Asymmetrical electrohydrogenation of CO2 to ethanol with copper-gold heterojunctions.

Copper is distinctive in electrocatalyzing reduction of CO2 into various energy-dense forms, but it often suffers from limited product selectivity including ethanol in competition with ethylene. Here, we describe systematically designed, bimetallic electrocatalysts based on copper/gold heterojunctions with a faradaic efficiency toward ethanol of 60% at currents in excess of 500 mA cm-2. In the modified catalyst, the ratio of ethanol to ethylene is enhanced by a factor of 200 compared to copper catalysts. Analysis by ATR-IR measurements under operating conditions, and by computational simulations, suggests that reduction of CO2 at the copper/gold heterojunction is dominated by generation of the intermediate OCCOH*. The latter is a key contributor in the overall, asymmetrical electrohydrogenation of CO2 giving ethanol rather than ethylene.

Spatially Confined in Situ Formed Sodiophilic-Conductive Network for High-Performance Sodium Metal Batteries.

The sodium (Na) metal anode encounters issues such as volume expansion and dendrite growth during cycling. Herein, a novel three-dimensional flexible composite Na metal anode was constructed through the conversion-alloying reaction between Na and ultrafine Sb2S3 nanoparticles encapsulated within the electrospun carbon nanofibers (Sb2S3@CNFs). The formed sodiophilic Na3Sb sites and the high Na+-conducting Na2S matrix, coupled with CNFs, establish a spatially confined "sodiophilic-conductive" network, which effectively reduces the Na nucleation barrier, improves the Na+ diffusion kinetics, and suppresses the volume expansion, thereby inhibiting the Na dendrite growth. Consequently, the Na/Sb2S3@CNFs electrode exhibits a high Coulombic efficiency (99.94%), exceptional lifespan (up to 2800 h) at high current densities (up to 5 mA cm-2), and high areal capacities (up to 5 mAh cm-2) in symmetric cells. The coin-type full cells assembled with a Na3V2(PO4)3/C cathode demonstrate significant enhancement in electrochemical performance. The flexible pouch cell achieves an excellent energy density of 301 Wh kg-1.

Highly Electrically Conductive Polyiodide Ionic Liquid Cathode for High-Capacity Dual-Plating Zinc-Iodine Batteries.

Zinc-iodine batteries are one of the most intriguing types of batteries that offer high energy density and low toxicity. However, the low intrinsic conductivity of iodine, together with high polyiodide solubility in aqueous electrolytes limits the development of high-areal-capacity zinc-iodine batteries with high stability, especially at low current densities. Herein, we proposed a hydrophobic polyiodide ionic liquid as a zinc-ion battery cathode, which successfully activates the iodine redox process by offering 4 orders of magnitude higher intrinsic electrical conductivity and remarkably lower solubility that suppressed the polyiodide shuttle in a dual-plating zinc-iodine cell. By the molecular engineering of the chemical structure of the polyiodide ionic liquid, the electronic conductivity can reach 3.4 × 10-3 S cm-1 with a high Coulombic efficiency of 98.2%. The areal capacity of the zinc-iodine battery can achieve 5.04 mAh cm-2 and stably operate at 3.12 mAh cm-2 for over 990 h. Besides, a laser-scribing designed flexible dual-plating-type microbattery based on a polyiodide ionic liquid cathode also exhibits stable cycling in both a single cell and 4 × 4 integrated cell, which can operate with the polarity-switching model with high stability.

Surface Redox Chemistry Regulates the Reaction Microenvironment for Efficient Hydrogen Peroxide Generation.

Electrosynthesis has emerged as an enticing solution for hydrogen peroxide (H2O2) production. However, efficient H2O2 generation encounters challenges related to the robust gas-liquid-solid interface within electrochemical reactors. In this work, we introduce an effective hydrophobic coating modified by iron (Fe) sites to optimize the reaction microenvironment. This modification aims to mitigate radical corrosion through Fe(II)/Fe(III) redox chemistry, reinforcing the reaction microenvironment at the three-phase interface. Consequently, we achieved a remarkable yield of up to 336.1 mmol h-1 with sustained catalyst operation for an extensive duration of 230 h at 200 mA cm-2 without causing damage to the reaction interface. Additionally, the Faradaic efficiency of H2O2 exceeded 90% across a broad range of test current densities. This surface redox chemistry approach for manipulating the reaction microenvironment not only advances long-term H2O2 electrosynthesis but also holds promise for other gas-starvation electrochemical reactions.

Hydrogen Peroxide Spillover on Platinum-Iron Hybrid Electrocatalyst for Stable Oxygen Reduction.

Iron-nitrogen-carbon (Fe-N-C) catalysts, although the most active platinum-free option for the cathodic oxygen reduction reaction (ORR), suffer from poor durability due to the Fe leaching and consequent Fenton effect, limiting their practical application in low-temperature fuel cells. This work demonstrates an integrated catalyst of a platinum-iron (PtFe) alloy planted in an Fe-N-C matrix (PtFe/Fe-N-C) to address this challenge. This novel catalyst exhibits both high-efficiency activity and stability, as evidenced by its impressive half-wave potential (E1/2) of 0.93 V versus reversible hydrogen electrode (vs RHE) and minimal 7 mV decay even after 50,000 potential cycles. Remarkably, it exhibits a very low hydrogen peroxide (H2O2) yield (0.07%) at 0.6 V and maintains this performance with negligible change after 10,000 potential cycles. Fuel cells assembled with this cathode PtFe/Fe-N-C catalyst show exceptional durability, with only 8 mV voltage loss at 0.8 A cm-2 after 30,000 cycles and ignorable current degradation at a voltage of 0.6 V over 85 h. Comprehensive in situ experiments and theoretical calculations reveal that oxygen species spillover from Fe-N-C to PtFe alloy not only inhibits H2O2 production but also eliminates harmful oxygenated radicals. This work paves the way for the design of highly efficient and stable ORR catalysts and has significant implications for the development of next-generation fuel cells.

Imidazolium-Functionalized Conjugated Polymer for On-Site Visual and Ultrasensitive Detection of Toxic Hexavalent Chromium.

Hexavalent chromium [Cr(VI)] is considered a serious environmental pollutant that possesses a hazardous effect on humans even at low concentrations. Thus, the development of a bifunctional material for ultratrace-selective detection and effective elimination of Cr(VI) from the environment remains highly desirable and scarcely reported. In this work, we explore an imidazolium-appended polyfluorene derivative PF-DBT-Im as a highly sensitive/selective optical probe and a smart adsorbent for Cr(VI) ions with an ultralow detection limit of 1.77 nM and removal efficiency up to 93.7%. In an aqueous medium, PF-DBT-Im displays obvious transformation in its emission color from blue to magenta on exclusively introducing Cr(VI), facilitating naked-eye colorimetric detection. Consequently, a portable sensory device integrated with a smartphone is fabricated for realizing real-time and on-site visual detection of Cr(VI). Besides, the imidazolium groups attached onto side chains of PF-DBT-Im are found to be highly beneficial for achieving selective and efficient elimination of Cr(VI) with capacity as high as 128.71 mg g-1. More interestingly, PF-DBT-Im could be easily regenerated following treatment with KBr and can be recycled at least five times in a row. The main factor behind ultrasensitive response and excellent removal efficiency is found to be anion-exchange-induced formation of a unique ground-state complex between PF-DBT-Im and Cr(VI), as evident by FT-IR, XPS, and simulation studies. Thus, taking advantage of the excellent signal amplification property and rich ion-exchange sites, a dual-functional-conjugated polymer PF-DBT-Im is presented for the concurrent recognition and elimination of Cr(VI) ions proficiently and promptly with great prospects in environmental monitoring and water decontamination.

Periodic Defect Engineering of Iron-Nitrogen-Carbon Catalysts for Nitrate Electroreduction to Ammonia.

Iron-nitrogen-carbon single atom catalyst (SAC) is regarded as one of the promising electrocatalysts for NO3 - reduction reaction (NO3 RR) to NH3 due to its high activity and selectivity. However, synergistic effects of topological defects and FeN4 active moiety in Fe-N-C SAC have rarely been investigated. By performing density functional theory (DFT) calculations, 13 defective graphene FeN4 with 585, 484, and 5775 topological line defects are constructed, yielding 585-68-FeN4 with optimal NO3 RR catalytic activity, high selectivity, as well as robust anti-dissolution stability. The high NO3 RR activity on 585-68-FeN4 is well explained by the high valence state of Fe center as well as asymmetric charge distribution on FeN4 moiety influenced by 5- and 8-member rings. This DFT work provides theoretical guidance for engineering NO3 RR performance of iron-nitrogen-carbon catalysts by modulating periodic topological defects.

Boosted Oxygen Kinetics of Hierarchically Mesoporous Mo2C/C for High-current-density Zn-air Battery.

The high-current-density Zn-air battery shows big prospects in next-generation energy technologies, while sluggish O2 reaction and diffusion kinetics barricade the applications. Herein, the sequential assembly is innovatively demonstrated for hierarchically mesoporous molybdenum carbides/carbon microspheres with a tunable thickness of mesoporous carbon layers (Meso-Mo2C/C-x, where x represents the thickness). The optimum Meso-Mo2C/C-14 composites (≈2 µm in diameter) are composed of mesoporous nanosheets (≈38 nm in thickness), which possess bilateral mesoporous carbon layers (≈14 nm in thickness), inner Mo2C/C layers (≈8 nm in thickness) with orthorhombic Mo2C nanoparticles (≈2 nm in diameter), a high surface area of ≈426 m2 g-1, and open mesopores (≈6.9 nm in size). Experiments and calculations corroborate the hierarchically mesoporous Mo2C/C can enhance hydrophilicity for supplying sufficient O2, accelerate oxygen reduction kinetics by highly-active Mo2C and N-doped carbon sites, and facilitate O2 diffusion kinetics over hierarchically mesopores. Therefore, Meso-Mo2C/C-14 outputs a high half-wave potential (0.88 V vs RHE) with a low Tafel slope (51 mV dec-1) for oxygen reduction. More significantly, the Zn-air battery delivers an ultrahigh power density (272 mW cm-2), and an unprecedented 100 h stability at a high-current-density condition (100 mA cm-2), which is one of the best performances.

A First-Principles Study of Anion Doping in LiFePO4 Cathode Materials for Li-Ion Batteries.

Doping anions into LiFePO4 can improve the electrochemical performance of lithium-ion batteries. In this study, structures, electronic properties and Li-ion migration of anion (F- , Cl- , and S2- ) doping into LiFePO4 were systematically investigated by means of density functional theory calculations. Anion substitution for oxygen atoms leads to an expansion of the LiFePO4 lattice, significantly facilitating Li-ion diffusion. For Cl- and F- anion doped into LiFePO4 , the energy barrier of Li-ion migration gets lowered to 0.209 eV and 0.283 eV from 0.572 eV. The introduction of anions narrows the forbidden band of LiFePO4 , enhancing its electronic conductivity. This work pays a way towards the rational design of high-performance lithium-ion batteries.

SnO2/SnS heterojunction anchoring on CMK-3 mesoporous network improves the reversibility of conversion reaction for lithium/sodium ions storage.

Tin oxide-based (SnO2) materials show high theoretical capacity for lithium and sodium storage benefiting from a double-reaction mechanism of conversion and alloying reactions. However, due to the limitation of the reaction thermodynamics and kinetics, the conversion reaction process of SnO2usually shows irreversibility, resulting in serious capacity decay and hindering the further application of the SnO2anode. Herein, SnO2/SnS heterojunction was anchored on the surface and inside of CMK-3 byinsitusynthesis method, forming a stable 3D structural material (SnO2/SnS@CMK-3). The electrochemical properties of SnO2/SnS@CMK-3 composite show high capacity and reversible conversion reaction, which was attributed to the synergistic effect of CMK-3 and SnO2/SnS heterojunction. To further investigate the influence of the heterojunction on the reversibility of the conversion reaction, the Gibbs free energy (ΔG) was calculated using density functional theory. The results show that SnO2/SnS heterojunction has a closer to zero ΔGfor lithium/sodium ion batteries compared to SnO2, indicating that the heterojunction enhances the reversibility of the conversion reaction in chemical reaction thermodynamics. Our work provides insights into the reversibility of the conversion reaction of SnO2-based materials, which is essential for improving their electrochemical performance.

RuO2 Catalysts for Electrocatalytic Oxygen Evolution in Acidic Media: Mechanism, Activity Promotion Strategy and Research Progress.

Proton Exchange Membrane Water Electrolysis (PEMWE) under acidic conditions outperforms alkaline water electrolysis in terms of less resistance loss, higher current density, and higher produced hydrogen purity, which make it more economical in long-term applications. However, the efficiency of PEMWE is severely limited by the slow kinetics of anodic oxygen evolution reaction (OER), poor catalyst stability, and high cost. Therefore, researchers in the past decade have made great efforts to explore cheap, efficient, and stable electrode materials. Among them, the RuO2 electrocatalyst has been proved to be a major promising alternative to Ir-based catalysts and the most promising OER catalyst owing to its excellent electrocatalytic activity and high pH adaptability. In this review, we elaborate two reaction mechanisms of OER (lattice oxygen mechanism and adsorbate evolution mechanism), comprehensively summarize and discuss the recently reported RuO2-based OER electrocatalysts under acidic conditions, and propose many advanced modification strategies to further improve the activity and stability of RuO2-based electrocatalytic OER. Finally, we provide suggestions for overcoming the challenges faced by RuO2 electrocatalysts in practical applications and make prospects for future research. This review provides perspectives and guidance for the rational design of highly active and stable acidic OER electrocatalysts based on PEMWE.

Interfacial Thermoconvection and Atomic Relay Catalysis Enable Equilibrium Shifting and Rapid Glucose-to-Fructose Isomerization.

The aqueous glucose-to-fructose isomerization is controlled by thermodynamics to an equilibrium limit of ~50% fructose yield. However, here we report an in-situ fructose removal strategy enabled by an interfacial local photothermal effect in combination with relay catalysis of geminal and isolated potassium single atoms (K SAs) on graphene-type carbon (Ksg/GT) to effectively bypass the equilibrium limit and markedly speed up glucose-to-fructose isomerization. At 25 ºC, an unprecedented fructose yield of 68.2% was obtained over Ksg/GT in an aqueous solution without any additives under 30-min solar-like irradiation. Mechanistic studies expounded that the interfacial thermoconvection caused by the local photothermal effect of the graphene-type carbon and preferable glucose adsorption on single-atom K could facilitate the release of in-situ formed fructose. The geminal K SAs were prone to form a stable metal-glucose complex via bidentate coordination, and could significantly reduce the C-H bond electron density by light-driven electron transfer toward K. This facilitated the hydride shift rate-determining step and expedited glucose isomerization. In addition, isolated K SAs favored the subsequent protonation and ring-closure process to furnish fructose. The integration of the interfacial thermoconvection-enhanced in-situ removal protocol and tailored atomic catalysis opens a prospective avenue for boosting equilibrium-limited reactions under mild conditions.

CO Intermediate-Assisted Dynamic Cu Sintering During Electrocatalytic CO2 Reduction on Cu-N-C Catalysts.

The electrochemical CO2 reduction reaction (eCO2RR) to multicarbon products has been widely recognized for Cu-based catalysts. However, the structural changes in Cu-based catalysts during the eCO2RR pose challenges to achieving an in-depth understanding of the structure-activity relationship, thereby limiting catalyst development. Herein, we employ constant-potential density functional theory calculations to investigate the sintering process of Cu single atoms of Cu-N-C single-atom catalysts into clusters under eCO2RR conditions. Systematic constant-potential ab initio molecular dynamics simulations revealed that the leaching of Cu-(CO)x moieties and subsequent agglomeration into clusters can be facilitated by synergistic adsorption of H and eCO2RR intermediates (e.g., CO). Increasing the Cu2+ concentration or the applied potential can efficiently suppress Cu sintering. Both microkinetic simulations and experimental results further confirm that sintered Cu clusters play a crucial role in generating C2 products. These findings provide significant insights into the dynamic evolution of Cu-based catalysts and the origin of their activity toward C2 products during the eCO2RR.

d-Electrons of Platinum Alloy Steering CO Pathway for Low-charge Potential Li-CO2 Batteries.

Aprotic Li-CO2 batteries suffer from sluggish solid-solid co-oxidation kinetics of C and Li2CO3, requiring extremely high charging potentials and leading to serious side reactions and poor energy efficiency. Herein, we introduce a novel approach to address these challenges by modulating the reaction pathway with tailored Pt d-electrons and develop an aprotic Li-CO2 battery with CO and Li2CO3 as the main discharge products. Note that the gas-solid co-oxidation reaction between CO and Li2CO3 is both kinetically and thermodynamically more favorable. Consequently, the Li-CO2 batteries with CoPt alloy-supported on nitrogen-doped carbon nanofiber (CoPt@NCNF) cathode exhibit a charging potential of 2.89 V at 50 µA cm-2, which is the lowest charging potential to date. Moreover, the CoPt@NCNF cathode also shows exceptional cycling stability (218 cycles at 50 µA cm-2) and high energy efficiency up to 74.6%. Comprehensive experiments and theoretical calculations reveal that the lowered d-band center of CoPt alloy effectively promotes CO desorption and inhibits further CO reduction to C. This work provides promising insights into developing efficient and CO-selective Li-CO2 batteries.

Suppressed Dissolution of Fluorine-Rich SEI Enables Highly Reversible Zinc Metal Anode for Stable Aqueous Zinc-Ion Batteries.

The instability of the solid electrolyte interface (SEI) is a critical challenge for the zinc metal anodes, leading to an erratic electrode/electrolyte interface and hydrogen evolution reaction (HER), ultimately resulting in anode failure. This study uncovers that the fluorine species dissolution is the root cause of SEI instability. To effectively suppress the F- dissolution, an introduction of a low-polarity molecule, 1,4-thioxane (TX), is proposed, which reinforces the stability of the fluorine-rich SEI. Moreover, the TX molecule has a strong affinity for coordinating with Zn2+ and adsorbing at the electrode/electrolyte interface, thereby diminishing the activity of local water and consequently impeding SEI dissolution. The robust fluorine-rich SEI layer promotes the high durability of the zinc anode in repeated plating/stripping cycles, while concurrently suppressing HER and enhancing Coulombic efficiency. Notably, the symmetric cell with TX demonstrates exceptional electrochemical performance, sustaining over 500 hours at 20 mA cm-2 with 10 mAh cm-2. Furthermore, the Zn||KVOH full cell exhibits excellent capacity retention, averaging 6.8 mAh cm-2 with 98 % retention after 400 cycles, even at high loading with a lean electrolyte. This work offers a novel perspective on SEI dissolution as a key factor in anode failure, providing valuable insights for the electrolyte design in energy storage devices.

Selective Increase in CO2 Electroreduction to Ethanol Activity at Nanograin-Boundary-Rich Mixed Cu(I)/Cu(0) Sites via Enriching Co-Adsorbed CO and Hydroxyl Species.

Selective producing ethanol from CO2 electroreduction is highly demanded, yet the competing ethylene generation route is commonly more thermodynamically preferred. Herein, we reported an efficient CO2-to-ethanol conversion (53.5 % faradaic efficiency at -0.75 V versus reversible hydrogen electrode (vs. RHE)) over an oxide-derived nanocubic catalyst featured with abundant "embossment-like" structured grain-boundaries. The catalyst also attains a 23.2 % energy efficiency to ethanol within a flow cell reactor. In situ spectroscopy and electrochemical analysis identified that these dualphase Cu(I) and Cu(0) sites stabilized by grain-boundaries are very robust over the operating potential window, which maintains a high concentration of co-adsorbed *CO and hydroxyl (*OH) species. Theoretical calculations revealed that the presence of *OHad not only promote the easier dimerization of *CO to form *OCCO (ΔG~0.20 eV) at low overpotentials but also preferentially favor the key *CHCOH intermediate hydrogenation to *CHCHOH (ethanol pathway) while suppressing its dehydration to *CCH (ethylene pathway), which is believed to determine the remarkable ethanol selectivity. Such imperative intermediates associated with the bifurcation pathway were directly distinguished by isotope labelling in situ infrared spectroscopy. Our work promotes the understanding of bifurcating mechanism of CO2ER-to-hydrocarbons more deeply, providing a feasible strategy for the design of efficient ethanol-targeted catalysts.

Customizing CO2 Electroreduction by Pulse-Induced Anion Enrichment.

Electrochemically converting CO2 into specified high-value products is critical for carbon neutral economics. However, governing the product distribution of the CO2 electroreduction on Cu-based catalysts remains challenging. Herein, we put forward an anion enrichment strategy to efficiently dictate the route of *CO reduction by a pulsed electrolysis strategy. Upon periodically applying a positive potential on the cathode, the anion concentration in the vicinity of the electrode increases apparently. By adopting KF, KCl, and KHCO3 as electrolytes, the dominant CO2 electroreduction product on commercial Cu foil can be tuned into CO (53% ± 2.5), C2+ (76.6 ± 2.1%), and CH4 (42.6 ± 2.1%) under pulsed electrolysis. Notably, one can delicately tailor the ratios of CO/CH4, CH4/C2+, and C2+/CO by simply changing the composition of the electrolyte. Density functional theory calculations demonstrate that locally enriched anions can affect the key CO2RR intermediates in different ways owing to their specific electronegativity and volume, which leads to the distinct selectivity. The present study highlights the importance of tuning ionic species at the electrode-electrolyte interface for customizing the CO2 electroreduction products.

Urchin-Like Structured MoO2 /Mo3 P/Mo2 C Triple-Interface Heterojunction Encapsulated within Nitrogen-Doped Carbon for Enhanced Hydrogen Evolution Reaction.

The development of highly efficient and cost-effective hydrogen evolution reaction (HER) catalysts is highly desirable to efficiently promote the HER process, especially under alkaline condition. Herein, a polyoxometalates-organic-complex-induced carbonization method is developed to construct MoO2 /Mo3 P/Mo2 C triple-interface heterojunction encapsulated into nitrogen-doped carbon with urchin-like structure using ammonium phosphomolybdate and dopamine. Furthermore, the mass ratio of dopamine and ammonium phosphomolybdate is found critical for the successful formation of such triple-interface heterojunction. Theoretical calculation results demonstrate that such triple-interface heterojunctions possess thermodynamically favorable water dissociation Gibbs free energy (ΔGH2O ) of -1.28 eV and hydrogen adsorption Gibbs free energy (ΔGH* ) of -0.41 eV due to the synergistic effect of Mo2 C and Mo3 P as water dissociation site and H* adsorption/desorption sites during the HER process in comparison to the corresponding single components. Notably, the optimal heterostructures exhibit the highest HER activity with the low overpotential of 69 mV at the current density of 10 mA cm-2 and a small Tafel slope of 60.4 mV dec-1 as well as good long-term stability for 125 h. Such remarkable results have been theoretically and experimentally proven to be due to the synergistic effect between the unique heterostructures and the encapsulated nitrogen-doped carbon.

Stratified Oxygen Vacancies Enhance the Performance of Mesoporous TiO2 Electron Transport Layer in Printable Perovskite Solar Cells.

The low electrical conductivity and the high surface defect density of the TiO2 electron transport layer (ETL) limit the power conversion efficiency (PCE) of corresponding perovskite solar cells (PSCs). Here, the conductivity and defect modulation of the mesoporous TiO2 (mp-TiO2 ) ETL via oxygen vacancy (OV) management by the reduction and oxidation treatment are reported. Reduction treatment via reducing agent introduces abundant OVs into the TiO2 nanocrystalline particles on the surface and at the subsurface. The following oxidation treatment via hydrogen peroxide removes the surface OVs while remains the subsurface OVs, resulting in stratified OVs. The stratified OVs improve the conductivity of TiO2 ETL by increasing carrier donors and decrease nonradiative centers by reducing surface defects. Such synergy ensures the capability of mp-TiO2 as the well-performed ETL with improved energy level alignment, suppressed interface recombination, enhanced carrier extraction, and transport. As a result, printable hole-conductor-free carbon-based mesoscopic PSCs based on the modulated mp-TiO2 ETL demonstrate a highest reported PCE of 18.96%.

Computational Study of Single Metal Atom Anchored on Black Phosphorus for Methane Oxidation to Methanol by Nitrous Oxide.

Direct conversion of methane to high-value-added transportable methanol is a great challenge, which requires high energy input to break the strong C-H bond. Developing efficient catalysts for methane oxidation to methanol under mild conditions is of vital importance. In this work, single transition metal atoms (TM=Fe, Co, Ni, Cu) anchored on black phosphorus (TM@BP) were studied as catalysts to assist the methane oxidation to methanol by means of first-principles calculations. The results indicate that Cu@BP exhibits an outstanding catalytic activity through the radical reaction pathways and the formation of the Cu-O active site is rate-determining with an energy barrier of 0.48 eV. Meanwhile, electronic structure calculations and dynamic simulations show that Cu@BP offers excellent thermal stability. Our calculations provide a new approach for the rational design of single atom catalysts for methane oxidation to methanol.