High-performance Hydrogen Evolution Reaction Research Articles

Plasma-assisted highly dispersed Pt single atoms on Ru nanoclusters electrocatalyst for pH-universal hydrogen evolution

Exploring highly active and stable electrocatalyst using trace noble metals for hydrogen evolution reaction (HER) is urgently needed but still challenging. Here, atomically dispersed Pt on ultrafine Ru nanoclusters (∼1.46 nm) loaded by the commercial acetylene black (Acet) support is fabricated by a facile one-step cold-plasma technique. The Pt single atoms on Ru nanoclusters electrocatalyst (Pt0.47-Ru/Acet) with 0.47 wt% content of Pt exhibit an excellent HER activity in all pH, achieving ultralow overpotential of only 17, 28, and 8 mV at 10 mA·cm−2 in 1 M KOH, 0.5 M H2SO4, and 1 M PBS, respectively. And the mass activity of Pt0.47-Ru/Acet catalyst in alkaline is about 5.54 and 2.15 times that of commercial Ru/C and Pt/C catalyst at an overpotential of 100 mV, respectively. Meanwhile, after 8000 CV cycles, there is barely performance decrease for Pt0.47-Ru/Acet, displaying good stability. DFT calculation reveals that the Pt single atoms could effectively regulate the electronic structure of Ru clusters, and reduce the energy barriers of water dissociation (Volmer step) as well as subsequent hydrogen evolution (Heyrovsky step), thus enhancing the alkaline HER performance effectively. This work provides an effective approach to designing a high-performance HER electrocatalyst with the atomic-dimension Pt surface modification.

In-situ porous flake heterostructured NiCoP/Ni foam as electrocatalyst for hydrogen evolution reaction

It is critical to produce highly efficient, inexpensive and long-term durability non-noble metal catalysts for hydrogen production by water electrolysis on basis of renewable energy. In this study, the porous flake heterostructured NiCoP grown directly on porous networked Ni foam (NiCoP/NF) was obtained by the hydrothermal and phosphating method. As electrocatalysts for hydrogen evolution reaction (HER), the impact of Ni/Co ratios on NiCoP/NF catalytic performance was studied in 1.0 M KOH. Electrochemical measurement results display that the HER catalytic activity of NiCoP/NF increased first and then decreased with the decrease of Ni in the Ni/Co ratio. The NiCoP/NF1–3 catalyst (Ni/Co = 1:3) exhibited the highest performance for HER. A low overpotential of 99 mV at 10 mA cm−2 was achieved with the Tafel slope of 65.4 mV dec−1. In addition, porous flake heterostructured NiCoP/NF1–3 showed a good stability in alkaline condition, which maintained 20 h for stable water electrolysis at 10 mA cm−2. This present study will pave the way for the porous flake architecture development with high-performance HER in alkaline water electrolysis.

MOF-derived NiSe2 nanoparticles grown on carbon fiber as a binder-free and efficient catalyst for hydrogen evolution reaction

It is challenging to grow inexpensive cathode material with superior catalytic properties for hydrogen evolution reaction (HER). Metal-organic frameworks (MOFs) have emerged as powerful platforms to synthesize efficient and ultrastable catalysts for hydrogen production. In this research, NiSe2 nanoparticles were derived from Ni-based MOF, which grown in situ on carbon fiber (NiSe2/C/CF) through pyrolysis and selenization processes. NiSe2/C/CF displays a higher HER performance than that of Ni/C/CF and Ni-MOF-74/CF. Notably, the NiSe2/C/CF electrode gives a low overpotential of 209 mV, a Tafel slope of 74.1 mV/dec, and outstanding stability with slight decay after operating for 12 h. The high HER catalytic activity of NiSe2/C/CF is mainly ascribed to the emerging effects of NiSe2 nanoparticles and three-dimensional conductive substrate CF, facilitating active moieties exposure and electron transfer during the electrocatalytic process. Therefore, this work illustrates a novel approach for the preparation of transition metal chalcogenides as low-cost and stable catalysts for HER.

An insight to catalytic synergic effect of Pd-MoS2 nanorods for highly efficient hydrogen evolution reaction

The electrocatalytic hydrogen evolution reaction (HER) is a sustainable energy production route using green chemistry. Transition metal dichalcogenides' application in catalytic hydrogen production is limited due to a lack of solutions that simultaneously address intrinsic activity, increased surface area, electrical conductivity, and stability problems. Herein we address these issues simultaneously by modifying the electronic structure of molybdenum disulfide (MoS2) nanorods using a low content of Pd (1 wt% and 2 wt%) dopant via a facile colloidal solvothermal route. The resulting MoS2 nanorods doped with (1 and 2 wt%) palladium demonstrate current density of 100 mA/cm2 at quit lower over-potentials of 137 mV and 119 mV than 273 mV for pure MoS2 nanorods, accompanied by high stability. This research proposes a strategy for designing high-performance HER electrocatalysts that work in acidic medium. In addition, the Tafel slop calculated for MoS2 is 112 mV/dec whereas for 1 and 2 wt% Pd-MoS2, the Tafel slopes are 70 mV/dec and 46 mV/dec.

Capture and recycling of toxic selenite anions by cobalt-based metal-organic-frameworks for electrocatalytic overall water splitting

A nanosheet-like cobalt-based metal-organic-framework (Co-MOF) is employed to uptake SeO32− anions, and the remove capacity of Co-MOF reaches a record of 280.0 mg g−1. After uptake SeO32− by Co-MOF, the recycling defect-rich CoSeO4 (R-CoSeO4) is used as an electrocatalyst for oxygen evolution reaction (OER), which displays an overpotential of 265 mV at 10 mA cm−2 in 1 M KOH. Furthermore, cobalt-cobalt selenide heterojunction nanoparticle (Co-Co0.85Se), a high-performance hydrogen evolution reaction (HER) electrocatalyst (overpotential of 97 mV at 10 mA cm−2 in 1 M KOH) is obtained by one-step calcining of R-CoSeO4. Series experiments and density functional theory calculations confirm the anion vacancy in R-CoSeO4 and heterojunction in Co-Co0.85Se can improve the OER and HER activity, respectively. Finally, two binder-free electrodes (R-CoSeO4/CC and Co-Co0.85Se/CC) are employed as anode and cathode, respectively, to construct a water electrolysis cell, which only needs 1.47 V to achieve 10 mA cm−2 in 1 M KOH.

Ni3Mo3N coupled with nitrogen-rich carbon microspheres as an efficient hydrogen evolution reaction catalyst and electrochemical sensor for H2O2 detection

Hydrogen evolution reaction (HER) and electrochemical analysis are two important fields of electrochemical research at present. We found that both HER and some electrochemical analytical reactions relied on the concentration of hydrogen ions (H+) in solution, so we intended to develop an electrode material that is sensitive to H+ and can be used for both HER and some electrochemical analyses. In this work, we synthesized Ni3Mo3N coupled with nitrogen-rich carbon microspheres (Ni3Mo3[email protected] MSs) as highly efficient electrode material for HER and detection of Hydrogen peroxide (H2O2), which plays an important role in physiological processes. Here the aniline was used as the nitrogen and carbon sources to synthesize Ni3Mo3[email protected] The Ni3Mo3[email protected] MSs showed high performance for HER in 1 M KOH solution with a small overpotential of 51 mV at 10 mA cm−2 and superior stability. For H2O2 detection, a detection limit of 1 μM (S/N = 3), sensitivity of 120.3 μA·mM−1 cm−2 and linear range of 5 μM–40 mM can be achieved, respectively. This work will open up a low-cost and easy avenue to synthesize transition metal nitrides coupled with N-doped carbon as bifunctional electrode material for HER and electrochemical detection.

Encapsulation of Fe-CoP with P, N-co-doped porous carbon matrix as a multifunctional catalyst for wide electrochemical applications

Hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR) serve as the most promising electrochemical processes for renewable energy. Developing multifunctional electrocatalysts with high performance for HER, OER and ORR still remains a challenge. Herein, we report a facile method to prepare P, N-co-doped porous carbon encapsulated Fe-CoP (A-Fe-CoP/CPN) electrocatalyst through freeze drying, carbonization, and KOH activation. The acquired A-Fe-CoP/CPN possesses abundant pores with large surface area, which provides sufficient defect-rich sites for HER, OER, and ORR, in alkaline or acidic electrolytes. The A-Fe-CoP/CPN shows low overpotential and good stability for HER and OER in alkaline electrolyte. Density functional theory (DFT) computations reveal that the addition of Fe greatly facilitates the rate-determining step and overall catalytic pathway for both HER and OER. A-Fe-CoP/CPN also exhibits low half-wave potential (E1/2) for ORR, which indicates an enhanced performance than that of the noble Pt/C catalyst. Zn-air battery equipped with the A-Fe-CoP/CPN catalyst exhibits a high energy density (849 mAh g−1) and a long-time stability at 5 mA cm−2. This finding not only offers a facile strategy to prepare porous carbon materials with defect-rich sites, but also provides guidance for developing multifunctional electrocatalysts for wide electrochemical reactions.

Universal low-temperature oxidative thermal redispersion strategy for green and sustainable fabrication of oxygen-rich carbons anchored metal nanoparticles for hydrogen evolution reactions

A simple and green low-temperature oxidative thermal redispersion strategy was developed for obtaining well-distributed Rh, Ru, Ir NPs on oxygen-rich mesoporous carbon with considerable activity toward hydrogen evolution compared with the counterpart without any pre-treatment. • Universal low-temperature oxidative thermal redispersion strategy was developed. • The strategy benefits for well-defined metal NPs anchored on oxygenated carbons. • As-formed AC was a universal carrier for selected Pt group metal (Ru, Rh, Ir) NPs. • Rh/C-300A-350H had the highest HER activity for AB hydrolysis and water splitting. • The small Rh NPs with electron-rich sites contributed to the high HER performance. Supported metal nanoparticles (MNPs) have shown great promise in catalytic hydrogen evolutions because of the highly efficient utilization of metal atoms, while the low binding strength between MNPs and supports results in the agglomeration of MNPs into larger particles, considerably decreasing the catalytic efficiency. Herein, we smartly develop a universal, green, and sustainable low-temperature oxidative thermal redispersion strategy to fabricate metal oxide precursors and subsequently well dispersing and stabilizing MNPs (M = Rh, Ru, Ir) over oxygenated carbons (Mesoporous carbon, Ketjen black, and Vulcan carbon), which can be utilized as efficient catalysts for hydrogen production from ammonia borane (AB) hydrolysis and hydrogen evolution reaction (HER). Such flexible modulation strategy enables the formation of oxidized metal species on oxygenated carbons, which is the key to synthesize ultrasmall MNPs against sintering and agglomeration during the reduction process. Attributing to the innately structural/componential/surficial superiorities, the optimal Rh/C-300A-350H exhibits the highest catalytic activity toward hydrogen evolution from AB hydrolysis and HER with turnover frequencies of 3308/5040 min −1 in aqueous/basic solutions and an overpotential of 29 mV at 10 mA cm −2 in 1.0 M KOH, respectively. With the similar activation mechanism for dissociation of O–H bond in H 2 O, the highly dispersed Rh NPs with ultrafine sizes and electronic metal-support interaction are responsible for the excellent catalytic activity toward the hydrogen evolution reactions. This study presents an extremely facile and sustainable modulation strategy for increasing the adhesion of MNP catalysts on oxygenated carbons for catalytic applications.

Boosting Electrocatalytic Activity of Ru for Acidic Hydrogen Evolution through Hydrogen Spillover Strategy

Pristine Ru generally shows unsatisfying activity for the electrocatalytic hydrogen evolution reaction (HER). How to activate its HER activity through facile methodologies is very challenging. Recently, metal-supported electrocatalysts integrating metals with efficient hydrogen adsorption and supports with facile hydrogen desorption delivered a high HER performance through a metal-to-support hydrogen spillover process, where the small metal–support work function difference (ΔΦ) was identified as the criterion for the successful interfacial hydrogen spillover. Herein, we demonstrate that a hydrogen spillover strategy significantly boosts the HER activity of Ru by depositing a Ru1Fe1 alloy on CoP (Ru1Fe1/CoP) with a small ΔΦ of 0.05 eV. Experimentally, Ru1Fe1/CoP (0.7 wt % Ru loading) delivered a high Ru utilization activity of 139.8 A/mgRu and a long-term durability in acid. Mechanism investigations authenticated that the small ΔΦ guaranteed the interfacial hydrogen spillover from Ru1Fe1 with efficient hydrogen adsorption to CoP with facile hydrogen desorption and thereafter boosted the HER activity of Ru.

Interface engineered hollow Co3O4@CoNi2S4 nanostructure for high efficiency supercapacitor and hydrogen evolution

Constructing interface is an efficient strategy to develop high-performance nanomaterials for energy storage and conversion. By adopting the combined strategies of interface engineering and constructing specific nanostructures, we fabricated a bifunctional hollow Co3O4@CoNi2S4 core-shell with dual interfaces for high-performance hybrid supercapacitor (HSC) and hydrogen evolution reaction (HER). The free-standing Co3O4 nanotube@nanosheets core was first obtained by calcinating ZIF-67 nanorods with homojunction interface on carbon cloth (CC) and then combined with the CoNi2S4 shell to improve the conductivity, as confirmed by first-principle calculations. The synthesized Co3O4@CoNi2S4-20/CC with surface holes and hollow cores exhibits a capacity of 1079 C g−1 (i.e., 299.7 mA h g−1, capacitance of 1798 F g−1) at 1 A g−1 and remains 841 C g−1 at 10 A g−1. The Co3O4@CoNi2S4-20/CC//AC HSC delivers an excellent energy density of 58.1 Wh kg−1 at the power density of 799.9 W kg−1 and excellent cycle stability. Additionally, the fabricated Co3O4@CoNi2S4-20/CC requires an overpotential of 185 mV at 10 mA cm−2 in 1 M KOH for HER. This work shed a light on the rational design of bifunctional electrodes for high-performance supercapacitor and HER.

Computation-guided design and preparation of durable and efficient WC-Mo2C heterojunction for hydrogen evolution reaction

Molybdenum and tungsten carbides (Mo 2 C and WC) are promising catalysts for hydrogen evolution reaction (HER), but their electrocatalytic activities are still inferior to theoretical predictions. Herein, density functional theory (DFT) calculations imply that WC-Mo 2 C heterostructure may exert a high HER performance since the hybridization of WC and Mo 2 C can optimize the proton adsorption energy and energy barrier for water dissociation. To test this predication, we prepare the WC-Mo 2 C heterostructure on a flexible carbon cloth (CC). The obtained WC-Mo 2 C@CC exhibits notable HER activity ( η10 = 122 mV; η500 = 309 mV) and stability (continuous 100 h at 500 mA cm −2 ) in alkaline media. Furthermore, a solar-panel-driven electrolyzer, including the WC-Mo 2 C@CC cathode and a NiFe-LDH@Ni f anode, operates at 10 mA cm −2 with a cell voltage of 1.51 V in 10 M KOH at 70°C, demonstrating its potential for practical applications. Overall, this work offers an atomic-level insight into designing advanced carbide HER electrocatalysts. • WC-Mo 2 C heterostructures are prepared by one-step co-deposition • WC-Mo 2 C show competitive alkaline catalytic HER performance • The optimized ΔG H∗ and super hydrophilic nature account for its good HER activity • A water electrolyzer driven by solar energy is operated at industrial conditions WC-Mo 2 C heterostructures are prepared by one-step co-deposition in KF-B 2 O 3 -Na 2 WO 4 -Na 2 MoO 4 molten salts by Liu et al. The WC-Mo 2 C heterostructures show a high HER performance owing to the optimized ΔG H∗ and low energy barrier for water spitting.

NiMo@C3N5 heterostructures with multiple electronic transmission channels for highly efficient hydrogen evolution from alkaline electrolytes and seawater

Designing highly efficient and stable electrocatalysts for hydrogen evolution reaction (HER), particularly in seawater, still remains a challenging task. Herein, the unique heterostructures composed of 1D NiMo cores and 2D C3N5 shells (NiMo@C3N5) are rationally designed and demonstrated as the robust HER catalysts in both alkaline electrolytes and natural seawater, where the carbon-based shell can effectively protect the catalyst core from seawater poisoning. Based on the experimental investigation and density functional theory calculation, multiple electronic transmission channels were found to establish at the interface between NiMo cores and C3N5 shells, thus providing efficiently optimized HER pathways to achieve minimized overpotential with a reduced energy barrier of the rate-determining step. More importantly, the NiMo@C3N5 hybrids exhibit stable HER performance with a high Faradaic efficiency of 94.8% in seawater, which is superior to that of commercial Pt/C. All these results can evidently highlight a feasible strategy to develop high-performance HER electrocatalysts via interface engineering.

Anderson-Type Polyoxometalate-Assisted Synthesis of Defect-Rich Doped 1T/2H-MoSe2 Nanosheets for Efficient Seawater Splitting and Mg/Seawater Batteries.

Designing high-performance hydrogen evolution reaction (HER) catalysts is crucial for seawater splitting. Herein, we demonstrate a facile Anderson-type polyoxometalate-assisted synthesis route to prepare defect-rich doped 1T/2H-MoSe2 nanosheets. As demonstrated, the optimized defect-rich doped 1T/2H-MoSe2 nanosheets display low overpotentials of 116 and 274 mV to gain 10 mA cm-2 in acidic and simulated seawater for the HER, respectively. A magnesium (Mg)/seawater battery was fabricated with the defect-rich doped 1T/2H-MoSe2 nanosheet cathode, displaying the highest power density of up to 7.69 mW cm-2 and stable galvanostatic discharging over 24 h. The theoretical and experimental investigations show that the superior HER and battery performances of the heteroatom-doped MoSe2 nanosheets are attributed to both the improved intrinsic catalytic activity (effective activation of water and favorable subsequent hydrogen desorption) and the abundant active sites, benefiting from the favorable catalytic factors of the doped heteroatom, 1T phase, and defects. Our work presents an intriguing structural modulation strategy to design high-performance catalysts toward both HER and Mg/seawater batteries.

Enhancing the electrochemical hydrogen evolution of CoP3/CoMoP nanosheets through the support of black TiO2−x nanotube arrays

The hydrogen evolution reaction (HER) is a crucial part of renewable energy application. It is still a huge challenge to enhance the intrinsically catalytic performance of non-noble metal-based electrocatalysts. Transition metal phosphides (TMPs) have been recognized as the effective HER catalysts. However, TMPs nanosheets suffer from low activity for water dissociation, which prohibits the HER properties of electrocatalyst in alkaline solution. Herein, a structure that decorates CoP3/CoMoP nanosheets on the black TiO2−x nanotube arrays substrate has been designed. The oxygen vacancy in the black TiO2−x substrate is expected to play an important role in the water dissociation and therefore enhance the initial Volmer step during HER. What’s more, the nanotube structure of black TiO2−x substrate provides a larger surface area for CoP3/CoMoP nano sheets decoration, the number of active sites enhanced during the reaction, resulting in higher HER performance. Experimental results demonstrate that CoP3/CoMoP/TiO2−x@Ti possesses much improved HER properties with a low overpotential of 143 mV at 10 mA−2 and a Tafel slope of 61 mV dec−1, it also provides long-term durability without significant degradation for 48 h. This work develops a low-cost and valuable approach to enhance the HER activity of transition metal phosphides in alkaline electrolytes.

Excellent Electrocatalytic Hydrogen Evolution Reaction Performances of Partially Graphitized Activated-Carbon Nanobundles Derived from Biomass Human Hair Wastes.

Carbonaceous materials play a vital role as an appropriate catalyst for electrocatalytic hydrogen production. Aiming at realizing the highly efficient hydrogen evolution reaction (HER), the partially graphitized activated-carbon nanobundles were synthesized as a high-performance HER electrocatalyst by using biomass human hair ashes through the high-temperature KOH activation at two different temperatures of 600 and 700 °C. Due to the partial graphitization, the 700 °C KOH-activated partially graphitized activated-carbon nanobundles exhibited higher electrical conductivity as well as higher textural porosity than those of the amorphous activated-carbon nanobundles that had been prepared by the KOH activation at 600 °C. As a consequence, the 700 °C-activated partially graphitized activated-carbon nanobundles showed the extraordinarily high HER activity with the very low overpotential (≈16 mV at 10 mA/cm2 in 0.5 M H2SO4) and the small Tafel slope (≈51 mV/dec). These results suggest that the human hair-derived partially graphitized activated-carbon nanobundles can be effectively utilized as a high-performance HER electrocatalyst in future hydrogen-energy technology.

Restructured Co‐Ru alloys via electrodeposition for efficient hydrogen production in proton exchange membrane water electrolyzers

The design of robust and high-performance hydrogen evolution reaction (HER) catalysts is crucial for the scalable production of hydrogen by electrochemical water splitting. In this work, we fabricated hierarchically porous Co-Ru catalysts with excellent catalytic activity and durability in acidic media. The morphology of the Co-Ru catalysts was successfully controlled through an optimized electrochemical process. Among all Co-Ru samples prepared in this study, the Co72Ru28 catalyst exhibited the largest catalytic surface area, as well as excellent HER activity (overpotential of 26.4 mV at −10 mA cm−2) and durability. X-ray photoelectron spectroscopy measurements revealed the electron transfer between Co and Ru, indicating that the formation of the Co-Ru alloy improved the activity and durability of the catalyst. Furthermore, a proton exchange membrane water electrolyzer (PEMWE) prepared with the Co72Ru28 sample showed excellent performances (3.4 A cm−2 at 2.0 Vcell), illustrating the promising potential of the present Co-Ru catalysts as cathode materials for PEMWE systems.

Edge terminated and interlayer expanded pristine MoS2 nanostructures with 1T on 2H phase, for enhanced hydrogen evolution reaction

Pristine molybdenum disulfide (MoS 2 ) nanostructures with 1T on 2H phase have been prepared by tuning the growth time in hydrothermal synthesis. The optimized sample has an expanded interlayer and it exhibits striking kinetic metrics with an onset potential of - 0.13 V, Tafel slope of 49 mV/decade, and an exchange current density of 3.98 × 10 −3 mA, performing best among the pristine MoS 2 based hydrogen evolution reaction (HER) catalysts reported so far. The edge terminated structure, together with the expanded interlayer, is believed to modify the electronic structure to enhance the conductivity of the compound. The Mott-Schottky analysis of the optimized sample indicated a decrease in band bending and an enhancement in the charge transfer. The promising HER response obtained with sufficiently low growth time and growth temperature for the pristine MoS 2 nanostructures suggests a potential way to design high-performance HER catalysts based on the compound. • Fabricated edge terminated, interlayer expanded 1T on 2H MoS 2 nanostructures. • 1T phase with HER active (001) plane obtained without the addition of any dopant. • Optimized sample has lower onset potential of −0.13 V and Tafel slope of 49 mV/dec. • High exchange current density of 3.98 × 10 −3 mA for the optimized sample. • Durable HER catalyst with high stability using MoS 2 nanostructures.

Electrospun nano-Ir anchored mesoporous carbon nanofibers for hydrogen evolution reaction

It is essential to develop high-performance hydrogen evolution reaction catalysts. Reducing the amount of precious metals is an effective approach to replace Pt-based catalyst. Here, an electrocatalyst of metallic iridium anchored on mesoporous carbon nanofibers (Ir- m CNFs) is reported. After optimized the nanostructure (pore-forming agent content) of Ir- m CNFs, at the current density of 10 mA cm −2 , the overpotential reaches 28 and 39 mV in alkaline and acid medium. Moreover, the content of Ir in this catalyst is just around 6 wt%. In conclusion, this paper reports an effective precious metal based HER catalysts with a lower amount of rare metals.

Photocatalytic reduction of water to hydrogen by CuPbSbS3 nanoflakes

The photocatalyst is a key component of efficient photocatalytic hydrogen evolution (PHE) via water splitting. Bournonite CuPbSbS3 has a great application potential in solar-to-energy due to its tremendous semiconductor properties and earth-abundant components. Although CuPbSbS3 has achieved the highest power conversion efficiency (PCE) of 2.65% in thin-film photovoltaics, its application in PHE via water splitting has been rarely studied. In this work, CuPbSbS3 nanoflakes with dominate (002) facet is fabricated by a facile butyldithiocarbamate acid (BDCA) solution process, which exhibits a PHE rate of 250.8 μmol g−1/h without any co-catalyst under simulated solar irradiation. Density functional theory calculations show that plentiful catalytic sites with low ΔGH∗ are responsible for the high hydrogen evolution reaction performance of CuPbSbS3. This study represents an effective approach to realize photovoltaic-to-photocatalyst hydrogen evolution of Cu-based quaternary chalcogenides.

Regulation of hydrogen evolution performance of titanium oxide–carbon composites at high current density with a Ti–O hybrid orbital

AbstractRational design and controllable synthesis of practical electrodes with high stability and activity at high current density for a hydrogen evolution reaction (HER) are critical for renewable and sustainable energy conversion. However, high‐performance TiO2‐based electrocatalysts for HER are quite limited, and the catalytic active centers still remain elusive. Herein, a simple strategy is demonstrated for the synthesis of TiO2–carbon composite (TiO2/C) with high HER performance and stability. The remarkable HER performance of TiO2/C can be ascribed to the doping of carbon atoms, which leads to stronger hybridization of Ti 3d and O 2p orbitals, thus substantially improving the electrocatalytic efficiency. This study elucidates that the hydrogen evolution activity of oxide electrocatalysts can be largely improved by regulating their electronic structures by doping carbon atoms and also provides an effective strategy for designing heterostructured electrocatalysts with high catalytic activity and stability at high current density for HER.