devised to enhance low-temperature conversion, taking into account factors such as crystal phase, valence states, and oxygen vacancies. Subsequently, the review outlines the challenges encountered by Fe-based catalysts and offers recommendations to improve their catalytic efficiency for use in low-temperature and oxygen-rich environments.

Electrothermal Conversion of Methane to Methanol at RoomTemperature with Phosphotungstic Acid.

Traditional methods for the aerobic oxidation of methane to methanol frequently require the use of noble metal catalysts or flammable H2-O2 mixtures. While electrochemical methods enhance safety and may avoid the use of noble metals, these processes suffer from low yields due to limited current density and/or low selectivity. Here, we design an electrothermal process to conduct aerobic oxidation of methane to methanol at room temperature using phosphotungstic acid (PTA) as a redox mediator. When electrochemically reduced, PTA activates methane with O2 to produce methanol selectively. The optimum productivity reaches 29.45 [[EQUATION]] with approximately 20.3% overall electron yield. Under continuous operation, we achieved 19.90 [[EQUATION]] catalytic activity, over 74.3% methanol selectivity, and 10 hours durability. This approach leverages reduced PTA to initiate thermal catalysis in solution phase, addressing slow methane oxidation kinetics and preventing overoxidations on electrode surfaces. The current density towards methanol production increased over 40 times compared with direct electrochemical processes. The in-situ generated hydroxyl radical, from the reaction of reduced PTA and oxygen, plays an important role in the methane conversion. This study demonstrates reduced polyoxotungstate as a viable platform to integrate thermo- and electrochemical methane oxidation at ambient conditions.

Electrothermal Conversion of Methane to Methanol at Room Temperature with Phosphotungstic Acid

Traditional methods for the aerobic oxidation of methane to methanol frequently require the use of noble metal catalysts or flammable H2‐O2 mixtures. While electrochemical methods enhance safety and may avoid the use of noble metals, these processes suffer from low yields due to limited current density and/or low selectivity. Here, we design an electrothermal process to conduct aerobic oxidation of methane to methanol at room temperature using phosphotungstic acid (PTA) as a redox mediator. When electrochemically reduced, PTA activates methane with O2 to produce methanol selectively. The optimum productivity reaches 29.45 [[EQUATION]] with approximately 20.3% overall electron yield. Under continuous operation, we achieved 19.90 [[EQUATION]] catalytic activity, over 74.3% methanol selectivity, and 10 hours durability. This approach leverages reduced PTA to initiate thermal catalysis in solution phase, addressing slow methane oxidation kinetics and preventing overoxidations on electrode surfaces. The current density towards methanol production increased over 40 times compared with direct electrochemical processes. The in‐situ generated hydroxyl radical, from the reaction of reduced PTA and oxygen, plays an important role in the methane conversion. This study demonstrates reduced polyoxotungstate as a viable platform to integrate thermo‐ and electrochemical methane oxidation at ambient conditions.

Improved Reductive Catalytic Fractionation of Lignocellulosic Biomass through the Application of a Recyclable Magnetic Catalyst.

The reductive catalytic fractionation (RCF) of second generation lignocellulosic biomass is an elegant one-pot process to obtain a highly delignified cellulose pulp, sugar-derived polyols, and depolymerized and stabilized lignin oils. However, the need of noble metal catalysts to prompt the reactions may impact the economic sustainability of the overall "lignin-first" biorefinery if the catalyst recovery and recyclability are not guaranteed. Herein, the use of a novel catalyst based on supported ruthenium over maghemite for the RCF of poplar sawdust is reported for the first time. This material allows us to obtain a pure cellulose pulp with a quantitative magnetic recovery efficiency after the first cycle. The obtained lignin oil is composed by a 12% yield in phenolic monomers (i.e., benzyl alcohol, 4-n-propylguaiacol, and 4-n-propylsyringol), together with dimers and trimers as confirmed by GPC analyses. The catalytic material was found to be stable and recyclable for three reaction cycles with only minor loss of RCF efficiency. On the other hand, the straightforward, lab-scale, magnetic recovery procedure needs to be further improved in the future to ensure quantitative recovery of the catalyst also after several RCF cycles.

Quasi-1D Oxides as Electrocatalysts for Water-Splitting: Case Study of Sr9M2Mn5O21 (M = Co, Ni, Cu, Zn).

We have demonstrated that multimetal oxides with a quasi-1D structure can be effective electrocatalysts for water electrolysis. Four materials have been systematically investigated, namely, Sr9Co2Mn5O21, Sr9Ni2Mn5O21, Sr9Cu2Mn5O21, and Sr9Zn2Mn5O21, comprising 1D chains of face-sharing MnO6 octahedra and MO6 trigonal prisms (M = Co, Ni, Cu or Zn), which are held together by strontium ions located between the chains. These materials show a consistent trend in electrocatalytic properties for both half-reactions of water-splitting, i.e., oxygen evolution and hydrogen evolution reactions (OER and HER). In particular, Sr9Ni2Mn5O21 has an outstanding performance for OER, with an overpotential of 0.37 V, which is lower than those of many 3D and 2D oxides, and rivals the activity of noble metal catalysts, such as RuO2. This is important given that the OER is considered the bottleneck of the water-slitting process. Chronopotentiometry studies, combined with X-ray photoelectron spectroscopy (XPS) and X-ray diffraction experiments pre- and post-reaction, indicate that Sr9Ni2Mn5O21 is highly stable and retains its structural integrity upon electrocatalytic reactions. This study highlights the potential of quasi-1D oxides as active electrocatalysts for water-splitting.

The Catalytic Mechanisms and Design Strategies of Noble Metal Catalysts for Selective Reduction of NOx with CO

AbstractThe selective catalytic reduction of NOx by CO (CO‐SCR) is a viable method for simultaneously mitigating NOx and CO emissions in motor vehicle exhaust and industrial flue gases. Extensive research has been conducted on noble metal catalysts because of their superior catalytic activity and stability compared to non‐noble metals. Noble metal catalysts demonstrate efficient NOx conversion and high selectivity for N2. However, achieving high conversion, selectivity, and stability over a wide temperature range in the presence of excess O2, H2O, and SO2 remains a significant challenge. This review summarizes recent advancements in CO‐SCR over noble metal catalysts, providing insights for the development of CO‐SCR catalysts. This paper first examines the reaction mechanisms of CO‐SCR, followed by a discussion on the design and optimization strategies of noble metal catalysts, with a focus on composition and structural effects. This includes creating active metal sites, selecting appropriate supports, integrating catalytic additives, choosing monometallic nanoparticles, alloying, and using single‐atom catalysts. Finally, remaining challenges and potential avenues for future research have been suggested. The discovery of negatively charged noble metal single‐atom‐site catalysts presents new research opportunities.

Exploring pyrolusite β-MnO2 as a robust support for noble metal catalysts in proton exchange membrane water electrolysis

Proton exchange membrane water electrolysis (PEMWE) represents a promising avenue for producing hydrogen sustainably. Nonetheless, its widespread adoption encounters hurdles owing to the sluggishness of the oxygen evolution reaction (OER) and the expensive noble metal catalysts, particularly iridium (Ir). Our investigation addresses these challenges by examining pyrolusite β-MnO2 as a robust substrate for noble metal catalysts, including iridium (Ir) and ruthenium (Ru), within PEMWE systems. We illustrate that nanostructured β-MnO2 effectively supports Ir and Ru catalysts, resulting in significantly improved catalytic activity for acidic OER compared to conventional IrO2 catalysts. The morphology shows nanorod structures with thicknesses ranging of 30–60 nm. The catalytic activity exhibits a lower overpotential of 215 mV and a higher Ir mass activity of 2268.7 A·gIr−1. The catalyst also exhibits lower Tafel slope value (37.82 mV/dec) and higher reaction kinetics. The catalyst also shows durability for the 12h under corrosive acidic OER conditions. The enhancements in performance can be attributed to the distinctive nanostructure of the Mn1-xTixO2 (MTO) support, which facilitates the even distribution of Ir and Ru catalysts. Additionally, the incorporation of titanium in pyrolusite β-MnO2 enhances the electrochemical durability of the MTO support under challenging acidic OER conditions.

Photocatalytic Semi-Hydrogenation of Acetylene to Polymer-Grade Ethylene with Molecular and Metal-Organic Framework Cobaloximes.

The semi-hydrogenation of acetylene in ethylene-rich gas streams is a high-priority industrial chemical reaction for producing polymer-grade ethylene. Traditional thermocatalytic routes for acetylene reduction to ethylene, despite progress, still require high temperatures and high H2 consumption, possess relatively low selectivity, and use a noble metal catalyst. Light-powered strategies are starting to emerge, given that they have the potential to use directly the abundant and sustainable solar irradiation, but are ineffective. Here an efficient, >99.9% selective, visible-light powered, catalytic conversion of acetylene to ethylene is reported. The catalyst is a homogeneous molecular cobaloxime that operates in tandem with a photosensitizer at room temperature and bypasses the use of non-environmentally friendly and flammable H2 gas feed. The reaction proceeds through a cobalt-hydride intermediate with ≈100% conversion of acetylene under competitive (ethylene co-feed) conditions after only 50 min, and with no evolution of H2 or over-hydrogenation to ethane. The cobaloxime is further incorporated as a linker in a metal-organic framework; the result is a heterogeneous catalyst for the conversion of acetylene under competitive (ethylene co-feed) conditions that can be recycled up to six times and remains catalytically active for 48 h, before significant loss of performance is observed.

Fast tailoring the ZIF-8 surface microenvironment at ambient temperature to boost glucose oxidase-like activity of AuNPs for biosensing

Rational design and tailoring of the surface microenvironment surrounding the catalytic sites, such as noble metal nanoparticles, is an effective way to enhance the catalytic activity of mimicking enzymes. However, it remains on-going challenges to regulate the microenvironment of the catalytic sites due to the lack of tunable variability in structural precision of conventional solid catalysts. Herein, three types of zeolitic imidazolate framework-8 (ZIF-8) with different major crystal facet orientations, i.e., cubic with (100) facets (denoted ZIF-8c), truncated dodecahedral with (100), (110) facets (denoted ZIF-8tr), and dodecahedral with (110) facets (denoted ZIF-8r), were developed facilely using an electrochemical method by switching the potential at ambient temperature. Because the Zn2+ nodes were predominantly exposed on the (100) facets of ZIF-8, while the ligands were mainly exposed on the (110) facets. Hence, gold nanoparticles (AuNPs) showed differential glucose oxidase (GOx)-like activities when anchored in situ on different crystal facets of ZIF-8 and obeyed the following order ZIF-8c/Au>ZIF-8tr/Au>ZIF-8r/Au. Notably, both the metal nodes and aromatic linkers of ZIF-8 interacted with AuNPs through coordination and π-π interactions. The Zn2+ nodes facilitated the formation of the electron-deficient Au species. The electron transfer from AuNPs to Zn2+ sites effectively boosted the catalytic activity. It was known that directly tailoring the microenvironment at the supporting sites of noble metal catalysts to boost catalysis through a facile electrochemical method was not reported. Based on the favorable GOx-like activity and long-term stability of ZIF-8tr/Au, a highly sensitive electrochemical biosensing platform for assaying squamous cell carcinoma antigen (SCCA) was developed. It enabled fg-level detection of cancer marker.

Dual Cocatalytic Sites Synergize NiFe Layered Double Hydroxide to Boost Oxygen Evolution Reaction in Anion Exchange Membrane Water Electrolyzer

AbstractNickel‐iron layered double hydroxide (LDH) is a promising cost‐efficient catalyst to replace noble metals for alkaline oxygen evolution reaction (OER), yet its intrinsic activity under high current density conditions is not satisfactory, which greatly constrains the industrial application of NiFe LDH catalysts. Herein, a new class of integrated Co and W co‐doped NiFe LDH catalysts is reported with dual cocatalytic sites for alkaline OER catalysis. The optimized Co2.8, W3.8‐NiFe LDH integrated catalyst has superior alkaline OER activity (255 mV@1000 mA cm−2) and excellent catalytic stability (200 h@500 mA cm−2). The turnover frequency value of Co2.8, W3.8‐NiFe LDH can reach 4.02 s−1 at 1.49 V versus RHE, which is 9.6 times higher than that of NiFe LDH and superior to the noble metal catalysts. Moreover, it can achieve 1.0 A cm−2 at 1.86 V and maintain 300‐h stable operation in anion exchange membrane water electrolyzer. Theoretical and experimental studies indicate that W sites promote the *OH adsorption and Co sites favor protons desorption of OH*. These dual cocatalytic sites jointly promote *O coverage, effectively accelerating alkaline OER kinetic.

Electronic effect in bromide-modified noble metal catalysts promotes highly stable and selective hydrogenation

Halides with strong affiliation to metals are traditionally viewed as positions in heterogeneous catalysis. This study introduces a method to enhance the selective hydrogenation performance of noble metal nanoparticle catalysts (Pd, Pt, and Rh hosted on N-doped carbon, SiO2, and Al2O3) by gas-phase bromination with 1-bromooctane. Brominated Pd catalysts, particularly those supported on N-doped carbon, show significant improvements in total butene selectivity and stability in butadiene hydrogenation reactions, displaying >97.5 % selectivity to total butenes at complete conversion with 50 h stable performance even at excessive H2 (H2:butadiene = 50) and a high temperature of 473 K. Comprehensive characterizations coupled with density functional theory calculations reveal that bromide species enhance selective hydrogenation by preferentially adsorbing at stepped Pd sites, altering reaction kinetics and preventing over-hydrogenation. Bromination influences reactant and intermediate adsorption, leading to increased competitive adsorption compared to pristine catalysts. Chemisorption studies on butadiene and 1-butene support altered kinetic behaviors post-bromination. X-ray photoelectron spectroscopy analysis demonstrate an increase in surface Pdδ+ species, owing to the electron-pulling character of nearby adsorbed bromide. In situ diffuse reflection infrared Fourier transform spectroscopy with CO probe molecules confirms Br species adsorption at unsaturated Pd sites. Overall, the study provides an effective approach to tuning the electronic properties of metal catalysts and highlights the positive impact of bromination on improving the hydrogenation performance.

In‐Situ Dynamic Carburization of Mo Oxide with Unprecedented High CO Formation Rate in Reverse Water‐Gas Shift Reaction

AbstractIn situ construction of active structure under reaction conditions is highly desired but still remains challenging in many important catalytic processes. Herein, we observe structural evolution of molybdenum oxide (MoOx) into highly active molybdenum carbide (MoCx) during reverse water‐gas shift (RWGS) reaction. Surface oxygen atoms in various Mo‐based catalysts are removed in H2‐containing atmospheres and then carbon atoms can accumulate on surface to form MoCx phase with the RWGS reaction going on, both of which are enhanced by the presence of intercalated H species or Pt‐dopants in MoOx. The structural evolution from MoOx to MoCx is accompanied by enhanced CO2 conversion, which is positively correlated with the surface C/Mo ratio but negatively with the surface O/Mo ratio. As a result, an unprecedented CO formation rate of 7544.6 mmol ⋅ gcatal−1 ⋅ h−1 at 600 °C has been achieved over in situ carbonized H‐intercalated MoO3 catalyst, which is even higher than those from noble metal catalysts. During 100 h stability test only a minimal deactivation rate of 2.3 % is observed.