Ru Nanoclusters Research Articles

High-silica faujasite zeolite-tailored metal encapsulation for the low-temperature production of pentanoic biofuels

Zeolite-encapsulated metal nanoclusters are at the heart of bifunctional catalysts, which hold great potential for petrochemical conversion and the emerging sustainable biorefineries. Nevertheless, efficient encapsulation of metal nanoclusters into a high-silica zeolite Y in particular with good structural integrity still remains a significant challenge. Herein, we have constructed Ru nanoclusters (∼1 nm) encapsulated inside a high-silica zeolite Y (SY) with a SiO2/Al2O3 ratio (SAR) of 10 via a cooperative strategy for direct zeolite synthesis and a consecutive impregnation for metal encapsulation. Compared with the benchmark Ru/H-USY and other analogues, the as-prepared Ru/H-SY markedly boosts the yields of pentanoic biofuels and stability in the direct hydrodeoxygenation of biomass-derived levulinate even at a mild temperature of 180 °C, which are attributed to the notable stabilization of transition states by the enhanced acid accessibility and properly sized constraints of zeolite cavities owing to the good structural integrity.

Design of Ru-Co/MgO-Al2O3 catalyst system for CO2 reforming of methane: Performance investigation concerning the Mg/Al ratio

This study explores the design of bimetallic Co-Ru nanoclusters deposited on surface-tuned mesoporous Mg-Al mixed oxide support for the CO2 reforming of methane (DRM) process. The evaporation-induced self-assembly technique was used to create a series of MgO-Al2O3 mixed oxide supports with various Mg/Al molar ratios. Co and Ru nanoclusters over the MgO-Al2O3 supports were decorated using a urea precipitation-deposition approach. Results revealed that the activity and stability of the DRM catalyst were substantially reliant on the Mg/Al molar ratio and Co-Ru metal combination. Among the series of Co-loaded catalysts, the best performance was obtained over an unpromoted CoMg20Al catalyst (20 wt.% Mg), with only a 10 % activity loss after 50 h of study. A modification of CoMg20Al by 0.5 wt.% Ru significantly enhanced the catalytic activity, demonstrating a 93 % methane conversion with raw feed and stable activity over a 100-h extended activity analysis. The catalyst characterization showed that Mg concentration increased basic sites over Mg-Al support. Due to the separation of crystalline phases as MgO-MgAl2O4, CoMg40Al had the most basic sites but poor DRM reaction performance. Balanced acidic/basic properties and well-dispersed Co-Rh nanoclusters-maintained DRM activity and stability. Ru-promoted CoMg20Al catalyzed the lowest activation energies.

Electrocatalytic Coenhancement of Bimetallic Polyphthalocyanine-Anchored Ru Nanoclusters Enabling Efficient Overall Water Splitting at Ampere-Level Current Densities.

Efficient electrocatalysts capable of operating continuously at industrial ampere-level current densities are crucial for large-scale applications of electrocatalytic water decomposition for hydrogen production. However, long-term industrial overall water splitting using a single electrocatalyst remains a major challenge. Here, bimetallic polyphthalocyanine (FeCoPPc)-anchored Ru nanoclusters, an innovative electrocatalyst comprising the hydrogen evolution reaction (HER) active Ru and the oxygen evolution reaction (OER) active FeCoPPc, engineered for efficient overall water splitting are demonstrated. By density functional theory calculations and systematic experiments, the electrocatalytic coenhancement effect resulting from unique charge redistribution, which synergistically boosts the HER activity of Ru and the OER activity of FeCoPPc by optimizing the adsorption energy of intermediates, is unveiled. As a result, even at a large current density of 2.0 A cm-2 , the catalyst exhibits low overpotentials of 220 and 308mV, respectively, for HER and OER. It exhibits excellent stability, requiring only 1.88V of cell voltage to achieve a current density of 2.0 A cm-2 in a 6.0m KOH electrolyte at 70°C, with a remarkable operational stability of over 100 h. This work provides a new electrocatalytic coenhancement strategy for the design and synthesis of electrocatalyst, paving the way for industrial-scale overall water splitting applications.

Green and active hydrogen production from hydrolysis of ammonia borane by using caffeine carbon quantum dot-supported ruthenium catalyst in methanol solvent by hydrothermal treatment

Here, carbon quantum dot (CQD) supported Ru nanoparticles from the caffeine in methanol or water by the hydrothermal method were synthesized for the first time to produce hydrogen (H2) by hydrolysis of ammonia borane(NH3BH3) and their catalytic activities were investigated. The chemical compositions and morphology structures of this caffeine carbon dot-supported Ru catalysts were carefully characterized by UV, PL, TEM, FTIR, and ICP/OES analyses. Well-dispersed Ru nanoclusters with ∼1.81 nm particle size on CQD by the hydrothermal method in methanol medium showed very good catalytic performance. The turnover frequency (TOF) obtained for H2 production from the catalytic hydrolysis of 5% NH3BH3 with CQD supported Ru catalyst obtained by the hydrothermal method in methanol and water was found to be 361 and 1895 mol H2 min−1 mol−1, respectively. The activation energies (Ea) for NH3BH3 hydrolysis with the same catalysts were measured as 33.32 and 27.80 kJmol-1, respectively.

Atomization-Induced High Intrinsic Activity of a Biocompatible MgAl-LDH Supported Ru Single-Atom Nanozyme for Efficient Radicals Scavenging.

Developing efficient nanozymes to mimic natural enzymes for scavenging reactive radicals remains a significant challenge owing to the insufficient activity of conventional nanozymes. Herein, we report a novel Ru single-atom nanozyme (SAE), featuring atomically dispersed Ru atoms on a biocompatible MgAl-layered double hydroxide (Ru1 /LDH). The prepared Ru1 /LDH SAE shows high intrinsic peroxidase (POD)-like catalytic activity, which outperforms the Ru nanoclusters (NCs) nanozyme by a factor of 20 and surpasses most SAEs. The density functional theory calculations reveal that the high intrinsic POD-like activity of Ru1 /LDH can be attributed to a heterolytic path of H2 O2 dissociation on the single Ru sites, which requires lower free energy (0.43 eV) compared to the homolytic path dissociation on Ru NC (0.63 eV). In addition, the Ru1 /LDH SAE shows excellent multiple free radicals scavenging ability, including superoxide anion radical (O2 ⋅- ), hydroxyl radical (⋅OH), nitric oxide radical (NO⋅) and 2, 2-diphenyl-1-picrylhydrazyl radical (DPPH⋅). Given the advantages of Ru1 /LDH with high enzymatic activities, biosafety, and ease to scale up, it paves the way for exploring SAEs in the practical biological immunity system.

Atomization‐Induced High Intrinsic Activity of a Biocompatible MgAl‐LDH Supported Ru Single‐Atom Nanozyme for Efficient Radicals Scavenging

AbstractDeveloping efficient nanozymes to mimic natural enzymes for scavenging reactive radicals remains a significant challenge owing to the insufficient activity of conventional nanozymes. Herein, we report a novel Ru single‐atom nanozyme (SAE), featuring atomically dispersed Ru atoms on a biocompatible MgAl‐layered double hydroxide (Ru1/LDH). The prepared Ru1/LDH SAE shows high intrinsic peroxidase (POD)‐like catalytic activity, which outperforms the Ru nanoclusters (NCs) nanozyme by a factor of 20 and surpasses most SAEs. The density functional theory calculations reveal that the high intrinsic POD‐like activity of Ru1/LDH can be attributed to a heterolytic path of H2O2 dissociation on the single Ru sites, which requires lower free energy (0.43 eV) compared to the homolytic path dissociation on Ru NC (0.63 eV). In addition, the Ru1/LDH SAE shows excellent multiple free radicals scavenging ability, including superoxide anion radical (O2⋅−), hydroxyl radical (⋅OH), nitric oxide radical (NO⋅) and 2, 2‐diphenyl‐1‐picrylhydrazyl radical (DPPH⋅). Given the advantages of Ru1/LDH with high enzymatic activities, biosafety, and ease to scale up, it paves the way for exploring SAEs in the practical biological immunity system.

A unique sandwich-structured Ru-TiO/TiO2@NC as an efficient bi-functional catalyst for hydrogen oxidation and hydrogen evolution reactions

Developing active and stable non-Pt electrocatalysts for hydrogen oxidation (HOR) and evolution reactions (HER) are critical for anion exchange membrane fuel cells and water electrolyzers. Herein, we report a highly active and robust electrocatalyst Ru-TiO/TiO2@NC, in which Ru nanoclusters are sandwiched between TiO/TiO2 nanosheets and nitrogen-doped carbon layers. Taking advantage of both the optimized Ru-TiO/TiO2 interaction and the conductive carbon coating layers, the Ru-TiO/TiO2@NC exhibits both exceptional HOR/HER activity and superior stability, outperforming Pt/C in the alkaline solution. The HOR mass activity reaches up to 107.2 A gRu-1 at an overpotential of 50 mV, and the specific exchange current density is 0.271 mA cm−2. The HER overpotential at 10 mA cm−2 is only 39 mV, 34 mV lower than required by Pt/C. More importantly, the Ru-based catalyst exhibits excellent anti-oxidation ability by virtue of the unique sandwich structure. Density functional theory calculations discover that the d-band center of Ru in Ru-TiO/TiO2 is downshifted by 0.29 eV compared to Ru-TiO2, decoupling and optimizing the Had/OHad adsorption on Ru, i.e., Had is promoted, while OHad is inhibited and transferred to TiO/TiO2. As a result, (i) the energy required by the potential determining step of HOR/HER is lowered, and (ii) the anti-oxidation ability of the Ru-TiO/TiO2 is enhanced. This work not only addresses the issue of Ru passivation at high anode potentials but also provides an innovative and versatile approach to designing advanced electrocatalysts.

Photophysical Characterization of Ru Nanoclusters on Nanostructured TiO2 by Time-Resolved Photoluminescence Spectroscopy.

Despite the promising performance of Ru nanoparticles or nanoclusters on nanostructured TiO2 in photocatalytic and photothermal reactions, a mechanistic understanding of the photophysics is limited. The aim of this study is to uncover the nature of light-induced processes in Ru/TiO2 and the role of UV versus visible excitation by time-resolved photoluminescence (PL) spectroscopy. The PL at a 267 nm excitation is predominantly due to TiO2, with a minor contribution of the Ru nanoclusters. Relative to TiO2, the PL of Ru/TiO2 following a 267 nm excitation is significantly blue-shifted, and the bathochromic shift with time is smaller. We show by global analysis of the spectrotemporal PL behavior that for both TiO2 and Ru/TiO2 the bathochromic shift with time is likely caused by the diffusion of electrons from the TiO2 bulk toward the surface. During this directional motion, electrons may recombine (non)radiatively with relatively immobile hole polarons, causing the PL spectrum to red-shift with time following excitation. The blue-shifted PL spectra and smaller bathochromic shift with time for Ru/TiO2 relative to TiO2 indicate surface PL quenching, likely due to charge transfer from the TiO2 surface into the Ru nanoclusters. When deposited on SiO2 and excited at 532 nm, Ru shows a strong emission. The PL of Ru when deposited on TiO2 is completely quenched, demonstrating interfacial charge separation following photoexcitation of the Ru nanoclusters with a close to unity quantum yield. The nature of the charge-transfer phenomena is discussed, and the obtained insights indicate that Ru nanoclusters should be deposited on semiconducting supports to enable highly effective photo(thermal)catalysis.

Highly Dispersed Ru Nanoclusters Anchored on Hexagonal Boron Nitride for Efficient and Stable Hydrogenation of Aromatic Amines to Alicyclic Amines

Highly Dispersed Ru Nanoclusters Anchored on Hexagonal Boron Nitride for Efficient and Stable Hydrogenation of Aromatic Amines to Alicyclic Amines

Synergistic Ru/CeO2 heterostructure for alkaline hydrogen oxidation with high activity and CO tolerance

The lack of highly efficient and stable electrocatalysts for anodic hydrogen oxidation reaction (HOR) has limited the large-scale industrial application of alkaline exchange membrane fuel cell. In this work, a Pt-free Ru/CeO2 heterostructure electrocatalyst with outstanding catalytic activity and stability for alkaline HOR is developed. The synthesized Ru/CeO2 with synergistic heterogeneous interface exhibits a high kinetic current density reaching 21.7 mA cm−2 at an overportentail of 50 mV, which is nearly 11-fold higher than that of the contrastive Ru/C catalyst and almost the same as that of commercial Pt/C catalyst. Importantly, this electrocatalyst also shows high CO resistance that Pt/C catalyst lacks. Electrochemical results and spectral studies show that CeO2 not only efficiently adjusts the electronic microenvironment of Ru site to promote Had adsorption, but also provides the adsorption sites for OHad at a low potential. As a result, the introduced CeO2 synergistically promotes hydrogen oxidation, H2O formation and CO removing, thereby enhancing the HOR performance of Ru nanoclusters.

Unique Ru nanoclusters confined in carbon molecular sieve coatings with tailoring sub-4 Å ultramicropores as a highly efficient and CO-tolerant hydrogen oxidation electrocatalyst

Developing highly efficient and CO-tolerant hydrogen oxidation electrocatalysts is crucial for anion exchange membrane fuel cells (AEMFC). In this work, a unique carbon molecular sieve (CMS) coating strategy is demonstrated for Ru nanoclusters, featuring strongly size sieving ultramicropores, which act as a highly efficient and CO-tolerant hydrogen electrocatalyst in alkaline conditions. The CMS coating thickness and pore size could be regulated by low-temperature carbonization of polydopamine which was beforehand in-situ polymerized over the Ru nanoclusters. It is demonstrated that dominant sub-4 Å ultramicropores in Ru@NC/C-400 are beneficial for H2/CO separation. Taking advantage of such a physical sieving barrier, along with the electronic modulation of Ru by the carbon coating layer, the CO adsorption over the Ru surface is suppressed and meanwhile, the hydrogen/oxygen species adsorption energy is optimized. The Ru@NC/C-400 catalyst exhibits exceptional HOR activity with a specific activity of 0.30 mA cm-2Ru and a mass activity of 0.25 A mg−1Ru, which are 3-folds and 1.7-folds of the counterpart Pt/C catalyst, respectively. More importantly, the catalyst is highly tolerant to CO. In the presence of 100 ppm CO, the HOR current with the Ru@NC/C-400 catalyst lowers by just 9.5%, but the Pt/C catalyst drops by 33.3% in the chronoamperometry test. This work highlights the tremendous potential of the encapsulating approach in refreshing catalyst performances via rationally engineering the encapsulating layer structures.

Selective electroreduction of nitrate wastewater to ammonia fertilizer via highly dispersed ruthenium nanocluster catalyst

Electrochemical reduction of nitrate (NO3-) wastewater to ammonia (NH3) offers a promising but challenging approach for wastewater treatment of nitrate pollutants and resource recovery of ammonia fertilizer. However, the low catalytic activities and selective efficiency have limited their development and application. Herein, we report a facile chemical reduction method for the successful preparation of Ru nanoclusters (NCs) on ultrathin MoO2 nanosheet substrates (Ru NCs/MoO2 NSs). The Ru NCs/MoO2 NSs electrocatalyst exhibits superior activity and selectivity for NO3- electroreduction to NH3, with an NH3 yield rate of 50.9 mg·h−1·g−1cat. at − 0.4 V and a faradaic efficiency of 83.5 % at − 0.3 V versus reversible hydrogen electrode. Operando electrochemical impedance spectroscopy further indicates the faster reaction kinetics of the Ru SCs/MoO2 NSs at the electrode-electrolyte interfaces compared with MoO2 NSs. In situ spectroscopic studies and on-line differential electrochemical mass spectrometry reveal the proposed reaction pathway for the conversion of NO3- to NH3, namely, deoxygenation reactions *NO3-→*NO2-→*NO and hydrogenation steps *NO→*NOH→*NH2OH→*NH3. Density functional theory calculations further verify the effective N-end NOH pathway with the conversion of *NO to *NOH as the rate-determining step requiring a low energy barrier of 0.44 eV, which is lower than that of the O-end ONH pathway (1.17 eV).

L-cysteine-protected ruthenium nanoclusters on CdS as efficient and reusable photocatalysts for hydrogen production

Nanocluster-modified semiconductor-based photocatalysts have been identified as a vital area of research in the area of photocatalytic hydrogen evolution from water. However, the existing ligand protection strategy for synthesizing ultrasmall metal nanoclusters remains confined to a few metals, including Au, Ag, Cu, and their alloys. In this investigation, we describe a facile solution-phase reduction synthesis method for the production of L-cysteine-protected Ru nanoclusters. Our findings demonstrate that these novel Ru nanoclusters function as cocatalysts, which notably increase the photocatalytic activity and photostability of CdS photocatalysts. Moreover, the hybrid CdS photocatalyst modified with Ru nanoclusters exhibits superior activity and stability relative to photoinduced Ru nanoparticles/CdS composite photocatalysts. The simplicity of the synthesized metal nanocluster cocatalyst and its effectiveness in enhancing photocatalyst activity, while reducing the use of precious metals, present new avenues for the development of advanced photocatalysts.

Ultrauniform Ru Nanoclusters as Efficient Hydrogenation Catalysts for Phthalates

Cyclohexane dicarboxylic acid (CHDA) ester, a kind of environmental-friendly plasticizer, can be produced by phthalates hydrogenation. However, the synthesis of catalysts with high activity and selectivity is a challenge due to the stability of aromatic rings. In this work, a series of ultrauniform Ru nanoclusters supported by γ-Al2O3 are synthesized for the hydrogenation of diisononyl phthalate (DINP). Results show that the conversion of DINP and the selectivity of diisononyl-cyclohexane-1,2-dicarboxylate (DINCH) both reach 100% at 140 °C and 3 MPa H2 pressure. Diisononyl-cyclohexene-1,2-dicarboxylate (4H-DINP) and 1,2-cyclohexanedicarboxylate-7-methyloctyl ester are found; the hydrogenation reaction network of DINP is constructed. Alkali metal ions adsorbed on the surface of Ru nanoclusters prepared by the polyol method can stabilize Ru3+-Hδ− species by electrostatic interaction, thus affecting the hydrogenation activity of the catalyst, following the order of Li+ > Na+ > K+ > Cs+. Ru-based catalysts prepared by the polyol method have good prospects for application in phthalates hydrogenation.

Boosting Polyethylene Hydrogenolysis Performance of Ru-CeO2 Catalysts by Finely Regulating the Ru Sizes.

Hydrogenolysis is an effective method for converting polyolefins into high-value chemicals. For the supported catalysts commonly used, the size of active metals is of great importance. In this study, it is discovered that the activity of CeO2 -supported Ru single atom, nanocluster, and nanoparticle catalysts shows a volcanic trend in low-density polyethylene (LDPE) hydrogenolysis. Compared with CeO2 supported Ru single atoms and nanoparticles, CeO2 -supported Ru nanoclusters possess the highest conversion efficiency, as well as the best selectivity toward liquid alkanes. Through comprehensive investigations, the metal-support interactions (MSI) and hydrogen spillover effect are revealed as the two key factors in the reaction. On the one hand, the MSI is strongly related to the Ru surface states and the more electronegative Ru centers are beneficial to the activation of CH and CC bonds. On the other hand, the hydrogen spillover capability directly affects the affinity of catalysts and active H atoms, and increasing this affinity is advantageous to the hydrogenation of alkane species. Decreasing the Ru sizes can promote the MSI, but it can also reduce the hydrogen spillover effect. Therefore, only when the two effects achieve a balance, as is the case in CeO2 -supported Ru nanoclusters, can the hydrogenolysis activity be promoted to the optimal value.

Size-Defined Ru Nanoclusters Supported by TiO2 Nanotubes Enable Low-Concentration Nitrate Electroreduction to Ammonia with Suppressed Hydrogen Evolution.

Anthropogenic nitrate pollution has an adverse impact on the environment and human health. As part of a sustainable nitrate management strategy, electrochemical denitrification is studied as an innovative strategy for nutrients recycling and recovering. It is, however, challenging to selectively electro-reduce nitrate with low-concentration for ammonia. Herein, the photo-deposition of size-defined Ru nanoclusters (NCs, average size: ≈1.66nm) on TiO2 nanotubes (NTs) is demonstrated, which show improved performance for nitrate-to-ammonia electroreduction with a maximum yield rate of ≈600µgh-1 cm-2 and a faradic efficiency (FE) of > 90.0% across a broad range of potentials in comparison with electrodeposited Ru nanoparticles (NPs, average size: ≈23.78nm) on TiO2 NTs. Experimental and theoretical evidence further suggests the small-size Ru NCs with the intrinsically enhanced selectivity and activity because of the strong metal/substrate interaction and unsaturated coordination state. The findings highlight the size effect on Ru-based catalyst supported on metal oxides, a versatile catalytic model, which allows the regulation of hydrogen adsorption to favor ammonia production over the competing hydrogen evolution reaction.

Highly Stable and Efficient Oxygen Evolution Electrocatalyst Based on Co Oxides Decorated with Ultrafine Ru Nanoclusters.

Exploring highly active and durable electrocatalysts for oxygen evolution reaction (OER) is significant to achieve efficient anion exchange membrane (AEM) water electrolysis. Herein, hollow Co-based N-doped porous carbon spheres decorated with ultrafine Ru nanoclusters (HS-RuCo/NC) are reported as efficient OER electrocatalysts via the pyrolysis of carboxylate-terminated polystyrene-templated bimetallic zeolite imidazolate frameworks accommodating Ru (III) ions. The unique hollow structure with hierarchically porous characteristics contributes to the electrolyte penetration for fast mass transport and the exposure of more metal sites. Theoretical and experimental studies reveal the synergistic effect between the in situ formed RuO2 and Co3 O4 as another critical factor for the high OER performance, where the coupling of RuO2 with Co3 O4 can optimize the electronic configuration of RuO2 /Co3 O4 heterostructure and decrease the energy barrier during OER. Meanwhile, the presence of Co3 O4 can efficiently suppress the over-oxidation of RuO2 , endowing the catalysts with high stability. As expected, when the resultant HS-RuCo/NCwas integrated into an AEM water electrolyzer, the obtained electrolyzer exhibits a cell voltage of 2.07 V to launch the current density of 1 A cm-2 and excellent long-term stability at 500 mA cm-2 under room temperature in alkaline solution, outperforming the commercial RuO2 -based AEM water electrolyzer (2.19 V).

Ruthenium nanoclusters modified by zinc species towards enhanced electrochemical hydrogen evolution reaction.

Ruthenium (Ru) has been considered a promising electrocatalyst for electrochemical hydrogen evolution reaction (HER) while its performance is limited due to the problems of particle aggregation and competitive adsorption of the reaction intermediates. Herein, we reported the synthesis of a zinc (Zn) modified Ru nanocluster electrocatalyst anchored on multiwalled carbon nanotubes (Ru-Zn/MWCNTs). The Ru-Zn catalysts were found to be highly dispersed on the MWCNTs substrate. Moreover, the Ru-Zn/MWCNTs exhibited low overpotentials of 26 and 119mV for achieving current intensities of 10 and 100mA cm-2 under alkaline conditions, respectively, surpassing Ru/MWCNTs with the same Ru loading and the commercial 5wt% Pt/C (47 and 270mV). Moreover, the Ru-Zn/MWCNTs showed greatly enhanced stability compared to Ru/MWCNTs with no significant decay after 10,000 cycles of CV sweeps and long-term operation for 90h. The incorporation of Zn species was found to modify the electronic structure of the Ru active species and thus modulate the adsorption energy of the Had and OHad intermediates, which could be the main reason for the enhanced HER performance. This study provides a strategy to develop efficient and stable electrocatalysts towards the clean energy conversion field.

Ru nanoclusters coupling with hierarchical phosphorus and oxygen dual-doped carbon nanotube architectures for effective hydrogen evolution reaction

The construction of an effective catalyst for hydrogen evolution reaction (HER) is a top priority. Herein, we demonstrate ruthenium (Ru) nanoclusters coupled with phosphorus and oxygen dual-doped carbon nanotube (CNT) architecture (Ru-POCA). The increased hydrophilicity and negatively charged surface of CNTs can strongly trap Ru ions. The hierarchical structure is favorable of providing abundant pathways and exposing more active sites for HER. Due to the synergistic effect of the hierarchical structure and modified surface chemistry, Ru-POCA exhibits excellent catalytic HER activity. The overpotential is 22 and 40 mV with a Tafel slope of 28.0 and 27.1 mV dec−1 in 1 M KOH and 0.5 M H2SO4 at 10 mA cm−2. Moreover, Ru-POCA processes good catalytic stability in both acidic and alkaline electrolytes, while the boosted catalytic HER activity is fundamentally studied by density functional theory calculation. This work provides a rational approach to constructing hierarchically structured Ru-CNTs-based catalysts for hydrogen evolution reaction.

Inducing electronic asymmetricity on Ru clusters to boost key reaction steps in basic hydrogen evolution

Modulating electronic asymmetricity of catalysts is a novel option to regulate the electrocatalytic performance. Nevertheless, the efficient regulation of asymmetric degree of heterostructured catalysts at the atomic level still remains challenging. Herein, Ru nanoclusters (NCs, average particle size of ∼ 1.3 nm) were anchored on carbon materials doped by controllable N functional groups to optimize the electronic asymmetricity toward efficient hydrogen evolution reaction (HER). The electronic interaction between Ru and N species, and hence, the asymmetric electronic distribution of Ru NCs is subjectively manipulated by precisely tailoring the type of N dopants, especially pyrrolic-N, of carbon substrates. As a result, the pyrrolic-N dominated Ru-based heterostructures exhibit excellent HER activity compared to most of the current Ru-based electrocatalysts in basic media. Multiple spectroscopy experiments and density functional theory simulations demonstrate that the asymmetric distribution of surface electron of Ru-based heterostructures not only accelerates H2O adsorption and dissociation at interfacial Ru sites with positive charge but also facilitates the adsorption behavior of hydrogen on surface Ru sites with negative charge, thereby simultaneously optimizing the elementary steps in basic HER process. The present findings would provide some crucial understanding in manipulating the local electronic asymmetricity toward reasonable design and fabrication of advanced catalysts and beyond.