Tunable and Efficient Tin Modified Nitrogen‐Doped Carbon Nanofibers for Electrochemical Reduction of Aqueous Carbon Dioxide

Efficient and selective earth‐abundant catalysts are highly desirable to drive the electrochemical conversion of CO₂ into value‐added chemicals. In this work, a low‐cost Sn modified N‐doped carbon nanofiber hybrid catalyst is developed for switchable CO₂ electroreduction in aqueous medium via a straightforward electrospinning technique coupled with a pyrolysis process. The electrocatalytic performance can be tuned by the structure of Sn species on the N‐doped carbon nanofibers. Sn nanoparticles drive efficient formate formation with a high current density of 11 mA cm^?2 and a faradaic efficiency of 62% at a moderate overpotential of 690 mV. Atomically dispersed Sn species promote conversion of CO₂ to CO with a high faradaic efficiency of 91% at a low overpotential of 490 mV. The interaction between Sn species and pyridinic‐N may play an important role in tuning the catalytic activity and selectivity of these two materials.     

Continuous 3D Titanium Nitride Nanoshell Structure for Solar‐Driven Unbiased Biocatalytic CO2 Reduction

Z‐scheme‐inspired tandem photoelectrochemical (PEC) cells have received attention as a sustainable platform for solar‐driven CO₂ reduction. Here, continuously 3D‐structured, electrically conductive titanium nitride nanoshells (3D TiN) for biocatalytic CO₂‐to‐formate conversion in a bias‐free tandem PEC system are reported. The 3D TiN exhibits a periodically porous network with high porosity (92.1%) and conductivity (6.72 × 10⁴ S m^?1), which allows for high enzyme loading and direct electron transfer (DET) to the immobilized enzyme. It is found that the W‐containing formate dehydrogenase from Clostridium ljungdahlii (ClFDH) on the 3D TiN nanoshell is electrically activated through DET for CO₂ reduction. At a low overpotential of 40 mV, the 3D TiN‐ClFDH stably converts CO₂ to formate at a rate of 0.34 µmol h^?1 cm^?2 and a faradaic efficiency (FE) of 93.5%. Compared to a flat TiN‐ClFDH, the 3D TiN‐ClFDH shows a 58 times higher formate production rate (1.74 µmol h^?1 cm^?2) at 240 mV of overpotential. Lastly, a bias‐free biocatalytic tandem PEC cell that converted CO₂ to formate at an average rate of 0.78 µmol h^?1 and an FE of 77.3% only using solar energy and water is successfully assembled.     

Electrocatalytic Reduction of Gaseous CO2 to CO on Sn/Cu‐Nanofiber‐Based Gas Diffusion Electrodes

Earth‐abundant Sn/Cu catalysts are highly selective for the electrocatalytic reduction of CO₂ to CO in aqueous electrolytes. However, CO₂ mass transport limitations, resulting from the low solubility of CO₂ in water, so far limit the CO partial current density for Sn/Cu catalysts to about 10 mA cm^?2. Here, a freestanding gas diffusion electrode design based on Sn‐decorated Cu‐coated electrospun polyvinylidene fluoride nanofibers is demonstrated. The use of gaseous CO₂ as a feedstock alleviates mass transport limitations, resulting in high CO partial current densities above 100 mA cm^?2, while maintaining high CO faradaic efficiencies above 80%. These results represent an important step toward an economically viable pathway to CO₂ reduction.     

Activation of Ni Particles into Single Ni–N Atoms for Efficient Electrochemical Reduction of CO2

Electrochemical reduction of carbon dioxide (CO₂) to fuels and value‐added industrial chemicals is a promising strategy for keeping a healthy balance between energy supply and net carbon emissions. Here, the facile transformation of residual Ni particle catalysts in carbon nanotubes into thermally stable single Ni atoms with a possible NiN₃ moiety is reported, surrounded with a porous N‐doped carbon sheath through a one‐step nanoconfined pyrolysis strategy. These structural changes are confirmed by X‐ray absorption fine structure analysis and density functional theory (DFT) calculations. The dispersed Ni single atoms facilitate highly efficient electrocatalytic CO₂ reduction at low overpotentials to yield CO, providing a CO faradaic efficiency exceeding 90%, turnover frequency approaching 12 000 h^?1, and metal mass activity reaching about 10 600 mA mg^?1, outperforming current state‐of‐the‐art single atom catalysts for CO₂ reduction to CO. DFT calculations suggest that the Ni@N₃ (pyrrolic) site favors *COOH formation with lower free energy than Ni@N₄, in addition to exothermic CO desorption, hence enhancing electrocatalytic CO₂ conversion. This finding provides a simple, scalable, and promising route for the preparation of low‐cost, abundant, and highly active single atom catalysts, benefiting future practical CO₂ electrolysis.     

Overpotentials and Faraday Efficiencies in CO2 Electrocatalysis–the Impact of 1‐Ethyl‐3‐Methylimidazolium Trifluoromethanesulfonate

The mixtures of room temperature ionic liquid 1‐ethyl‐3‐methylimidazolium trifluoromethanesulfonate ([EMIM]TFO) and water as electrolytes for reduction of CO₂ to CO are reported. Linear sweep voltammetry shows overpotentials for CO₂ reduction and the competing hydrogen evolution reaction (HER), both of which vary as a function of [EMIM]TFO concentration in the range from 4 × 10^?3m (0.006 mol%) to 4869 × 10^?3m (50 mol%). A steady lowering of overpotentials up to an optimum for 334 × 10?³m is identified. At 20 mol% and more of [EMIM]TFO, a significant CO₂ reduction plateau and inhibition of HER, which is limited by H₂O diffusion, is noted. Such a plateau in CO₂ reduction correlates to high CO Faraday efficiencies. In case of 50 mol% [EMIM]TFO, a broad plateau spanning over a potential range of 0.58 V evolves. At the same time, the overpotential for HER is increased by 1.20 V when compared to 334 × 10^?3m and, in turn, HER is largely inhibited. The Faraday efficiencies for CO and H₂ formation feature 95.6% ± 6.8% and 0.5% ± 0.3%, respectively, over a period of 3 h in a separator divided cell. Cathodic as well as anodic electrochemical stability of the electrolyte throughout this time period is corroborated in ¹H NMR spectroscopic measurements.     

Engineering Surface Amine Modifiers of Ultrasmall Gold Nanoparticles Supported on Reduced Graphene Oxide for Improved Electrochemical CO2 Reduction

Ultrasmall gold (Au) nanoparticles with high mass activity have great potential for practical applications in CO₂ electroreduction. However, these nanoparticles often suffer from poor product selectivity since their abundant low‐coordinated sites are favorable for H₂ evolution. In this work, a catalyst, reduced graphene oxide supported ultrasmall Au nanoparticles (≈2.4 nm) is developed which delivers high Au‐specific mass activities (>100 A g^?1) and good Faradaic efficiencies (32–60%) for the CO₂‐to‐CO conversion at moderate overpotentials (450–600 mV). The efficiencies can be improved to 59–75% while retaining the ultrahigh mass activities via a simple amine‐modification strategy. In addition, an amine‐structure‐dependent effect is revealed: linear amines promote the CO formation whereas the branched polyamine greatly depresses it; the increasing alkyl chain length boosts the promotion effect of linear amines. The strong Au‐amine interaction and molecular configuration induced amine coverage on the ultrasmall Au NPs may contribute to this effect.     

Edge‐Exposed Molybdenum Disulfide with N‐Doped Carbon Hybridization: A Hierarchical Hollow Electrocatalyst for Carbon Dioxide Reduction

Electrochemical CO₂ reduction (CO₂RR) is a promising technology to produce value‐added fuels and weaken the greenhouse effect. Plenty of efforts are devoted to exploring high‐efficiency electrocatalysts to tackle the issues that show poor intrinsic activity, low selectivity for target products, and short‐lived durability. Herein, density functional theory calculations are firstly utilized to demonstrate guidelines for design principles of electrocatalyst, maximum exposure of catalytic active sites for MoS₂ edges, and electron transfer from N‐doped carbon (NC) to MoS₂ edges. Based on the guidelines, a hierarchical hollow electrocatalyst comprised of edge‐exposed 2H MoS₂ hybridized with NC for CO₂RR is constructed. In situ atomic‐scale observation for catalyst growth is performed by using a specialized Si/SiN_x nanochip at a continuous temperature‐rise period, which reveals the growth mechanism. Abundant exposed edges of MoS₂ provide a large quantity of active centers, which leads to a low onset potential of ≈40 mV and a remarkable CO production rate of 34.31 mA cm^?2 with 92.68% of Faradaic efficiency at an overpotential of 590 mV. The long‐term stability shows negligible degradation for more than 24 h. This work provides fascinating insights into the construction of catalysts for efficient CO₂RR.     

A Water‐Soluble Cu Complex as Molecular Catalyst for Electrocatalytic CO2 Reduction on Graphene‐Based Electrodes

A structurally simple molecular 1,10‐phenanthroline‐Cu complex on a mesostructured graphene matrix that can be active and selective toward CO₂ reduction over H₂ evolution in an aqueous solution is reported. The active sites consist of Cu(I) center in a distorted trigonal bipyramidal geometry, which enables the adsorption of CO₂ with η¹‐COO‐like configuration to commence the catalysis, with a turnover frequency of ≈45 s^?1 at ?1 V versus reversible hydrogen electrode. Using in situ infrared spectroelectrochemical investigation, it is demonstrated that the Cu complex can be reversibly heterogenized near the graphene surface via potential control. An increase of electron density in the complex is observed as a result of the interaction from the electric field, which further tunes the electron distribution in the neighboring CO₂. It is also found that the mesostructure of graphene matrix favored CO₂ reduction on the Cu center over hydrogen evolution by limiting mass transport from the bulk solution to the electrode surface.     

Simultaneous Achieving of High Faradaic Efficiency and CO Partial Current Density for CO2 Reduction via Robust,Noble‐Metal‐Free Zn Nanosheets with Favorable Adsorption Energy

Electrocatalytic CO₂ reduction to fuels is considered a promising strategy for the sustainable carbon cycle. However, the improvement of the catalytic performance of CO₂ electrocatalysts still poses many challenges, especially achieving the large partial current density of product and high faradaic efficiency simultaneously, which are essential for future applications of the electrochemical CO₂ reduction reaction. In response, herein, an in situ porous Zn catalyst is prepared and exhibits high faradaic efficiency and large CO partial current density at the same time, benefiting from the porous architecture with increased exposure and accessibility of active sites. Furthermore, density functional theory calculations demonstrate that the high faradaic efficiency is attributed to the favorable adsorption energy of the key intermediate, which promotes CO₂ electroreduction to CO.     

Nanoporous Au Thin Films on Si Photoelectrodes for Selective and Efficient Photoelectrochemical CO2 Reduction

An Si photoelectrode with a nanoporous Au thin film for highly selective and efficient photoelectrochemical (PEC) CO₂ reduction reaction (CO₂RR) is presented. The nanoporous Au thin film is formed by electrochemical reduction of an anodized Au thin film. The electrochemical treatments of the Au thin film critically improve CO₂ reduction catalytic activity of Au catalysts and exhibit CO Faradaic efficiency of 96% at 480 mV of overpotential. To apply the electrochemical pretreatment of Au films for PEC CO₂RR, a new Si photoelectrode design with mesh‐type co‐catalysts independently wired at the front and the back of the photoelectrode is demonstrated. Due to the superior CO₂RR activity of the nanoporous Au mesh and high photovoltage from Si, the Si photoelectrode with the nanoporous Au thin film mesh shows conversion of CO₂ to CO with 91% Faradaic efficiency at positive potential than the CO₂/CO equilibrium potential.     

Electrochemical CO2 Reduction with Atomic Iron‐Dispersed on Nitrogen‐Doped Graphene

Electrochemical reduction of CO₂ provides an opportunity to reach a carbon‐neutral energy recycling regime, in which CO₂ emissions from fuel use are collected and converted back to fuels. The reduction of CO₂ to CO is the first step toward the synthesis of more complex carbon‐based fuels and chemicals. Therefore, understanding this step is crucial for the development of high‐performance electrocatalyst for CO₂ conversion to higher order products such as hydrocarbons. Here, atomic iron dispersed on nitrogen‐doped graphene (Fe/NG) is synthesized as an efficient electrocatalyst for CO₂ reduction to CO. Fe/NG has a low reduction overpotential with high Faradic efficiency up to 80%. The existence of nitrogen‐confined atomic Fe moieties on the nitrogen‐doped graphene layer is confirmed by aberration‐corrected high‐angle annular dark‐field scanning transmission electron microscopy and X‐ray absorption fine structure analysis. The Fe/NG catalysts provide an ideal platform for comparative studies of the effect of the catalytic center on the electrocatalytic performance. The CO₂ reduction reaction mechanism on atomic Fe surrounded by four N atoms (Fe–N₄) embedded in nitrogen‐doped graphene is further investigated through density functional theory calculations, revealing a possible promotional effect of nitrogen doping on graphene.     

Earth‐Abundant Iron Diboride (FeB2) Nanoparticles as Highly Active Bifunctional Electrocatalysts for Overall Water Splitting

Developing efficient, durable, and earth‐abundant electrocatalysts for both hydrogen and oxygen evolution reactions is important for realizing large‐scale water splitting. The authors report that FeB₂ nanoparticles, prepared by a facile chemical reduction of Fe²⁺ using LiBH₄ in an organic solvent, are a superb bifunctional electrocatalyst for overall water splitting. The FeB₂ electrode delivers a current density of 10 mA cm^?2 at overpotentials of 61 mV for hydrogen evolution reaction (HER) and 296 mV for oxygen evolution reaction (OER) in alkaline electrolyte with Tafel slopes of 87.5 and 52.4 mV dec^?1, respectively. The electrode can sustain the HER at an overpotential of 100 mV for 24 h and OER for 1000 cyclic voltammetry cycles with negligible degradation. Density function theory calculations demonstrate that the boron‐rich surface possesses appropriate binding energy for chemisorption and desorption of hydrogen‐containing intermediates, thus favoring the HER process. The excellent OER activity of FeB₂ is ascribed to the formation of a FeOOH/FeB₂ heterojunction during water oxidation. An alkaline electrolyzer is constructed using two identical FeB₂‐NF electrodes as both anode and cathode, which can achieve a current density of 10 mA cm^?2 at 1.57 V for overall water splitting with a faradaic efficiency of nearly 100%, rivalling the integrated state‐of‐the‐art Pt/C and RuO₂/C.     

Controlling the Active Sites of Sulfur‐Doped Carbon Nanotube–Graphene Nanolobes for Highly Efficient Oxygen Evolution and Reduction Catalysis

Controlling active sites of metal‐free catalysts is an important strategy to enhance activity of the oxygen evolution reaction (OER). Many attempts have been made to develop metal‐free catalysts, but the lack of understanding of active‐sites at the atomic‐level has slowed the design of highly active and stable metal‐free catalysts. A sequential two‐step strategy to dope sulfur into carbon nanotube–graphene nanolobes is developed. This bidoping strategy introduces stable sulfur–carbon active‐sites. Fluorescence emission of the sulfur K‐edge by X‐ray absorption near edge spectroscopy (XANES) and scanning transmission electron microscopy electron energy loss spectroscopy (STEM‐EELS) mapping and spectra confirm that increasing the incorporation of heterocyclic sulfur into the carbon ring of CNTs not only enhances OER activity with an overpotential of 350 mV at a current density of 10 mA cm^?2, but also retains 100% of stability after 75 h. The bidoped sulfur carbon nanotube–graphene nanolobes behave like the state‐of‐the‐art catalysts for OER but outperform those systems in terms of turnover frequency (TOF) which is two orders of magnitude greater than (20% Ir/C) at 400 mV overpotential with very high mass activity 1000 mA cm^?2 at 570 mV. Moreover, the sulfur bidoping strategy shows high catalytic activity for the oxygen reduction reaction (ORR). Stable bifunctional (ORR and OER) catalysts are low cost, and light‐weight bidoped sulfur carbon nanotubes are potential candidates for next‐generation metal‐free regenerative fuel cells.     

Surface Engineering of 3D Gas Diffusion Electrodes for High‐Performance H2 Production with Nonprecious Metal Catalysts

In this work, a methodology is demonstrated to engineer gas diffusion electrodes for nonprecious metal catalysts. Highly active transition metal phosphides are prepared on carbon‐based gas diffusion electrodes with low catalyst loadings by modifying the O/C ratio at the surface of the electrode. These nonprecious metal catalysts yield extraordinary performance as measured by low overpotentials (51 mV at ?10 mA cm^?2), unprecedented mass activities (>800 A g^?1 at 100 mV overpotential), high turnover frequencies (6.96 H₂ s^?1 at 100 mV overpotential), and high durability for a precious metal‐free catalyst in acidic media. It is found that a high O/C ratio induces a more hydrophilic surface directly impacting the morphology of the CoP catalyst. The improved hydrophilicity, stemming from introduced oxyl groups on the carbon electrode, creates an electrode surface that yields a well‐distributed growth of cobalt electrodeposits and thus a well‐dispersed catalyst layer with high surface area upon phosphidation. This report demonstrates the high‐performance achievable by CoP at low loadings which facilitates further cost reduction, an important part of enabling the large‐scale commercialization of non‐platinum group metal catalysts. The fabrication strategies described herein offer a pathway to lower catalyst loading while achieving high efficiency and promising stability on a 3D electrode.     

Exploiting Synergistic Effect by Integrating Ruthenium–Copper Nanoparticles Highly Co‐Dispersed on Graphene as Efficient Air Cathodes for Li–CO2 Batteries

Li–CO₂ batteries are attractive electrical energy storage devices; however, they still suffer from unsatisfactory electrochemical performance, and the kinetics of CO₂ reduction and evolution reactions must be improved significantly. Herein, a composite of ruthenium–copper nanoparticles highly co‐dispersed on graphene (Ru–Cu–G) as efficient air cathodes for Li–CO₂ batteries is designed. The Li–CO₂ batteries with Ru–Cu–G cathodes exhibit ultra‐low overpotential and can be operated for 100 cycles with a fixed capacity of 1000 mAh g^?1 at 200 and 400 mA g^?1. The synergistic effect between Ru and Cu not only regulates the growth of discharge products, but also promotes CO₂ reduction and evolution reactions by changing the electron cloud density of the surface between Ru and Cu. This work may provide new directions and strategies for developing highly efficient air cathodes for Li–CO₂ batteries, or even practical Li–air batteries.     

Ni–Fe–La(Sr)Fe(Mn)O3 as a New Active Cermet Cathode for Intermediate‐Temperature CO2 Electrolysis Using a LaGaO3‐Based Electrolyte

Various additives to Ni–Fe systems are studied as cermet cathodes for CO₂ electrolysis (973–1173 K) using a La_0.9Sr_0.1Ga_0.8Mg_0.2O₃ (LSGM) electrolyte, which is one of the most promising oxide‐ion conductors for intermediate‐temperature solid‐oxide electrolysis cells in terms of ionic‐transport number and conductivity. It is found that Ni–Fe–La_0.6Sr_0.4Fe_0.8Mn_0.2O₃ (Ni–Fe–LSFM) exhibits a remarkable performance with a current density of 2.32 A cm^?2 at 1.6 V and 1073 K. The cathodic overpotential is significantly decreased by mixing the LSFM powder with Ni–Fe, which is related to the increase in the number of reaction sites for CO₂ reduction. For Ni–Fe–LSFM, much smaller particles (<200 nm) are sustained under CO₂ electrolysis conditions at high temperatures than for Ni–Fe. X‐ray diffraction analysis suggests that the main phases of Ni–Fe–LSFM are Ni and LaFeO₃; thus, the oxide phase of LaFeO₃ is also maintained during CO₂ electrolysis. Analysis of the gaseous products indicates that only CO is formed, and the rate of CO formation agrees well with that of a four‐electron reduction process, suggesting that the reduction of CO₂ to CO proceeds selectively. It is also confirmed that almost no coke is deposited on the Ni–Fe–LSFM cathode after CO₂ electrolysis.     

Absorption characteristics and kinetics of CO2 capture into N-methyldiethanolamine aqueous solution catalyzed by the immobilized carbonic anhydrase

Abstract

Carbonic anhydrase (CA) is the most effective CO₂ hydratase catalyst, but the poor storage stability and repeatability of CA limit its development. Therefore, CA was immobilized on the epoxy magnetic composite microspheres to enhance the CO₂ absorption into N-methyldiethanolamine (MDEA) aqueous solution in this work. In the presence of immobilized CA, the CO₂ absorption rate of MDEA solution (10?wt%) (0.63?mmol·min^?1) was greatly improved by almost 40%, and their reaction equilibrium time was shortened from 150?min to 90?min compared with that into MDEA solution. The results indicated that the absorption of CO₂ into MDEA solution had been significantly enhanced by using CA. After the 7th reuse recycle, the activity of the immobilized CA was still closed to its initial value at 313.15?K. Moreover, enzyme catalytic kinetics of immobilized CA was investigated using the p-nitrophenyl acetate (p-NPA) as substrate. The values of Michaelis–Menten constant (K_m) and the maximum velocity (V_max) of the immobilized CA were calculated to be 27.61?mmol/L and 20.14?×?10^?3?mmol·min^?1·mL^?1, respectively. Besides, the kinetics of CO₂ reaction into MDEA with or without CA were also compared. The results showed that CO₂ absorption into CA/MDEA aqueous solution obeyed the pseudo first order regime and the second order kinetics rate constant (k₂) was calculated to be 929?m³·kmol^?1·s^?1, which was twice higher than that of MDEA aqueous solution without immobilized CA (k₂=414 m³·kmol^?1·s^?1) at 313.15?K.     

Bi‐Based Metal‐Organic Framework Derived Leafy Bismuth Nanosheets for Carbon Dioxide Electroreduction

Electroreduction of carbon dioxide (CO₂) into high‐value and readily collectable liquid products is vital but remains a substantial challenge due to the lack of highly efficient and robust electrocatalysts. Herein, Bi‐based metal‐organic framework (CAU‐17) derived leafy bismuth nanosheets with a hybrid Bi/Bi? O interface (Bi NSs) is developed, which enables CO₂ reduction to formic acid (HCOOH) with high activity, selectivity, and stability. Specially, the flow cell configuration is employed to eliminate the diffusion effect of CO₂ molecules and simultaneously achieve considerable current density (200 mA cm^?2) for industrial application. The faradaic efficiency for transforming CO₂ to HCOOH can achieve over 85 or 90% in 1 m KHCO₃ or KOH for at least 10 h despite a current density that exceeds 200 mA cm^?2, outperforming most of the reported CO₂ electroreduction catalysts. The hybrid Bi/Bi? O surface of leafy bismuth nanosheets boosts the adsorption of CO₂ and protects the surface structure of the as‐prepared leafy bismuth nanosheets, which benefits its activity and stability for CO₂ electroreduction. This work shows that modifying electrocatalysts by surface oxygen groups is a promising pathway to regulate the activity and stability for selective CO₂ reduction to HCOOH.     

Shape‐Controlled CO2 Electrochemical Reduction on Nanosized Pd Hydride Cubes and Octahedra

Electrochemical CO₂ reduction reaction (CO₂RR) provides a potential pathway to mitigate challenges related to CO₂ emissions. Pd nanoparticles have shown interesting properties as CO₂RR electrocatalysts, while how different facets of Pd affect its performance in CO₂ reduction to synthesis gas with controlled H₂ to CO ratios has not been understood. Herein, nanosized Pd cubes and octahedra particles dominated by Pd(100) and Pd(111) facets are, respectively, synthesized. The Pd octahedra particles show higher CO selectivity (up to 95%) and better activity than Pd cubes and commercial particles. For both Pd octahedra and cubes, the ratio of H₂/CO products is tunable between 1 and 2, a desirable ratio for methanol synthesis and the Fischer–Tropsch processes. Further studies of Pd octahedra in a 25 cm² flow cell show that a total CO current of 5.47 A is achieved at a potential of 3.4 V, corresponding to a CO partial current density of 220 mA cm^?2. In situ X‐ray absorption spectroscopy studies show that regardless of facet Pd is transformed into Pd hydride (PdH) under reaction conditions. Density functional theory calculations show that the reduced binding energies of CO and HOCO intermediates on PdH(111) are key parameters to the high current density and Faradaic efficiency in CO₂ to CO conversion.     

Tailored Electron Transfer Pathways in Aucore/Ptshell–Graphene Nanocatalysts for Fuel Cells

Au_core/Pt_shell–graphene catalysts (G‐Cys‐Au@Pt) are prepared through chemical and surface chemical reactions. Au–Pt core–shell nanoparticles (Au@Pt NPs) covalently immobilized on graphene (G) are efficient electrocatalysts in low‐temperature polymer electrolyte membrane fuel cells. The 9.5 ± 2 nm Au@Pt NPs with atomically thin Pt shells are attached on graphene via l ‐cysteine (Cys), which serves as linkers controlling NP loading and dispersion, enhancing the Au@Pt NP stability, and facilitating interfacial electron transfer. The increased activity of G‐Cys‐Au@Pt, compared to non‐chemically immobilized G‐Au@Pt and commercial platinum NPs catalyst (C‐Pt), is a result of (1) the tailored electron transfer pathways of covalent bonds integrating Au@Pt NPs into the graphene framework, and (2) synergetic electronic effects of atomically thin Pt shells on Au cores. Enhanced electrocatalytic oxidation of formic acid, methanol, and ethanol is observed as higher specific currents and increased stability of G‐Cys‐Au@Pt compared to G‐Au@Pt and C–Pt. Oxygen reduction on G‐Cys‐Au@Pt occurs at 25 mV lower potential and 43 A g_Pt^?1 higher current (at 0.9 V vs reversible hydrogen electrode) than for C–Pt. Functional tests in direct fomic acid, methanol and ethanol fuel cells exhibit 95%, 53%, and 107% increased power densities for G‐Cys‐Au@Pt over C–Pt, respectively.