Coupling Interface Constructions of MoS2/Fe5Ni4S8 Heterostructures for Efficient Electrochemical Water Splitting

Water splitting is considered as a pollution‐free and efficient solution to produce hydrogen energy. Low‐cost and efficient electrocatalysts for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) are needed. Recently, chemical vapor deposition is used as an effective approach to gain high‐quality MoS₂ nanosheets (NSs), which possess excellent performance for water splitting comparable to platinum. Herein, MoS₂ NSs grown vertically on FeNi substrates are obtained with in situ growth of Fe₅Ni₄S₈ (FNS) at the interface during the synthesis of MoS₂. The synthesized MoS₂/FNS/FeNi foam exhibits only 120 mV at 10 mA cm^?2 for HER and exceptionally low overpotential of 204 mV to attain the same current density for OER. Density functional theory calculations further reveal that the constructed coupling interface between MoS₂ and FNS facilitates the absorption of H atoms and OH groups, consequently enhancing the performances of HER and OER. Such impressive performances herald that the unique structure provides an approach for designing advanced electrocatalysts.     

In Situ Porousized MoS2 Nano Islands Enhance HER/OER Bifunctional Electrocatalysis

2D molybdenum disulfide (MoS₂) is developed as a potential alternative non-precious metal electrocatalyst for energy conversion. It is well known that 2D MoS₂ has three main phases 2H, 1T, and 1T′. However, the most stable 2H-phase shows poor electrocatalysis in its basal plane, compared with its edge sites. In this work, a facile one-step hydrothermal-driven in situ porousizing of MoS₂ into self-supporting nano islands to maximally expose the edges of MoS₂ grains for efficient utilization of the active stable sites at the edges of MoS₂ is reported. The results show that such active, aggregation-free nano islands greatly enhance MoS₂'s hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) bifunctional electrocatalytic activities. At a low overpotential of 248 and 300 mV, the porous MoS₂ nano islands can generate a current density of 10 mA cm⁻² in HER and OER, which is much better than typical nanosheet morphology. Surprisingly, the porous MoS₂ nano islands even exhibit better performance than the current commercial RuO₂ catalyst in OER. This discovery will be another effective strategy to promote robust 2H-phase, instead of 1T/1T′-phase, MoS₂ to achieve efficient endurable bifunctional HER/OER, which is expected to further replace precious metal catalysts in industry.     

Ruthenium Nanoparticles on Cobalt‐Doped 1T′ Phase MoS2 Nanosheets for Overall Water Splitting

2D MoS₂ nanostructures have recently attracted considerable attention because of their outstanding electrocatalytic properties. The synthesis of unique Co–Ru–MoS₂ hybrid nanosheets with excellent catalytic activity toward overall water splitting in alkaline solution is reported. 1T′ phase MoS₂ nanosheets are doped homogeneously with Co atoms and decorated with Ru nanoparticles. The catalytic performance of hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is characterized by low overpotentials of 52 and 308 mV at 10 mA cm^?2 and Tafel slopes of 55 and 50 mV decade^?1 in 1.0 m KOH, respectively. Analysis of X‐ray photoelectron and absorption spectra of the catalysts show that the MoS₂ well retained its metallic 1T′ phase, which guarantees good electrical conductivity during the reaction. The Gibbs free energy calculation for the reaction pathway in alkaline electrolyte confirms that the Ru nanoparticles on the Co‐doped MoS₂ greatly enhance the HER activity. Water adsorption and dissociation take place favorably on the Ru, and the doped Co further catalyzes HER by making the reaction intermediates more favorable. The high OER performance is attributed to the catalytically active RuO₂ nanoparticles that are produced via oxidation of Ru nanoparticles.     

Highly Robust Non‐Noble Alkaline Hydrogen‐Evolving Electrocatalyst from Se‐Doped Molybdenum Disulfide Particles on Interwoven CoSe2 Nanowire Arrays

Developing efficient non‐noble and earth‐abundant hydrogen‐evolving electrocatalysts is highly desirable for improving the energy efficiency of water splitting in base. Molybdenum disulfide (MoS₂) is a promising candidate, but its catalytic activity is kinetically retarded in alkaline media due to the unfavorable water adsorption and dissociation feature. A heterogeneous electrocatalyst is reported that is constructed by selenium‐doped MoS₂ (Se‐MoS₂) particles on 3D interwoven cobalt diselenide (CoSe₂) nanowire arrays that drives the hydrogen evolution reaction (HER) with fast reaction kinetics in base. The resultant Se‐MoS₂/CoSe₂ hybrid exhibits an outstanding catalytic HER performance with extremely low overpotentials of 30 and 93 mV at 10 and 100 mA cm^–2 in base, respectively, which outperforms most of the inexpensive alkaline HER catalysts, and is among the best alkaline catalytic activity reported so far. Moreover, this hybrid catalyst shows exceptional catalytic performance with very low overpotentials of 84 and 95 mV at 10 mA cm^–2 in acidic and neutral electrolytes, respectively, implying robust pH universality of this hybrid catalyst. This work may provide new inspirations for the development of high‐performance MoS₂‐based HER electrocatalysts in unfavorable basic media for promising catalytic applications.     

Facile synthesis of Co-CoO<Subscript>x</Subscript>/N-doped carbon nanotubes hybrids as efficient and bifunctional catalysts for hydrogen and oxygen evolution

Developing low-cost, efficient, and bifunctional electrocatalysts for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is an attractive yet challenging task. Herein, we report a novel, simple and one-pot method to fabricate ultrafinely dispersed Co-CoO_x nanoparticles encapsulated in a nitrogen doped carbon nanotubes (denoted as Co-CoO_x/CN) via an efficient thermal condensation of d-glucosamine hydrochloride, melamine and Co(NO₃)₂·H₂O. A well-designed Co-CoO_x based hybrid that possesses high activity and excellent durability for the OER and HER in alkaline solution has been fabricated. The catalyst displays good stability for 30,000 s and small Tafel slope of 82 mV per decade for OER and 110 mV per decade for HER. Detailed electrochemical and physical studies indicate that the high OER and HER activity of the hybrid catalyst arises from the strong interaction between Co-based NPs and N-doped carbon nanotubes, and especially the synergistic effect of Co and cobalt oxide.     

Zirconium‐Regulation‐Induced Bifunctionality in 3D Cobalt–Iron Oxide Nanosheets for Overall Water Splitting

The design of high‐efficiency non‐noble bifunctional electrocatalysts for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is paramount for water splitting technologies and associated renewable energy systems. Spinel‐structured oxides with rich redox properties can serve as alternative low‐cost OER electrocatalysts but with poor HER performance. Here, zirconium regulation in 3D CoFe₂O₄ (CoFeZr oxides) nanosheets on nickel foam, as a novel strategy inducing bifunctionality toward OER and HER for overall water splitting, is reported. It is found that the incorporation of Zr into CoFe₂O₄ can tune the nanosheet morphology and electronic structure around the Co and Fe sites for optimizing adsorption energies, thus effectively enhancing the intrinsic activity of active sites. The as‐synthesized 3D CoFeZr oxide nanosheet exhibits high OER activity with small overpotential, low Tafel slope, and good stability. Moreover, it shows unprecedented HER activity with a small overpotential of 104 mV at 10 mA cm^?2 in alkaline media, which is better than ever reported counterparts. When employing the CoFeZr oxides nanosheets as both anode and cathode catalysts for overall water splitting, a current density of 10 mA cm^?2 is achieved at the cell voltage of 1.63 V in 1.0 m KOH.     

Structure Engineering of MoS2 via Simultaneous Oxygen and Phosphorus Incorporation for Improved Hydrogen Evolution

Oxygen and phosphorus dual‐doped MoS₂ nanosheets (O,P‐MoS₂) with porous structure and continuous conductive network are fabricated using a one‐pot NaH₂PO₂‐assisted hydrothermal approach. By simply changing the precursor solution, the chemical composition and resulting structure can be effectively controlled to obtain desired properties toward the hydrogen evolution reaction (HER). Thanks to the beneficial structure and strong synergistic effects between the incorporated oxygen and phosphorus, the optimal O,P‐MoS₂ exhibit superior electrocatalytic performances compared with those of oxygen single‐doped MoS₂ nanosheets (O‐MoS₂). Specifically, a low HER onset overpotential of 150 mV with a small Tafel slope of 53 mV dec^?1, excellent conductivity, and long‐term durability are achieved by the structural engineering of MoS₂ via O and P co‐doping, making it an efficient HER electrocatalyst for water electrocatalysis. This work provides an alternative strategy to manipulate transition metal dichalcogenides as advanced materials for electrocatalytic and related energy applications.     

Nickel@Nitrogen‐Doped Carbon@MoS2 Nanosheets: An Efficient Electrocatalyst for Hydrogen Evolution Reaction

Developing cheap, abundant, and easily available electrocatalysts to drive the hydrogen evolution reaction (HER) at small overpotentials is an urgent demand of hydrogen production from water splitting. Molybdenum disulfide (MoS₂) based composites have emerged as competitive electrocatalysts for HER in recent years. Herein, nickel@nitrogen‐doped carbon@MoS₂ nanosheets (Ni@NC@MoS₂) hybrid sub‐microspheres are presented as HER catalyst. MoS₂ nanosheets with expanded interlayer spacings are vertically grown on nickel@nitrogen‐doped carbon (Ni@NC) substrate to form Ni@NC@MoS₂ hierarchical sub‐microspheres by a simple hydrothermal process. The formed Ni@NC@MoS₂ composites display excellent electrocatalytic activity for HER with an onset overpotential of 18 mV, a low overpotential of 82 mV at 10 mA cm^?2, a small Tafel slope of 47.5 mV dec^?1, and high durability in 0.5 H₂SO₄ solution. The outstanding HER performance of the Ni@NC@MoS₂ catalyst can be ascribed to the synergistic effect of dense catalytic sites on MoS₂ nanosheets with exposed edges and expanded interlayer spacings, and the rapid electron transfer from Ni@NC substrate to MoS₂ nanosheets. The excellent Ni@NC@MoS₂ electrocatalyst promises potential application in practical hydrogen production, and the strategy reported here can also be extended to grow MoS₂ on other nitrogen‐doped carbon encapsulated metal species for various applications.     

Transition‐Metal‐Doped RuIr Bifunctional Nanocrystals for Overall Water Splitting in Acidic Environments

The establishment of electrocatalysts with bifunctionality for efficient oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in acidic environments is necessary for the development of proton exchange membrane (PEM) water electrolyzers for the production of clean hydrogen fuel. RuIr alloy is considered to be a promising electrocatalyst because of its favorable OER performance and potential for HER. Here, the design of a bifunctional electrocatalyst with greatly boosted water‐splitting performance from doping RuIr alloy nanocrystals with transition metals that modify electronic structure and binding strength of reaction intermediates is reported. Significantly, Co‐RuIr results in small overpotentials of 235 mV for OER and 14 mV for HER (@ 10 mA cm^?2 current density) in 0.1 m HClO₄ media. Therefore a cell voltage of just 1.52 V is needed for overall water splitting to produce hydrogen and oxygen. More importantly, for a series of M‐RuIr (M = Co, Ni, Fe), the catalytic activity dependence at fundamental level on the chemical/valence states is used to establish a novel composition‐activity relationship. This permits new design principles for bifunctional electrocatalysts.     

Constructing Pure Phase Tungsten‐Based Bimetallic Carbide Nanosheet as an Efficient Bifunctional Electrocatalyst for Overall Water Splitting

Carbides are commonly regarded as efficient hydrogen evolution reaction (HER) catalysts, but their poor oxygen evolution reaction (OER) catalytic activities seriously limit their practical application in overall water splitting. Here, vertically aligned porous cobalt tungsten carbide nanosheet embedded in N‐doped carbon matrix (Co₆W₆C@NC) is successfully constructed on flexible carbon cloth (CC) as an efficient bifunctional electrocatalyst for overall water splitting via a facile metal–organic framework (MOF) derived method. The synergistic effect of Co and W atoms effectively tailors the electron state of carbide, optimizing the hydrogen‐binding energy. Thus Co₆W₆C@NC shows an enhanced HER performance with an overpotential of 59 mV at a current density of ?10 mA cm^?2. Besides, Co₆W₆C@NC easily in situ transforms into tungsten actived cobalt oxide/hydroxide during the OER process, serving as OER active species, which provides an excellent OER activity with an overpotential of 286 mV at a current density of ?10 mA cm^?2. The water splitting device, by applying Co₆W₆C@NC as both the cathode and anode, requires a low cell voltage of 1.585 V at 10 mA cm^?2 with the great stability in alkaline solution. This work provides a feasible strategy to fabricate bimetallic carbides and explores their possibility as bifunctional catalysts toward overall water splitting.     

Understanding the Role of (W,Mo, Sb) Dopants in the Catalyst Evolution and Activity Enhancement of Co3O4 during Water Electrolysis via In Situ Spectroelectrochemical Techniques

Unlocking the potential of the hydrogen economy is dependent on achieving green hydrogen (H₂) production at competitive costs. Engineering highly active and durable catalysts for both oxygen and hydrogen evolution reactions (OER and HER) from earth-abundant elements is key to decreasing costs of electrolysis, a carbon-free route for H₂ production. Here, a scalable strategy to prepare doped cobalt oxide (Co₃O₄) electrocatalysts with ultralow loading, disclosing the role of tungsten (W), molybdenum (Mo), and antimony (Sb) dopants in enhancing OER/HER activity in alkaline conditions, is reported. In situ Raman and X-ray absorption spectroscopies, and electrochemical measurements demonstrate that the dopants do not alter the reaction mechanisms but increase the bulk conductivity and density of redox active sites. As a result, the W-doped Co₃O₄ electrode requires ≈390 and ≈560 mV overpotentials to reach ±10 and ±100 mA cm⁻² for OER and HER, respectively, over long-term electrolysis. Furthermore, optimal Mo-doping leads to the highest OER and HER activities of 8524 and 634 A g⁻¹ at overpotentials of 0.67 and 0.45 V, respectively. These novel insights provide directions for the effective engineering of Co₃O₄ as a low-cost material for green hydrogen electrocatalysis at large scales.     

Graphene Composites with Cobalt Sulfide: Efficient Trifunctional Electrocatalysts for Oxygen Reversible Catalysis and Hydrogen Production in the Same Electrolyte

Nitrogen and sulfur‐codoped graphene composites with Co₉S₈ (NS/rGO‐Co) are synthesized by facile thermal annealing of graphene oxides with cobalt nitrate and thiourea in an ammonium atmosphere. Significantly, in 0.1 m KOH aqueous solution the best sample exhibits an oxygen evolution reaction (OER) activity that is superior to that of benchmark RuO₂ catalysts, an oxygen reduction reaction (ORR) activity that is comparable to that of commercial Pt/C, and an overpotential of only ?0.193 V to reach 10 mA cm^?2 for hydrogen evolution reaction (HER). With this single catalyst for oxygen reversible electrocatalysis, a potential difference of only 0.700 V is observed in 0.1 m KOH solution between the half‐wave potential in ORR and the potential to reach 10 mA cm^?2 in OER; in addition, an overpotential of only 450 mV is needed to reach 10 mA cm^?2 for full water splitting in the same electrolyte. The present trifunctional catalytic activities are markedly better than leading results reported in recent literature, where the remarkable trifunctional activity is attributed to the synergetic effects between N,S‐codoped rGO, and Co₉S₈ nanoparticles. These results highlight the significance of deliberate structural engineering in the preparation of multifunctional electrocatalysts for versatile electrochemical reactions.     

Dual Electronic Modulations on NiFeV Hydroxide@FeOx Boost Electrochemical Overall Water Splitting

Nickel-iron based hydroxides have been proven to be excellent oxygen evolution reaction (OER) electrocatalysts, whereas they are inactive toward hydrogen evolution reaction (HER), which severely limits their large-scale applications in electrochemical water splitting. Herein, a heterostructure consisted of NiFeV hydroxide and iron oxide supported on iron foam (NiFeV@FeO_x/IF) has been designed as a highly efficient bifunctional (OER and HER) electrocatalyst. The V doping and intimate contact between NiFeV hydroxide and FeO_x not only improve the entire electrical conductivity of the catalyst but also afford more high-valence Ni which serves as active sites for OER. Meanwhile, the introduction of V and FeO_x reduces the electron density on lattice oxygen, which greatly facilitates desorption of H_ads. All of these endow the NiFeV@FeO_x/IF with exceptionally low overpotentials of 218 and 105 mV to achieve a current density of 100 mA cm⁻² for OER and HER, respectively. More impressively, the electrolyzer requires an ultra-low cell voltage of 1.57 V to achieve 100 mA cm⁻² and displays superior electrochemical stability for 180 h, which outperforms commercial RuO₂||Pt/C and most of the representative catalysts reported to date. This work provides a unique route for developing high-efficiency electrocatalyst for overall water splitting.     

Synergistic Coupling of Ni Nanoparticles with Ni3C Nanosheets for Highly Efficient Overall Water Splitting

Exploring earth‐abundant bifunctional electrocatalysts with high efficiency for water electrolysis is extremely demanding and challenging. Herein, density functional theory (DFT) predictions reveal that coupling Ni with Ni₃C can not only facilitate the oxygen evolution reaction (OER) kinetics, but also optimize the hydrogen adsorption and water adsorption energies. Experimentally, a facile strategy is designed to in situ fabricate Ni₃C nanosheets on carbon cloth (CC), and simultaneously couple with Ni nanoparticles, resulting in the formation of an integrated heterostructure catalyst (Ni–Ni₃C/CC). Benefiting from the superior intrinsic activity as well as the abundant active sites, the Ni–Ni₃C/CC electrode demonstrates excellent bifunctional electrocatalytic activities toward the OER and hydrogen evolution reaction (HER), which are superior to all the documented Ni₃C‐based electrocatalysts in alkaline electrolytes. Specifically, the Ni–Ni₃C/CC catalyst exhibits the low overpotentials of only 299 mV at the current density of 20 mA cm^?2 for the OER and 98 mV at 10 mA cm^?2 for the HER in 1 m KOH. Furthermore, the bifunctional Ni–Ni₃C/CC catalyst can propel water electrolysis with excellent activity and nearly 100% faradic efficiency. This work highlights an easy approach for designing and constructing advanced nickel carbide‐based catalysts with high activity based on the theoretical predictions.     

Superior Hydrogen Evolution Reaction Performance in 2H‐MoS2 to that of 1T Phase

In the hydrogen evolution reaction (HER), energy‐level matching is a prerequisite for excellent electrocatalytic activity. Conventional strategies such as chemical doping and the incorporation of defects underscore the complicated process of controlling the doping species and the defect concentration, which obstructs the understanding of the function of band structure in HER catalysis. Accordingly, 2H‐MoS₂ and 1T‐MoS₂ are used to create electrocatalytic nanodevices to address the function of band structure in HER catalysis. Interestingly, it is found that the 2H‐MoS₂ with modulated Fermi level under the application of a vertical electric field exhibits excellent electrocatalytic activity (as evidenced by an overpotential of 74 mV at 10 mA cm^?2 and a Tafel slope of 99 mV per decade), which is superior to 1T‐MoS₂. This unexpected excellent HER performance is ascribed to the fact that electrons are injected into the conduction band under the condition of back‐gate voltage, which leads to the increased Fermi level of 2H‐MoS₂ and a shorter Debye screen length. Hence, the required energy to drive electrons from the electrocatalyst surface to reactant will decrease, which activates the 2H‐MoS₂ thermodynamically.     

Conversion of Intercalated MoO3 to Multi-Heteroatoms-Doped MoS2 with High Hydrogen Evolution Activity

Lack of effective strategies to regulate the internal activity of MoS₂ limits its practical application for hydrogen evolution reactions (HERs). Doping of heteroatoms without forming aggregation or an edge enrichment is still challenging, and its effect on the HER needs to be further explored. Herein, a two-step method is developed to obtain multi-metal-doped H-MoS₂, which includes intercalation of the layered MoO₃ precursor with a following sulfurization. Benefiting from the capability of the intercalation method to uniformly and simultaneously introduce different elements into the van der Waals gap, this method is universal to obtain multi-heteroatoms co-doped MoS₂ without forming clusters, phase separation, and an edge enrichment. It is demonstrated that the doping of adjacent cobalt and palladium monomers on MoS₂ greatly enhances the HER catalytic activity. The overpotential at 10 mA cm⁻² and Tafel slope of Co and Pd co-doped MoS₂ is found to be 49.3 mV and 43.2 mV dec⁻¹, respectively, representing a superior acidic HER catalytic activity. This intercalation-assisted method also provides a new and general strategy to synthesize uniformly doped transition metal dichalcogenides for various applications.     

IrPd Nanoalloy-Structured Bifunctional Electrocatalyst for Efficient and pH-Universal Water Splitting

The lack of high efficiency and pH-universal bifunctional electrocatalysts for water splitting to hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) hinders the large-scale production of green hydrogen. Here, an IrPd electrocatalyst supported on ketjenblack that exhibits outstanding bifunctional performance for both HER and OER at wide pH conditions is presented. The optimized IrPd catalyst exhibits a specific activity of 4.46 and 3.98 A mg_Ir⁻¹ in the overpotential of 100 and 370 mV for HER and OER, respectively, in alkaline conditions. When applied to the anion exchange membrane electrolyzer, the Ir₄₄Pd₅₆/KB catalyst shows a stability of >20 h at a current of 250 mA cm⁻² for water decomposition, indicating promising prospects for practical applications. Beyond offering an advanced electrocatalyst, this work also guides the rational design of desirable bifunctional electrocatalysts for HER and OER by regulating the microenvironments and electronic structures of metal catalytic sites for diverse catalysis.     

Unveiling the Interfacial Effects for Enhanced Hydrogen Evolution Reaction on MoS2/WTe2 Hybrid Structures

Using the MoS₂‐WTe₂ heterostructure as a model system combined with electrochemical microreactors and density function theory calculations, it is shown that heterostructured contacts enhance the hydrogen evolution reaction (HER) activity of monolayer MoS₂. Two possible mechanisms are suggested to explain this enhancement: efficient charge injection through large‐area heterojunctions between MoS₂ and WTe₂ and effective screening of mirror charges due to the semimetallic nature of WTe₂. The dielectric screening effect is proven minor, probed by measuring the HER activity of monolayer MoS₂ on various support substrates with dielectric constants ranging from 4 to 300. Thus, the enhanced HER is attributed to the increased charge injection into MoS₂ through large‐area heterojunctions. Based on this understanding, a MoS₂/WTe₂ hybrid catalyst is fabricated with an HER overpotential of ?140 mV at 10 mA cm^?2, a Tafel slope of 40 mV dec^?1, and long stability. These results demonstrate the importance of interfacial design in transition metal dichalcogenide HER catalysts. The microreactor platform presents an unambiguous approach to probe interfacial effects in various electrocatalytic reactions.     

3D 1T‐MoS2/CoS2 Heterostructure via Interface Engineering for Ultrafast Hydrogen Evolution Reaction

Metallic phase (1T) MoS₂ has been regarded as an appealing material for hydrogen evolution reaction. In this work, a novel interface‐induced strategy is reported to achieve stable and high‐percentage 1T MoS₂ through highly active 1T‐MoS₂/CoS₂ hetero‐nanostructure. Herein, a large number of heterointerfaces can be obtained by interlinked 1T‐MoS₂ and CoS₂ nanosheets in situ grown from the molybdate cobalt oxide nanorod under moderate conditions. Owing to the strong interaction between MoS₂ and CoS₂, high‐percentage of metallic‐phase (1T) MoS₂ of 76.6% can be achieved, leading to high electroconductivity and abundant active sites compared to 2H MoS₂. Furthermore, the interlinked MoS₂ and CoS₂ nanosheets can effectively disperse the nanosheets so as to enlarge the exposed active surface area. The near zero free energy of hydrogen adsorption at the heterointerface can also be achieved, indicating the fast kinetics and excellent catalytic activity induced by heterojunction. Therefore, when applied in hydrogen evolution reaction (HER), 1T‐MoS₂/CoS₂ heterostructure delivers low overpotential of 71 and 26 mV at the current density of 10 mA cm^?2 with low Tafel slops of 60 and 43 mV dec^?1, respectively in alkaline and acidic conditions.     

Amorphous Molybdenum Sulfide/Carbon Nanotubes Hybrid Nanospheres Prepared by Ultrasonic Spray Pyrolysis for Electrocatalytic Hydrogen Evolution

Developing cost‐effective electrocatalysts with high activity and stability for hydrogen evolution reaction (HER) plays an important role in modern hydrogen economy. Amorphous molybdenum sulfide (MoS_x ) has recently emerged as one of the most promising alternatives to Pt‐based catalysts in HER, especially in acidic electrolytes. Here this study reports a simple ultrasonic spray pyrolysis method to synthesize hybrid HER catalysts composed of MoS_x firmly attached on entangled carbon nanotube nanospheres (MoS_x /CNTs). This synthetic process is fast, continuous, highly durable, and amenable to high‐volume production with high yields and exceptional quality. The MoS_x /CNTs hybrid catalyst prepared at 300 °C exhibits a low overpotential of 168 mV at the current density of 10 mA cm^?2 with a small Tafel slope of 36 mV dec^?1. Electrochemical measurements and X‐ray photoelectron spectroscopy analyses reveal that the CNT network not only promotes the charge transfer in corresponding HER process but also enhances the stability of the active sites in MoS_x . This work demonstrates that ultrasonic spray pyrolysis is a reliable and versatile approach for synthesizing amorphous MoS_x‐based HER catalysts.