Metal-support Interaction Effect Research Articles

In-situ carbon integration on atomically dispersed platinum metal oxide nanocomposites for hydrogen evolution reaction

In this study, a novel in-situ carbon growth technique by a modified sol gel synthesis method is presented. The carbon support developed on a transition metal oxide composite transforms the electronic conductivity and is engineered for hydrogen evolution reaction by a dispersion of unit atomic concentration of platinum. Through two different synthesis techniques, platinum dispersion is implemented on the metal oxide-carbon system, one by direct sol-gel technique and another by chemical reduction technique, whereby a homogeneous dispersion of the noble metal on the composite is achieved. Carbon-based cerium oxide and titanium oxide composites are used as the base material, and one atomic percentage of platinum metal is ensured while synthesizing each of the carbon composites. The functionality of these catalysts towards hydrogen evolution reaction in a 0.5 M H2SO4 acidic media revealed the synthesis technique's uniqueness and the effect of metal support interaction that plays a vital role in the electrocatalytic activity. The intrinsic activity of the titania system, along with enhanced metal support interaction due to highly enriched platinum availability on the surface of the substrate, provides for strong electrochemical activity. The titanium oxide carbon composite with platinum dispersed by hydrazine reduction exhibited the finest activity with an overpotential of just 44 mV at j = 10 mA/cm2 and a tafel slope of 118 mV/dec. The gas chromatographic analysis on platinum supported titania catalyst showcased better performance by a margin of four times than the commercial three weight percentage platinum supported carbon.

Deciphering promotion of MoP over MoC in Pt catalysts for methanol-assisted water splitting reaction

Molybdenum-based compounds show promising promotion effects on Pt catalysts for energy-relevant catalysis reactions. Herein, a more effective promotion effect of MoP than MoC was found in assisting Pt nanoparticles for methanol-assisted hydrogen generation in light of the strong metal-support interaction and synergistic effect between Pt and MoP/C nanospheres. Electrochemical analyses and theoretical calculations demonstrated that Pt-MoP/C facilitated the oxidation and removal of CO intermediates more effectively than Pt-MoC/C. This enhanced performance was attributed to the distinct 6-coordination environment of hexagonal MoP and the elevated electron density of Mo induced by phosphorus. These structural and electronic features significantly enhanced electron transfer to Pt, thereby creating strong metal-support interaction and synergistic effect to improve the overall catalytic efficiency. Especially, the unique activities of Moδ+ and Moδ- in the MoP modified the surface structure of Pt, lowered the Pt d-band center, and optimized the local chemical state of Pt atoms, which resulted in more optimized adsorption energy and charge transfer capabilities of intermediates. The Pt-MoP/C electrolyzer thus showed both lower cell voltage than that of Pt-MoC/C and Pt/C electrolyzers in water splitting and methanol-assisted water splitting for hydrogen generation. This study offers insightful information about the promotion effect of molybdenum-based compounds in Pt catalyst systems in energy-relevant catalysis reactions.

Direct quantitative assessment of single-atom metal sites supported on powder catalysts

Rational design of effective catalyst demands a profound understanding of active-site structures. Single-atom supported powder catalysts, depicting unique features like enhanced metal dispersion, hold promise in different applications. Here, we present an approach to directly quantify the detailed structural nature of metal sites in single-atom, high surface area, powder catalysts. By combining advanced high-resolution scanning-transmission electron microscopy, deep learning and density functional theory calculations, we determine, with statistical significance, the exact location and coordination environment of Pd single-atoms supported on MgO nanoplates. Our findings reveal a preferential interaction of Pd single-atoms with cationic vacancies (V-centers), followed by occupation of anionic defects on the {001} MgO surface. The former interaction results in stabilization of PdO species within V-centers, while partially embedded Pd states are found in F-defects. This methodology opens a route to the ultimate structural analysis of metal-support interaction effects, key in the design of advanced nanocatalysts for sustainable and energy-efficient processes.

CO2 hydrogenation to methanol over Cu-CeO2-ZrO2 catalysts: The significant effect of metal-support interaction

CO2 hydrogenation to methanol is an important pathway to achieving carbon neutrality, with metal-support interaction (MSI) being crucial in the design and optimization of catalysts for this process. In this study, Cu-CeO2-ZrO2 catalysts (CuCe + Zr, CuZr + Ce, CeZr + Cu, and CuCeZr) with different interactions between metal Cu and supports were successfully prepared. We mainly address the problem that how the MSI affects the catalytic performance. The CuCeZr prepared by one step solid-phase method shows the optimal catalytic activity and stability for CO2 hydrogenation, even better than the benchmark commercial Cu-ZnO-Al2O3 catalyst for syngas to methanol. Based on the investigation of the structure-performance relationship of catalysts, we propose that the excellent catalytic activity of CuCeZr is mainly determined by its largest surface area of metallic Cu (SCu) and the most amount of Cu species at Cu-support interface, both resulting from the strongest MSI between metallic Cu and CeO2-ZrO2 support. Furthermore, in situ DRIFTS showed that the strong SMI in CuCeZr promotes the formation of formate and its rapid transfer to methoxy, thereby efficiently producing methanol. This work reveals the intrinsic active sites of Cu-CeO2-ZrO2 catalysts from a MSI perspective, providing useful insights for researchers to design highly efficient Cu-based catalysts.

Hydrogen activation by rhodium under the cover of a copper oxide thin film

The activation of reactants by catalytically active metal sites at metal-oxide interfaces is important for understanding the effect of metal-support interactions on nanoparticle catalysts and for tuning activity and selectivity. Using a combined experimental and theoretical approach, we studied the activation of H2 and the effect of CO poisoning on isolated Rh atoms completely or partially covered by a copper oxide (Cu2O) thin film. Temperature-programmed desorption (TPD) experiments conducted in ultra-high vacuum (UHV) show that neither a partially nor a fully oxidized Cu2O layer grown on a Rh/Cu(111) single-atom alloy can activate hydrogen in UHV. However, in situ ambient pressure X-ray photoelectron spectroscopy (AP-XPS) experiments performed at elevated H2 pressures reveal that Rh significantly accelerates the reduction of these Cu2O thin films by hydrogen. Remarkably, the fastest reduction rate is observed for the fully oxidized sample with all Rh sites covered by Cu2O. Both TPD and AP-XPS data demonstrate that these covered Rh sites are inaccessible to CO, indicating that Rh under Cu2O is active for H2 dissociation but cannot be poisoned by CO. In contrast, an incomplete oxide film leaves some of the Rh sites exposed and accessible to CO, and hence prone to CO poisoning. Density functional theory calculations demonstrate that unlike many reactions in which hydrogen activation is rate limiting, the rate-determining step in the dissociation of H2 on thin-film Cu2O with Rh underneath is the adsorption of H2 on the buried Rh site, and once adsorbed, the dissociation of H2 is barrierless. These calculations also explain why H2 can only be activated at higher pressures. Together, these results highlight how different the reactivity of atomically dispersed Rh in Cu can be depending on its accessibility through the oxide layer, providing a way to engineer Rh sites that are active for hydrogen activation but resilient to CO poisoning.

Efficient hydrogen production from formic acid dehydrogenation over ultrasmall PdIr nanoparticles on amine-functionalized yolk-shell mesoporous silica

Developing heterogeneous catalysts with exceptional catalytic activity over formic acid (HCOOH, FA) dehydrogenation is imperative to employ FA as an effective hydrogen (H2) carrier. In this work, ultrasmall (1.4 nm) and well-dispersed PdIr nanoparticles (NPs) immobilized on amine-functionalized yolk-shell mesoporous silica nanospheres (YSMSNs) with radially oriented mesoporous channels have been synthesized by a co-reduction strategy. The optimized catalyst Pd4Ir1/YSMSNs-NH2 (Pd/Ir molar ratio = 4:1) exhibited a remarkable turnover frequency (TOF) of 5818 h−1 and remarkable stability at 50 °C with the addition of sodium formate (SF), resulting in complete FA conversion and H2 selectivity, exceeding most of the solid heterogeneous catalysts in previous reports under similar circumstances. Kinetic isotope effect (KIE) exploration indicates the cleavage of the CH bond is regarded as the rate-determining step (RDS) during the FA dehydrogenation process. Such excellent catalytic properties arise from the ultrafine and well-dispersed PdIr NPs supported on the nanosphere support YSMSNs-NH2, the electronic synergistic effect of PdIr alloy NPs, and the strong metal-support interaction (MSI) effect between the introduced PdIr NPs and YSMSNs-NH2 support. This work offers a new paradigm for exploiting the highly effective silica-supported Pd-based heterogeneous catalysts over the dehydrogenation of FA.

Constructing ultralow-loading Cu single atoms/Fe2O3 particles on Nb2C MXenes for efficient utilization of atomic H to boost electrochemical debromination

Bromate is a commonly identified carcinogenic and genotoxic disinfection byproduct in water. Electrochemical debromination is an environmentally friendly and effective approach but it often suffers the limited reducing atomic H (H*) ability and high metal catalyst dosage. In this study, a unique composite catalyst comprised of ultra-low loading Cu single atoms (0.016 wt%) and Fe2O3 nanoparticles supported on a Nb2C MXene (denoted as Cu0.2/Fe0.1/Nb2C) was synthesized by one-step high-temperature molten salt method. The Cu0.2/Fe0.1/Nb2C significantly outperformed the Nb2C, Cu0.2/Nb2C and Fe0.1/Nb2C counterparts in the electrochemical debromination with a 94.2 % removal efficiency of bromate. It is revealed that the introducing of Cu single atoms, efficiently promotes the adsorption of H* and inhibition of competitive H2 evolution. The incorporation of Fe2O3 nanoparticles significantly increased the electronic metal-support interaction effect between the metal components and Nb2C, thereby forming a noticeable electronic cloud bridge to facilitate efficient charge transfer. Ultimately, the synergistic interplay between Cu single atoms and Fe2O3 nanoparticles plays a crucial role in achieving the remarkable removal performance of bromate. This work not only presents a significant instance of a synergistic catalyst involving metal single atoms and metal nanoparticles for effective electrochemical debromination but also advances the understanding of the electronic metal-support interaction.

Electronic interaction and band alignment between Cu sub-nanometric clusters and ZnIn2S4 nanosheets towards selective photoreduction of CO2 to CO

Engineering the electronic properties of heterogeneous photocatalysts with charge transfer regulated is an effective strategy to boost their CO2 reduction activity. Here, we drew inspiration from the strong metal-support interaction effect, and fabricated ZnIn2S4 supported-Cu sub-nanometric clusters photocatalyst. Within this catalyst, the formed CuS bond would redistribute interfacial charge, resulting in diverse chemical states of Cu atoms and the establishment of Ohmic contact between ZIS and Cu. The built-in electric field of such Ohmic contact benefited the migration of photoexcited electrons from ZIS to Cu. Further mechanistic studies unveiled the crucial role of positively charged Cu atom near the interface in facilitating H2O dissociation, and its adjacent Cu atom at the top-surface adopting a distinct chemical state could activate linear CO2 molecule into a bent configuration. These features substantially lowered energy barriers for CO2 adsorption and subsequent *COOH formation, and Cu-ZIS, accordingly, exhibited a remarkable CO production rate of 60.2 μmol g-1h−1, approximately 20.8-fold enhancement compared to ZIS counterpart.

Enhanced coke resistant Ni/SiO2@SiO2 core–shell nanostructured catalysts for dry reforming of methane: Effect of metal-support interaction and SiO2 shell

Suppressing coke formation on nickel-based catalysts used in methane-dry reforming is one of the most important issues. We investigate the effect of nickel metal-support interaction and outer porous silica shells on the coke formation in methane dry reforming over Ni/SiO2@SiO2 core–shell catalysts. Using a simple ammonia evaporation method, the Ni/SiO2_AE catalyst, which has highly dispersed nickel nanoparticles with ca. 7 nm, was synthesized and coated with an outer porous silica shell to produce a Ni/SiO2_AE/SiO2 core shell catalyst. Based on the TEM and N2 isotherm results, a 20 nm thick SiO2 shell having pores with a size of about 2 nm was uniformly coated on the Ni/SiO2_AE catalyst. H2-TPR, and XPS analysis results suggest that the Ni/SiO2_AE and Ni/SiO2_AE@SiO2 catalysts have high nickel dispersion. This high dispersion is due to strong metal-support interactions and the formation of Ni phyllosilicate species. On the other hand, the ones synthesized by wet impregnation method have low nickel dispersion due to weaker metal-support interactions. The Ni/SiO2_AE@SiO2 core–shell catalyst showed stable catalytic activity under methane dry reforming conditions at 600 °C. On the other hand, the Ni/SiO2_WI and Ni/SiO2_AE catalysts showed rapid deactivation due to severe coke formation. It can be concluded that the strong metal-support interaction and the silica shell can suppress catalyst deactivation caused by coke formation very effectively.

Catalytic Oxidation of Toluene over Pt/CeO2 Catalysts: A Double-Edged Sword Effect of Strong Metal-Support Interaction.

Strong metal-support interaction (SMSI), which has drawn widespread attention in heterogeneous catalysis, is thought to significantly affect the catalytic performance for volatile organic chemical (VOC) abatement. In the present study, strong interactions between platinum and ceria are constructed by modulating the oxygen vacancy concentration of CeO2 through a NaBH4 reduction method. For a catalyst with higher content of oxygen vacancy, more electrons would transfer from ceria to Pt, which is attributed to the stronger effect of SMSI. The obtained electron-richer Pt sites exhibit higher ability for toluene activation, contributing to better performance for toluene oxidation. On the other hand, the stronger metal-support interaction would facilitate CeOx species migrating to the Pt nanoparticle surface and forming an encapsulated structure. Smaller Pt dispersion leads to fewer sites for toluene adsorption and activation, which is to the disadvantage of the reaction. Therefore, taking the negative and positive effects together, the Pt/CeO2-0.5 catalyst has the highest catalytic performance for toluene abatement. Our study provides new insights into strong metal-support interaction on toluene oxidation and contributes to designing noble metal catalysts for VOC abatement.

Crystal Facet Controlled Metal-Support Interaction in Uricase Mimics for Highly Efficient Hyperuricemia Treatment.

The effect of strong metal-support interaction (SMSI) has never been systematically studied in the field of nanozyme-based catalysis before. Herein, by coupling two different Pd crystal facets with MnO2, i.e., (100) by Pd cube (Pdc) and (111) by Pd icosahedron (Pdi), we observed the reconstruction of Pd atomic structure within the Pd-MnO2 interface, with the reconstructed Pdc (100) facet more disordered than Pdi (111), verifying the existence of SMSI in such coupled system. The rearranged Pd atoms in the interface resulted in enhanced uricase-like catalytic activity, with Pdc@MnO2 demonstrating the best catalytic performance. Theoretical calculations suggested that a more disordered Pd interface led to stronger interactions with intermediates during the uricolytic process. In vitro cell experiments and in vivo therapy results demonstrated excellent biocompatibility, therapeutic effect, and biosafety for their potential hyperuricemia treatment. Our work provides a brand-new perspective for the design of highly efficient uricase-mimic catalysts.

Modulation effect of support on active metals in the Fe-Ni based catalysts: Insight into the electronic metal-support interaction (EMSI) effect in the CO-SCR reaction

Supported catalysts have been extensively investigated and implemented in the industry due to their cost-effectiveness and promising catalytic performance. However, due to the general inert nature of the support itself, its role in the catalyst performance is often neglected and therefore not well understood despite the consideration of the physical properties of the support. This study applies the concept of electronic metal-support interaction (EMSI) to explore the impact of various supports on the active metals in Fe-Ni-based catalysts for the CO-selective catalytic reduction reaction. Through density functional theory calculations and several advanced characterizations, it can be confirmed that the EMSI effect can modify the valence states of active metals and foster interaction between different active metals, thereby influencing the reactant adsorption and catalyst performance greatly. These findings highlight the significant impact of the support on the chemical states of active metals, having far-reaching implications for designing and optimizing the supported industrial catalysts.

Ni-Co alloy supported on CeO2 by SiO2 encapsulation for dry reforming of methane

Dry reforming of methane (DRM) is a highly endothermic reaction that needs harsh condition of high temperature for syngas production, which is challenged by developing catalysts with properties of anti-sintering and low carbon deposition. This work synthesized confined catalysts of (Co-Ni/CeO2)@SiO2 for DRM reaction. The catalysts possessed multifunction including size and alloy effects, metal-support interaction and confinement effect, which contributed to high rates of CH4 and CO2, marginal sintering of NiCo alloy and trace carbon deposition. The (3Ni-3Co/CeO2)@SiO2 catalyst reached rates as high as 4.74 mmol/(gNi·s) and 5.57 mmol/(gNi·s) for CH4 and CO2, respectively, at 1023 K. The rates were keeping stable for at least 36 h on stream. The characterizations of used samples revealed the limited size change of NiCo alloy and the low carbon deposition. The work provides valuable guidance for developing stable catalysts for DRM and other high temperature reactions.

CO2 Conversion via Low-Temperature RWGS Enabled by Multicomponent Catalysts: Could Transition Metals Outperform Pt?

AbstractIn the context of CO2 valorisation, the reverse water–gas shift reaction (RWGS) is gathering momentum since it represents a direct route for CO2 reduction to CO. The endothermic nature of the reaction posses a challenge when it comes to process energy demand making necessary the design of effective low-temperature RWGS catalysts. Herein, multicomponent Cs-promoted Cu, Ni and Pt catalysts supported on TiO2 have been studied in the low-temperature RWGS. Cs resulted an efficient promoter affecting the redox properties of the different catalysts and favouring a strong metal-support interaction effect thus modulating the catalytic behaviour of the different systems. Positive impact of Cs is shown over the different catalysts and overall, it greatly benefits CO selectivity. For instance, Cs incorporation over Ni/TiO2 catalysts increased CO selectivity from 0 to almost 50%. Pt-based catalysts present the best activity/selectivity balance although CuCs/TiO2 catalyst present comparable catalytic activity to Pt-studied systems reaching commendable activity and CO selectivity levels, being an economically appealing alternative for this process.

Experimental and theoretical unraveling of the electrocatalytic hydrodechlorination of chlorinated phenol using Pd promoted by oxygen vacancies in TiO2 array

The electrocatalytic dichlorination (EHDC) shows a promising potential to degrade chlorinated phenols (CPs). It is also a green technology in reducing the corresponding hazardous impact on the environment. In this study, we constructed a catalytic structure which was Pd on a TiO2 array with oxygen vacancies on carbon fibre paper substrate (Pd/TiO2/CFP) by a relatively mild route. Due to the presence of the oxygen vacancies, the resulting strong metal-support interaction (SMSI) effect has been identified which featured a redistribution of spatial charge in Pd/TiO2. The electron flow from the oxygen vacancies in the TiO2 to Pd facilitated the adsorption of Pd with 4-chlorophenol (4-CP) and endowed the Pd metal with an improved chemical reaction kinetics even at a low Pd loading. Experimentally, we studied the dependence of pH, concentration of 4-CP, and working potential on the reaction conditions of EHDC. The results showed that the conversion of 4-CP reached 100 % within 180 min with an apparent rate constant of 2.9 × 10-2 min−1 and the dominant product was phenol (P). The multi-cycle test illustrated that the Pd/TiO2/CFP electrode showed superior stability. The results also revealed that the comprehensive catalytic behavior was much better than those of the Pd/CFP and the TiO2/CFP electrodes. The density function theory (DFT) calculations indicated that 4-CP was more preferably absorbed on Pd/TiO2/CFP than Pd/CFP due to the SMSI assistance. This study provides a valuable guide in the preparation of precious metal-based electrodes for EHDC with a reduced loading and cost but without performance compromise.

Research progress of metal oxide supports for fuel cells electrocatalysts

AbstractFuel cell technology, as a new way of energy conversion, is widely used in various fields. At present, the electrocatalyst, as one of the key components of the electrochemical reaction of fuel cells, still suffers from the problems of high cost, low activity and poor stability. Excellent fuel cell electrocatalysts must have excellent catalytic activity, anti‐poisoning ability, electrical conductivity and stability. Metal oxides with corrosion resistance, electrochemical stability and strong metal support interaction effects have been intensively studied. The influence of the synthesis method on the catalytic performance is also crucial. In this review, the importance of fuel cells and their catalysts is introduced. The characteristics of catalysts with three metal oxides, titanium dioxide, cerium dioxide and tungsten oxide, as supports, preparation methods and applications in different fuel cells are reviewed. The synthesis of metal oxide supported catalysts by impregnation, precipitation and hydrothermal methods is described. Finally, the research on metal oxide supported catalysts is prospected.

Which is better for converting furfural into furfuryl alcohol: The strong metal-support interaction effect or the formation of alloy?

Furfural, one of biomass raw materials, can be seen as a clean alternative energy to fossil energy. Cu-based catalysts have been studied mostly due to the excellent selectivity to furfuryl alcohol. While keeping the stability of Cu-based catalysts under high temperature is still a challenge. Thus, a more active and stable Ni-based catalyst is researched. While the high yield of furfuryl alcohol was difficult to obtained over Ni catalysts. A catalyst (5 % Ni/Ce0.9Sn0.1O2) that combines stability and selectivity was prepared with enhanced activity which was different with the NiSn alloy. Combined with the characterizations of XRD, XPS, TEM, CO-TPD and H2-TPR, it has been proven that the enhanced strong interaction between Ni and Ce0.9Sn0.1O2 is much more effective in forming furfuryl alcohol than the effect of the Ni3Sn4 alloy.

TiO2 Nanolayer–Coated Carbon as Pt Support for Enhanced Methanol Oxidation Reaction

Abstract To facilitate the large-scale application of direct methanol fuel cells (DMFCs), the issue of low Pt/C durability due to Pt degradation and carbon corrosion in harsh DMFC operating conditions must be addressed. A promising strategy is to hybridize metal oxides with carbon materials, resulting in a durable and conductive support that exhibits a strong metal-support interaction (SMSI) effect on platinum nanoparticles (Pt NPs). In this study, we introduced a TiO2 coating on carbon black, creating a TiO2 nanolayer between Pt and carbon black. The nanolayer not only protects the carbon black but also activates the SMSI effect on Pt. The resulting Pt/C@TiO2 electrocatalyst exhibits superior durability than commercial Pt/C. After the accelerated durability test, the mass activity loss of the methanol oxidation reaction (MOR) of Pt/C@TiO2 (32%) is significantly lower than that of Pt/C (46.8%). Moreover, the MOR activity of Pt/C@TiO2 is higher than Pt/C as well. It suggests that Pt/C@TiO2 shows great potential as a highly durable and active electrocatalyst for DMFCs.

Regulating electronic metal-support interaction (EMSI) via pore-confinement to enhance non-thermal plasma catalytic oxidation of toluene

The non-thermal plasma catalysis holds great promise for VOCs removal, and the development of catalysts with electronic metal-support interaction (EMSI) effect is beneficial for VOCs removal. In this study, we prepared three Mn@M catalysts with EMSI coordination structures by encapsulating MnOx particles within the mesoporous molecular sieve (MCM-41) with different pore size (2.9 nm, 4.4 nm, and 7.9 nm), and investigated the effect of pore size on EMSI and non-thermal plasma catalytic performance of Mn@M for toluene. Among three catalysts, Mn@M2 with an average pore size of 4.38 nm exhibited the strongest EMSI and superior redox capabilities, thus demonstrating the highest mineralization rate, carbon balance, and CO2 selectivity for plasma catalytic oxidation of toluene. The EMSI effect leads to the formation of electron-rich and electron-poor centers on the Si-O-Mn-O bond, facilitating the generation of reactive oxygen species and enhancing the oxygen cycle. In addition, the reaction degradation pathway was investigated using in situ DRIFTS and GC–MS. This study provides valuable insights for designing highly effective supported catalysts by pore confinement to degrade VOCs in adsorption-plasma catalysis system.

Facile synthesis of surface oxygen vacancy and Ti3+ defects in SrTiO3 perovskite coupled g-C3N4 decorated with Au ternary nanocomposites for enhancing electrocatalytic activity from acidic and natural seawater conditions

The development of efficient electrocatalysts became vital to resolving the ongoing clean energy crises and environmental issues, wherein high-performance catalysts for the improved electrocatalytic hydrogen evolution reaction (EHER) are demanded. To meet this goal, an advanced and green ultrasonic-assisted pulsed laser ablation in liquid technique was used to prepare surface oxygen vacancy and Ti3+ defects in perovskite-based ternary nanocomposites (PTNCs) decorated with Au@SrTiO3/g-C3N4. An effective cathode was designed using Au@SrTiO3/g–C3N4–decorated PTNCs for EHER that operated in an acidic media of 0.5 M H2SO4. The optimized Au@SrTiO3/g-C3N4 PTNCs revealed an improved EHER at a very low over-potential of 0.082 V at a cathodic current density (J) of −10 mA/cm2, high double-layer capacitance (679.8 μF/cm2), large electrochemical surface area (19.4 cm2), high mass activity (198.35 A/g), high specific activity (2.91 mA/cm2), high surface charge density (0.0404 C/cm2), high catalytic active sites (4.19 × 10−7 mol/cm2), and exceptional long-term stability at 50 h, respectively. The Tafel slope of 45.36 mV/dec confirmed the presence of the Volmer-Heyrovsky mechanism to explain the enhanced EHER cycle of the prepared PTNCs. The improved electrocatalytic EHER performance was attributed to the induced synergistic strong metal-support interaction (SMSI) effect of the surface oxygen vacancy and Ti3+ defects in PTNCs that increased electrochemical surface area, high exposure of abundant active sites, improved intrinsic kinetics, and fast charge transport, respectively. Moreover, Au@SrTiO3/g–C3N4–decorated PTNCs exhibit excellent natural seawater electrolysis in terms of EHER at a low over-potential of 0.300 V at a J = −10 mA/cm2 and long-term stability at 10 h, respectively. It is demonstrated that the proposed novel surface oxygen vacancy and Ti3+ defects in Au@SrTiO3/g-C3N4 PTNCs are effective electrocatalysts can be beneficial for producing hydrogen from green technologies in future energy applications via interface engineering.