Metal Dispersion Research Articles

Surface property tuning of LaCr0.7Ni0.3O3 based perovskite catalysts enable efficient operation of SOFCs on liquid fuels

A-site Sr or Ca substituted perovskite LaCr0.7Ni0.3O3 (LSCN, LCCN) are prepared in this work as catalysts of simulated diesel fuel (N-hexadecane) steam reforming for the on-board hydrogen supplement of solid oxide fuel cells (SOFCs). The effect of different dopants on active metals dispersion and surface properties on catalyst performance is analyzed. The results of the investigation reveal that LCCN possesses the highest catalytic activity coupled with exceptional stability, achieving full fuel conversion at WHSV = 5 mL/g·h, S/C = 3.0, and 750 °C and keeping stable for 200 h, thereby emerging as a potential candidate for liquid fuel processing. SEM, H2-pulse chemisorption and XPS results confirm that the excellent performance is due to the high metal dispersion and steam activation capacity. The poor catalytic performance observed in LSCN is primarily attributed to the presence of Sr segregation and the formation of the SrCrO4 second phase. Sr segregation decreases the steam activation ability of the catalyst as confirmed by XPS. DFT calculation also shows that Sr dopant and Sr segregation decrease the exsolution trend of metal Ni in the perovskite matrix, leading to poor metal dispersion. A simulated reforming gas is used in SOFC and the cell can keep stable for 120 h at a discharging current density of 0.4 A/cm2. This study analyzes the difference between Ca and Sr dopants, and reveals the detrimental effect of Sr segregation, which could enlighten the effect of surface tunning on the performance of perovskite catalysts.

Single atom catalyst induced by redox reaction between iron ion and aniline monomer

The effective design of a low-cost, efficient, and stable non-noble metal electrocatalyst to substitute the noble metal electrocatalyst for oxygen reduction reaction is highly significant. Even though atomically dispersed metal catalyst shows excellent catalytic activity with maximized atom efficiency, the challenge often lies in achieving uniform distribution for single-atom catalysts owing to their tendency to aggregate. In this work, we present a sequential method that involves the reduction of iron (Fe) mediated by aniline (anchored on support), followed by pyrolysis to fabricate the Fe-Nx moieties and achieve the high density of single atom active sites. The resulting Fe SA 900 catalyst exhibited a half-wave potential of 0.84 V vs. reversible hydrogen electrode (RHE) for oxygen reduction reaction and outstanding stability in alkaline condition. Using various analysis techniques and electrochemical analysis, we demonstrated that the electrocatalytic activity of the catalyst arises from Fe single atom. To validate the practical applicability of Fe-N-C catalysts, we conducted an anion exchange membrane fuel cell (AEMFC) test, which demonstrated a high performance of 212 mW cm−2 at maximum power density. This study proves that the effectiveness of a sequential strategy adopting redox reaction and following pyrolysis for precise synthesis of a single atom Fe catalyst.

Terpyridine-Decorated Polymer Nanosphere Latex: Template Nanocarriers for the Synthesis of Cu-CeO2 Hollow Spheres.

Water-soluble polymers with the ability to complex metal ions through complexing ligands have attracted significant interest in diverse domains, such as optical or catalyst applications. In this paper, we successfully synthesized, through a one-pot process combining polymerization-induced self-assembly and reversible addition-fragmentation chain transfer polymerization, aqueous dispersions of terpyridine-decorated poly[poly(ethylene glycol)methyl ether methacrylate]-b-poly(methyl methacrylate) (tpy-PPEGMA-b-PMMA) amphiphilic block copolymers. The in-situ formation of well-defined amphiphilic block copolymers and their self-assembly led to nanosphere latex with the hydrodynamic diameters increasing from 17 to 52 nm and the length of the copolymers increasing from 21,000 to 51,000 g·mol-1. These aqueous dispersed tpy-PPEGMA-b-PMMA nanospheres effectively complex metal ions, such as Cu2+, in a stoichiometric ratio of 2:1. Subsequently, these metal-complexed nanospheres were employed as soft template nanocarriers to control, on the nanometer scale, the dispersion of metal on a nanostructured support. This is exemplified by the synthesis of copper supported on cerium oxide hollow spheres (Cu-CeO2) using Cu2+-tpy-PPEGMA-b-PMMA as template nanocarriers and CeO2 nanoparticles. This novel assembly engineering strategy for the preparation of atomically dispersed metal on a nanostructured support was highlighted through the utilization of Cu-CeO2 hollow spheres as an electrocatalyst for the nitrate reduction reaction (NO3RR) to NH3. These encouraging outcomes emphasize the potential of metal-metal oxide-nanostructured materials to treat contaminated water sources with nitrate while allowing the green production of ammonia.

Hidden Impurities Generate False Positives in Single Atom Catalyst Imaging

AbstractSingle‐atom catalysts (SACs) are an emerging class of materials, leveraging maximum atom utilization and distinctive structural and electronic properties to bridge heterogeneous and homogeneous catalysis. Direct imaging methods, such as aberration‐corrected high‐angle annular dark‐field scanning transmission electron microscopy, are commonly applied to confirm the atomic dispersion of active sites. However, interpretations of data from these techniques can be challenging due to simultaneous contributions to intensity from impurities introduced during synthesis processes, as well as any variation in position relative to the focal plane of the electron beam. To address this matter, this paper presents a comprehensive study on two representative SACs containing isolated nickel or copper atoms. Spectroscopic techniques, including X‐ray absorption spectroscopy, were employed to prove the high metal dispersion of the catalytic atoms. Employing scanning transmission electron microscopy imaging combined with single‐atom‐sensitive electron energy loss spectroscopy, we scrutinized thin specimens of the catalysts to provide an unambiguous chemical identification of the observed single‐atom species and thereby distinguish impurities from active sites at the single‐atom level. Overall, the study underscores the complexity of SACs characterization and establishes the importance of the use of spectroscopy in tandem with imaging at atomic resolution to fully and reliably characterize single‐atom catalysts.

Hidden Impurities Generate False Positives in Single Atom Catalyst Imaging.

Single-atom catalysts (SACs) are an emerging class of materials, leveraging maximum atom utilization and distinctive structural and electronic properties to bridge heterogeneous and homogeneous catalysis. Direct imaging methods, such as aberration-corrected high-angle annular dark-field scanning transmission electron microscopy, are commonly applied to confirm the atomic dispersion of active sites. However, interpretations of data from these techniques can be challenging due to simultaneous contributions to intensity from impurities introduced during synthesis processes, as well as any variation in position relative to the focal plane of the electron beam. To address this matter, this paper presents a comprehensive study on two representative SACs containing isolated nickel or copper atoms. Spectroscopic techniques, including X-ray absorption spectroscopy, were employed to prove the high metal dispersion of the catalytic atoms. Employing scanning transmission electron microscopy imaging combined with single-atom-sensitive electron energy loss spectroscopy, we scrutinized thin specimens of the catalysts to provide an unambiguous chemical identification of the observed single-atom species and thereby distinguish impurities from active sites at the single-atom level. Overall, the study underscores the complexity of SACs characterization and establishes the importance of the use of spectroscopy in tandem with imaging at atomic resolution to fully and reliably characterize single-atom catalysts.

Advances in the Development of Dual‐Atom Catalysts: Structural Characterization and Diversified Catalytic Applications

AbstractAtomically dispersed metal atoms on supports exhibit distinctive advantages in maximizing atomic utilization, which plays an indispensable role in the fabrication of cost‐effective catalysts. In particular, dual‐atom catalysts (DACs) containing dual active sites not only retain the merits of single‐atom catalysts (SACs), but also introduce diverse interactions between the two adjacent metal atoms, endowing them with superior catalytic performance and a broad range of applications. With the development of DACs, it is important to identify active sites and establish intrinsic catalytic mechanisms relationship. The general characterization methods for DACs are comprehensively summarized here, especially the structural nature of dual active sites is discussed in detail. Subsequently, the representative scientific research efforts in various applications including thermocatalysis, electrocatalysis, and photocatalysis are described, with emphasis on structure‐property relationships. Finally, a summary and some prospects for the future of advanced DACs are presented.

Single-Atom Alloy Formation via Reaction-Driven Catalyst Restructuring.

We demonstrate that single-atom alloy catalysts can be made by exposing physical mixtures of monometallic supported Cu and Pd catalysts to vinyl acetate (VA) synthesis reaction conditions. This reaction induces the formation of mobile clusters of metal diacetate species that drive extensive metal nanoparticle restructuring, leading to atomic dispersion of the precious metal, smaller nanoparticle sizes than the parent catalysts, and high activity and selectivity for both VA synthesis and ethanol dehydrogenation reactions. This approach is scalable and appears to be generalizable to other alloy catalysts.

The promotion of rare earth on Pt-SiO2-Al2O3 catalyst for NO oxidation in diesel exhaust

The effective oxidation of NO is the key to the catalytic treatment of diesel vehicle exhaust. Improving the NO oxidation ability is mainly to optimize the chemical state of the active site (Pt), followed by increasing the number of active centers. Considering that the atoms with electronegativity weaker than Pt can provide electrons to change the chemical state of Pt, rare earth elements with weak electronegativity are selected as additives to obtain Pt/M-SiO2-Al2O3 (M = Sc, Y, La, Ce, Pr, Nd, Sm, Eu) catalysts by co-impregnation method. Among them, the Pt/La-SiO2-Al2O3 catalyst has the best NO oxidation performance, compared with the Pt-SiO2-Al2O3, the NO conversion rate increased by 28 %. Due to the special outer electron arrangement of La, its electronegativity is the smallest in rare earth, which makes its outer electrons easy to transfer to Pt atoms, and has the strongest electron interaction. Thus, the highest content of Pt0 was detected in CO diffuse reflectance infrared Fourier transform spectroscopy (CO-DRIFTS) and X-ray photoelectron spectroscopy (XPS). In addition, CO chemisorption and transmission electron microscopy (TEM) confirmed that the introduction of La in the catalyst can significantly improve the dispersion of precious metals. Notably, this simple approach of affecting electron interaction by introducing weakly electronegative elements provides a reference for the design of noble metal catalysts with different valence states to solve complex problems.

Stable loading of MOF-derived carbon skeleton encapsulated Ni and BiOBr on carbonized cellulose fibers for fabricating high-performance and recyclable photocatalytic paper

The highly dispersed small-size metal co-catalysts can effectively improve the photocatalytic efficiency of semiconductor photocatalysts by separating photogenerated electrons and enriching active sites. However, this system tends to aggregate in the absence of carrier, resulting in the decrease of active sites. Here, MOF-derived carbon skeleton (MDCS) encapsulated Ni nanoparticles (Ni@MDCS) and BiOBr was loaded onto carbonized cellulose fibers (CCF) with the help of polydopamine (PDA) to construct high-performance and recyclable photocatalytic paper for photocatalytic degradation of organic dyes in water. The characterization results showed that MDCS promoted good dispersion of Ni nanoparticles and provided sufficient active sites. And Ni@MDCS as a co-catalyst accelerated the separation of photogenerated carriers in BiOBr. The PDA improved the loading state of Ni@MDCS on CCF and converted into N-doped C in the carbonization process for further increasing the transfer efficiency of photogenerated electrons. In the composite paper, the stable loading of Ni@MDCS/BiOBr hybrid on CCF improved the dispersion and reusability of photocatalyst. The degradation rate of rhodamine B on CCF/PDA-C/Ni@MDCS/BiOBr paper was as high as 94.6 % after 60 min visible light irradiation, which was about 2.5 times higher than that of CCF/BiOBr paper. During 10 cycles, CCF/PDA-C/Ni@MDCS/BiOBr paper maintained high photocatalytic efficiency and good structural stability. This study provides a new way for developing high-performance and recyclable photocatalytic paper.

CO2 Hydrogenation to Methanol over Mesoporous SiO2-Coated Cu-Based Catalysts.

Although chemical promotion led to essential improvements in Cu-based catalysts for CO2 hydrogenation to methanol, surpassing structural limitations such as active phase aggregation under reaction conditions remains challenging. In this report, we improved the textural properties of Cu/In2O3/CeO2 and Cu/In2O3/ZrO2 catalysts by coating the nanoparticles with a mesoporous SiO2 shell. This strategy limited particle size up to 3.5 nm, increasing metal dispersion and widening the metal-metal oxide interface region. Chemometric analysis revealed that these structures could maintain high activity and selectivity in a wide range of reaction conditions, with methanol space-time yields up to 4 times higher than those of the uncoated catalysts.

Single-atom catalysts activate persulfate to degrade emerging organic contaminants in aqueous environments.

Single-atom catalysts (SACs) exhibit outstanding catalytic activity due to their highly dispersed metal centers. Activating persulfates (PS) with SACs can generate various reactive oxygen species (ROS) to efficiently degrade emerging organic contaminants (EOCs) in aqueous environments, offering unique advantages such as high reaction rates and excellent stability. This technique has been extensively researched and holds enormous potential applications. In this paper, we comprehensively elaborated on the synthesis methods of SACs and their limitations, and factors influencing the catalytic performance of SACs, including metal center characteristics, coordination environment, and types of substrates. We also analyzed practical considerations for application. Subsequently, we discussed the mechanism of SACs activating PS for EOCs degradation, encompassing adsorption processes, radical pathways, and non-radical pathways. Finally, we provide prospects and outline our vision for future research, aiming to guide advancements in applying this technique.

What Is the Current State of Sustainability in the Decorative Electroplating Industry? A Close Look at New Practices and Advances

Electroplating is a key process in many industrial fields such as automotive, electronics and decorative applications; this process makes it possible to provide new properties to substrates materials such as corrosion resistance, hardness and aesthetic value. Nonetheless, electroplating is considered one of the most non-sustainable industries related to the manufacturing sector, from both an environmental and a social point of view. With the approaching deadlines set by the United Nations for the 2030 Agenda, electroplating companies have started a trend of innovating their production processes with a focus on sustainability, acting on several fronts: performing simulations to predict criticalities and optimize working procedures, reducing the material used and recovering it from processing water. The purpose of this communication is to highlight the state of the art of sustainable practices peculiar to the electroplating industry, critically analyzing ongoing challenges to achieve and exceed the targets set by regulatory agencies. Both atomistic and multiphysics simulations will be analyzed as powerful tools to design both new sustainable formulations and items; then, the problem of metal dispersion will be discussed, evaluating different industrial approaches; finally, the focus will be shifted towards the general procedures to recover metal from wastewater.

Preparation and evaluation of germanium concentrate by ultrasonic purification of tannin germanium residue

Germanium (Ge) is a dispersed metal primarily recovered from secondary Ge-containing resources. The traditional treatment method is hindered by incomplete impurity removal, resulting in a low grade of tannin germanium residue (TGR) and Ge concentrate, high production costs, and significant hazardous waste. This study proposes a new technology involving ultrasonic pre-purification of TGR to enhance the quality of Ge concentrate prepared by roasting. Under optimal conditions (ultrasonic power 225 W, liquid-solid ratio 7:1, H2SO4 concentration 20 g/L, reaction time 30 min, and reaction temperature 40 °C), the removal efficiencies of impurities Zn, Mg, Fe, As, and S from purified tannin germanium residue (PTGR) increased by 4.2%, 4.2%, 17.4%, 8.7%, and 2.9% respectively. Moreover, the Ge content in PTGR increased from 2.9% to 4.1%. The mechanism of ultrasonic action indicated the ultrasonic energy reduced the particle size of the reactants from 67.698 μm to 31.768 μm, thereby accelerating impurity removal. Roasting ultrasonic-purified tannin germanium residue (U-PTGR) at 650 °C with 40 L/h air flow for 120 min produced Ge concentrate with a Ge grade of 33.26%, which is 6.11% higher than the regular method. Analysis using XRD and HRTEM, combined with crystallite size calculation, revealed that the Ge concentrate prepared by U-PTGR exhibited low sintering degree, good crystal properties, and high crystallinity. Implementing this technology could save enterprises approximately $57,412 annually in production costs. Additionally, it holds significant practical importance in reducing hazardous waste emissions and promoting the high-quality development of the Ge industry.

Atomically dispersed Co/Mn immobilized on O, N dual doped hollow carbon spheres as sulfur host for lithium sulfur batteries

The regulation of the chemical coordination environment in the electrocatalyst can effectively suppress the shuttle effect of sulfur species in lithium-sulfur batteries. However, the mechanism of the atomically dispersed dual metal atom with the coordination of various heteroatoms used as the sulfur cathode catalyst and trapper remains unknown. This study introduces, for the first time, atomically dispersed Co and Mn in-situ immobilized on O, N dual-doped hollow carbon spheres (SACoMn/C-(N, O)) as sulfur host. Experiments combined with density functional theory calculations reveal that the synergy between Co-(N, O) and Mn-(N, O) sites enhances the nucleation/deposition and decomposition capabilities of Li2S. This enhancement is attributed to the anchoring-coupling-conversion behavior of sulfur species on the SACoMn/C-(N, O) surface, which effectively restrains the shuttle effect and facilitates the conversion kinetics. Moreover, the cooperation of dual metal atoms with O, N non-metal atoms embedded in the carbon network structure accelerates electric transport and ion diffusion kinetics. The cathode demonstrates a high initial specific capacity of 890 mAh·g−1 at 1 C and show exceptional long-term cycling durability, with a low capacity degradation of 0.037 % per cycle after 1700 cycles. This research may offer novel insights into the design of dual metal atom-decorated, functionalized carbon materials to improve the conversion reaction in sulfur cathodes.

Improving the catalytic activity and thermal stability of Pt-supported catalyst via modulating Ce/Zr molar ratio

The synthesis of Pt-supported catalysts with high stability faces an enormous challenge, especially for applications in high-temperature environments. Here we attempt to improve the catalytic activity and thermal stability of Pt-supported catalyst via modulating Ce/Zr molar ratio. The crystalline structure, texture and metal dispersion of the Pt/CexZr1-x samples were studied by XRD, Raman, XPS, HRTEM and H2-TPR. The results indicate that decreasing Ce/Zr molar ratio can improve the thermal stability, the reducibility of surface lattice oxygen of the catalyst, and enhance the oxygen vacancy content. On the contrary, a higher Ce/Zr molar ratio facilitates the interaction between Pt and CeO2 and inhibits the growth of Pt particles thereby maintaining high Pt dispersion. The Pt/CexZr1-x catalysts with Ce/Zr molar ratio of ∼1.0 might exhibited the best overall catalytic performance within long-term use. The effect of the valence state of Pt on catalytic activity is greater than that of the Pt dispersion. Our findings contribute to a depth understanding of Pt/CeZr catalysts and provide insights into the design of more efficient and durable catalysts for automotive exhaust purification.

Atomically dispersed Rh catalysts formed on defective CeO2 surfaces with hydroformylation activity

The electron density of the metal active sites depends on the surface properties of the support. This study aimed to demonstrate that the formation of atomically dispersed Rh on ceria and the corresponding Rh electron density can be tuned depending on ceria concentration. The highly optimized Rh/CeO2-Al2O3 catalyst exhibited the highest activity during propylene hydroformylation, which was similar to that of the commercially available homogeneous catalyst RhCl(PPh3)3. Combined analytical results and theoretical calculations demonstrated that the increased Ce3+ fraction promoted high Rh electron density and attenuated CO adsorption strength, resulting in an increased hydroformylation activity. Additionally, the catalyst achieved separation and high added value by converting olefins to aldehydes through hydroformylation of olefins in a mixed C2–C4 olefin/paraffin gas. This study showed that atomically dispersed metal supported catalysts can be designed as recyclable heterogeneous catalysts by tailoring the local environment and corresponding electron density of the metal to achieve high activity similar to that of the homogeneous catalysts that manipulate ligands around the metal.

Atomically dispersed dual iron and manganese anchored nitrogen doped reduced graphene as robust cathode catalyst for direct methanol fuel cell and aluminium air battery

A noble metal-free atomically dispersed dual metal (Fe and Mn) anchored nitrogen (N)-doped reduced graphene oxide (rGO) is synthesized as a high-performance oxygen reduction reaction (ORR) electrocatalyst for alkaline direct methanol fuel cell and aluminium-air battery (AAB). The as-synthesized FeMn-NrGO catalyst exhibits a half-wave potential of 0.84 V for ORR and a low onset potential of 0.96 Vvs (RHE). The theoretical study reveals that the synergetic coupling of Mn and Fe with pyridinic and pyrrolic nitrogen weakening adsorption bond strength of the O* intermediates to the active site of the catalyst, thereby improving the for ORR performance. The synthesized Fe3Mn1-NrGO cathode catalyst assembled alkaline direct methanol fuel cell (DMFC) demonstrates a peak power density of 65 mW/cm2 extending an effective strategy to enhance the ORR kinetics of the non-noble metal-based catalyst for fuel cell application. Furthermore, the synthesized Fe3Mn1-NrGO also exhibits excellent ORR activity in 3.5 wt% NaCl solution and demonstrates a peak power density of 11.2 mW/cm2 aqueous NaCl electrolyte-based AAB system.

Dry reforming of methane at high temperature and elevated pressure over nickel spinellized powder catalyst and pellets prepared from a metallurgical residue

AbstractThe coke deposition on catalysts is a significant problem in the dry reforming of methane at elevated pressures. Understanding and controlling the mechanisms of such deposition is essential in developing a techno‐economically viable industrial application for the production of synthesis gas and/or hydrogen. The patent‐pending nickel‐supported upgraded slag oxide (Ni‐UGSO) catalysts, in powder form, have demonstrated excellent performance and achieved equilibrium in dry reforming, steam reforming and mixed methane reforming in a gram‐scale laboratory packed bed reactor under barometric pressure. In this extended study, Ni‐UGSO pellets were prepared using the wet impregnation method. The pelletized form of said catalyst was studied under elevated pressure to imitate the industrial operating conditions in a kilogram‐scale laboratory packed bed reactor. The characterization of the fresh and used catalytic formulation produced data allowing the investigation of the physicochemical properties of catalysts and the effects of metal dispersion, reaction pressure and crystallite size, as well as the role of side reactions on the nature of the coke. The metal support nature favored the interaction between the Ni metal and spinels (UGSO), and the presence of the clay binder (kaolinite, quartz) improved the pellet morphology, provided higher Ni dispersion, maintained the crystallite size, reduced the coke formation and achieved similar or higher performance with respect to Ni‐UGSO powder despite having 85% less surface area. The Ni‐UGSO pellet showed negligible coke deposits from 1 to 6.5 atm and operated successfully for 24 h at 5.5 atm, 800°C and gas hourly space velocity 810 L/(h kg cat). This study provides new insight into the design of a more efficient and robust catalyst for methane dry reforming at elevated pressures, which is critical for potential future transfer at the industrial level.

Catalytic Refining Lignin‐Derived Monomers: Seesaw Effect between Nanoparticle and Single‐Atom Pt

AbstractPt automatically adsorbed on oxygen vacancy of TiO2 via an in situ interfacial redox reaction, resulting in atomically dispersion of Pt on TiO2. In the upgrading of lignin‐derived 4‐propylguaiacol, single‐atom catalyst (SAC) Pt/TiO2−H achieved a conversion of 96.9 % and a demethoxylation selectivity of 93.3 % under 3 MPa H2 at 250 °C for 3 h, markedly different from the performance of nanoparticle counterpart that gave deep deoxygenation selectivity over 99.0 %. The high demethoxylation activity of SAC Pt/TiO2−H is mainly attributed to its weak hydrogen spillover capacity that suppressed the benzene ring hydrogenation and the deep deoxygenation. Additionally, SAC Pt/TiO2−H reduced the energy barrier of CAr−OCH3 bond cleavage and accordingly lowered the Gibbs free energy of the demethoxylation reaction. This facile method could fabricate single‐atom Au, Pd, Ir, and Ru supported on TiO2−H, demonstrating the generality of this strategy for the establishment of a library of SACs. Moreover, SAC exhibited versatile capacity in demethoxylation of different lignin‐derived monomers and high stability. This study showcases the superiority of atomically dispersed metal catalysts for selective demethoxylation reactions and proposes a renewable alternative to fossil‐based 4‐alkylphenols through upgrading of lignin‐derived monomers.

Catalytic Refining Lignin-Derived Monomers: Seesaw Effect between Nanoparticle and Single-Atom Pt.

Pt automatically adsorbed on oxygen vacancy of TiO2 via an in situ interfacial redox reaction, resulting in atomically dispersion of Pt on TiO2. In the upgrading of lignin-derived 4-propylguaiacol, single-atom catalyst (SAC) Pt/TiO2-H achieved a conversion of 96.9 % and a demethoxylation selectivity of 93.3 % under 3 MPa H2 at 250 °C for 3 h, markedly different from the performance of nanoparticle counterpart that gave deep deoxygenation selectivity over 99.0 %. The high demethoxylation activity of SAC Pt/TiO2-H is mainly attributed to its weak hydrogen spillover capacity that suppressed the benzene ring hydrogenation and the deep deoxygenation. Additionally, SAC Pt/TiO2-H reduced the energy barrier of CAr-OCH3 bond cleavage and accordingly lowered the Gibbs free energy of the demethoxylation reaction. This facile method could fabricate single-atom Au, Pd, Ir, and Ru supported on TiO2-H, demonstrating the generality of this strategy for the establishment of a library of SACs. Moreover, SAC exhibited versatile capacity in demethoxylation of different lignin-derived monomers and high stability. This study showcases the superiority of atomically dispersed metal catalysts for selective demethoxylation reactions and proposes a renewable alternative to fossil-based 4-alkylphenols through upgrading of lignin-derived monomers.