Integrating Polyoxometalates and Silver Clusters into Atomically Precise Molecular Heterojunction.

The Ag cluster-POM assemblies have been shown to possess interesting and potentially useful properties. However, there is no precedent example of atomically precise Ag cluster-POM assemblies showing heterojunction effects in photocatalysis. Herein, the synthesis and total structure determination of the periodically distributed molecular heterojunction [Ag12(SCy)6(CH3CN)12(PW12O40)]n (Ag12-PW12) are reported. The assembly of Ag/W clusters into 3D network can endow the resulting binary structure with an aesthetic topology and unique physicochemical properties. More remarkably, the incorporation of Ag12 cluster with PW12 can efficiently facilitate the separation of photogenerated electrons and holes, thus significantly promoting the catalytic efficiency in selective oxidation of sulfides. The Ag12-PW12 heterojunction can be recovered and reused five times with no drastic change in the catalytic performance. This research is expected to assist in the rational design of cluster-based heterojunction catalysts. The increase of catalytic activity of the Ag12-PW12 assembly in comparison with the unassembled Ag12 and PW12 clusters is attributed to the synergistic effect of Ag12 and PW12 clusters, offering the splendid opportunity for deciphering structure-reactivity relationship of heterostructure-coupled photosystem.

Anchoring Pt Single-Atom Sites on Vacancies of MgO(Al) Nanosheets as Bifunctional Catalysts to Accelerate Hydrogenation-Cyclization Cascade Reactions.

The direct hydrogenation of 2-nitroacylbenzene to 2,1-benzisoxazole presents a significant challenge in the pharmaceutical and fine chemicals industries. In this study, a defect engineering strategy is employed to create bifunctional single-atom catalysts (SACs) by anchoring Pt single atoms onto metal vacancies within MgO(Al) nanosheets. The resultant Pt1/MgO(Al) SAC displays an exceptional catalytic activity and selectivity in the hydrogenation-cyclization of 2-nitroacylbenzene, achieving a 97.5% yield at complete conversion and a record-breaking turnover frequency of 458.8 h-1 under the mild conditions. The synergistic catalysis between the fully exposed single-atom Pt sites within a unique Pt-O-Mg/Al moiety and the abundant basic sites of the MgO(Al) support is responsible for this outstanding catalytic performance. The current work, therefore, paves the way for developing bifunctional or multifunctional SACs that can enhance efficient organocatalytic conversions.

Catalytic (4+2) Annulation via Regio- and Enantioselective Interception of in-situ Generated Alkylgold Intermediate.

A regio- and stereoselective stepwise (4+2) annulation of N-propargylamides and α,ß-unsaturated imines/ketones has been accomplished with synergetic catalysis by a combination of a gold-complex and a chiral quinine-derived squaramide (QN-SQA), leading to highly functionalized chiral tetrahydropyridines/dihydropyrans in good to high yields with generally excellent enantioselectivity. Mechanistic studies and DFT calculations indicate that the in situ formed alkylgold species is the key intermediate in this transformation, and the amide group served as a traceless directing group in this highly selective transformation. This method complements the enantioselective (4+2) annulation of allene reagents, providing the formal internal C-C π-bond cycloaddition products, which is challenging and remains elusive.

Hydrogenation Reactions with Synergistic Catalysis of Pd single atoms and nanoparticles under Near-Ambient Conditions.

Due to the limited resources and high cost of noble metals, boosting their catalytic activities is highly desired in the current catalysis industry. Here, we report a synergetic catalyst, combining Pd2+ and Pd0 species in a nitrogen-doped porous carbons (NPC), which shows boosted catalytic activities in hydrogenation reactions of organic nitro compounds (nitrobenzene, 4-nitrophenol, 1-nitronaphthalene and 1-nitropropane) under near ambient conditions. This synergetic catalyst NPC-[Pd] was synthesized by partial reduction of a palladium-loaded NPC. The catalytic activities and selectivity of NPC-[Pd] for hydrogenation were enhanced significantly compared with those of NPC-Pd2+ or NPC-Pd0 nanoparticles. Theoretical calculations show that H2 preferentially dissociates on Pd nanoparticles, and then organic molecules (nitrobenzene) can be captured and react with the dissociated H atom on Pd2+ sites. Similar reaction procedure also occur on Pt or Rh. Hydrogenation of different aromatic compounds with different functional groups (naphthalene, 4-nitrochlorobenzene, benzaldehyde and acetophenone) confirmed the broad excellent catalytic activity of this synergistic catalyst.

Incorporation of Active Metal Species in Crystalline Porous Materials for Highly Efficient Synergetic Catalysis.

The design and development of efficient catalytic materials with synergistic catalytic sites always has long been known to be a thrilling and very dynamic research field. Crystalline porous materials (CPMs) mainly including metal-organic frameworks and zeolites with high scientific and industrial impact have recently been the subject of extensive research due to their essential role in modern chemical industrial processes. The rational incorporation of guest species in CPMs can synergize the respective strengths of these components and allow them to collaborate with each other for synergistic catalysis, leading to enhanced catalytic activity, selectivity, and stability in a broad range of catalytic processes. In this review, the recent advances in the development of CPMs-confined active metal species, including metal nanoparticles, metal/metal oxides heteroparticles, metal oxide, subnanometric metal clusters, and polyoxometalates, for heterogeneous catalysis, with a particular focus on synergistic effects between active components that result in an enhanced performance are highlighted. Insights into catalysts design strategies, host-guest interactions, and structure-property relationships have been illustrated in detail. Finally, the existing challenges and possible development directions in CPMs-based encapsulation-structured synergistic catalysts are discussed.

Simultaneous removal of gaseous CO and elemental mercury over Cu-Co modified activated coke at low temperature.

Cu-Co multiple-oxides modified on HNO3-pretreated activated coke (ACN) were optimized for the simultaneous removal of gaseous CO and elemental mercury (Hg0) at low temperature (< 200 °C). It was found that 2%CuOx-10%CoOx/ACN catalyst calcined at 400°C resulted in the coexistence of complex oxides including CuO, Cu2O, Co3O4, Co2O3 and CoO phases, which might be good for the simultaneous catalytic oxidation of CO by Co-species and removal of Hg0 by Cu-species, benefiting from the synergistic catalysis during the electro-interaction between Co and Cu cations (CoO ⇌ Co3O4 and Cu2O ⇌ CuO). The catalysis removal of CO oxidation was obviously depended on the reaction temperature obtaining 94.7% at 200 °C, while no obvious promoting effect on the Hg0 removal (68.3%-78.7%). These materials were very substitute for the removal of CO and Hg° from the flue gas with the conditions of 8-20 vol.% O2 and flue-gas temperature below 200 °C. The removal of Hg° followed the combination processes of adsorption and catalytic oxidation reaction via Langmuir-Hinshelwood mechanism, while the catalysis of CO abided by the Mars-van Krevelen mechanism with lattice oxygen species.

Hydrogen peroxide sensing in body fluids and tumor cells via in situ produced redox couples on two-dimensional holey CuCo2O4 nanosheets.

A novel nanomaterial of two-dimensional holey CuCo2O4 (2D HCCO) nanosheets was synthesized via a general template-directed method and employed for the first time to construct an effective electrochemical platform for H2O2 sensing with the combination of cerium oxide (CeO2). During the electrocatalytic reduction of H2O2, the synergetic catalysis of CeO2/HCCO/MWCNTs/GCE owing to the naturally holey frameworks and the mediator of CeO2 results in the ultra-sensitive detection of H2O2. The current was greatly enhanced owing to the unique holey structure that can minimize the charge transfer distance and provide more active sites to boost the signals, and the dual oxidation state of Ce3+/Ce4+ on the surface of 2D HCCO nanosheets can promote the in situ production of Cu2+/Cu+ and Cu+/Cu and further amplify the detection signal. The CeO2/HCCO/MWCNTs/GCE showed a wide linear range from 1 µM to 7.31 mM using chronoamperometry at the potential of - 0.25 V and a relatively low detection limit of 0.16 µM in physiological environment, which was also utilized for tracking the trace H2O2 released from Hela cells. This study shows great promise for the emerging application of holey HCCO-based biosensors in bioanalysis and early cancer diagnosis. Graphical abstract.

Lewis Acid Transition-Metal-Catalyzed Hydrogen Activation: Structures, Mechanisms, and Reactivities.

As a new type of bifunctional catalyst, the Lewis acid transition-metal (LA-TM) catalysts have been widely applied for hydrogen activation. This study presents a mechanistic framework to understand the LA-TM-catalyzed H2 activation through DFT studies. The mer(trans)-homolytic cleavage, the fac(cis)-homolytic cleavage, the synergetic heterolytic cleavage, and the dissociative heterolytic cleavage should be taken as general mechanisms for the field of LA-TM catalysis. Four typical LA-TM catalysts, the Z-type κ4 -L3 B-Rh complex tri(azaindolyl)borane-Rh, the X-type κ3 -L2 B-Co complex bis-phosphino-boryl (PBP)-Co, the η2 -BC-type κ3 -L2 B-Pd complex diphosphine-borane (DPB)-Pd, and the Z-type κ2 -LB-Pt complex (boryl)iminomethane (BIM)-Pt are selected as representative models to systematically illustrate their mechanistic features and explore the influencing factors on mechanistic variations. Our results indicate that the tri(azaindolyl)borane-Rh catalyst favors the synergetic heterolytic mechanism; the PBP-Co catalyst prefers the mer(trans)-homolytic mechanism; the DPB-Pd catalyst operates through the fac(cis)-homolytic mechanism, whereas the BIM-Pt catalyst tends to undergo the dissociative heterolytic mechanism. The mechanistic variations are determined by the coordination geometry, the LA-TM bonding nature, the electronic structure of the TM center, and the flexibility or steric effect of the LA ligands. The presented mechanistic framework should provide helpful guidelines for LA-TM catalyst design and reaction developments.

Synergistic enhancement of wearable biosensor through Pt single-atom catalyst for sweat analysis.

Real-time monitoring of biological markers in sweat is a valuable tool for health assessment. In this study, we have developed an innovative wearable biosensor for precise analysis of glucose in sweat during physical activities. The sensor is based on a single-atom catalyst of platinum (Pt) uniformly dispersed on tricobalt tetroxide (Co3O4) nanorods and reduced graphene oxide (rGO), featuring a unique three-dimensional nanostructure and excellent glucose electrocatalytic performance with a wide detection range of 1-800 µM. Additionally, density functional theory calculations have revealed the synergetic role of Pt active sites in the Pt single-atom catalyst (Co3O4/rGO/Pt) in glucose adsorption and electron transfer, thereby enhancing sensor performance. To enable application in wearable devices, we designed an S-shaped microfluidic chip and a point-of-care testing (POCT) device, both of which were validated for effectiveness through actual use by volunteers. This research provides valuable insights and innovative approaches for analyzing sweat glucose using wearable devices, contributing to the advancement of personalized healthcare.

Regulate catalytic performance by engineering non-regular structure of extradiol dioxygenase: An entrance to bottom strategy.

Extradiol dioxygenase Tcu3516 is a home-sourced enzyme demonstrating potent aromatic phenol degradation capacity. To add to the advantageous modifications inside active cavity, this work reported a novel strategy to engineer rarely concerned non-regular structures around the entrance towards the active site at the bottom of cavity. Three structures, Loop region 1 (Loop1: Met173-Arg185), Loop region 2 (Loop2: Ala201-Val212) and C-terminal (C-tail: His290-Lys306) were therefore identified through structural flexibility analysis. Highly rigid prolines within the structures were mutated into smaller alanine, glycine, or serine to improve structural flexibilities; while only P183S on Loop1 showed 3-fold activity enhancement vs the WT when subjected to cleavage of mono-cyclic catechol analogues. The analysis of Root Mean Square Fluctuation showed that P183S presents certain enhancement on Loop1 flexibility without dramatic changes of other domains. Furthermore, the synergetic effects from mutation P183S and cavity-based mutations V186L, V212N and D285A were evaluated by characterizing combinatorial mutants. Temperature dependence and thermostability of the combined mutants showed a more flexible catalytic domain without sacrificing structural integrity and stability. kcat value of P183S/V186L (SL) towards monocyclic catechols significantly surpasses any other combinatorial mutants around Tcu3516 active sites. Moreover, the synergetic effects on conformational plasticity were analyzed by molecular dynamic simulations to shed light into the interplay between structural changes and catalytic performance.

Hydrophobic Trinuclear Copper Cluster-Containing Organic Framework for Synergetic Electrocatalytic Synthesis of Amino Acids.

Electrocatalytic synthesis of amino acids provides a promising green and efficient pathway to manufacture the basic substances of life. Herein, reaction of 2,5-perfluroalkyl-terepthalohydrazide and tris(4-µ2 -O-carboxaldehyde-pyrazolato-N, N')-tricopper affords a crystalline trinuclear copper cluster-containing organic framework, named F-Cu3 -OF. Incorporation of abundant hydrophobic perfluroalkyl groups inside the channels of F-Cu3 -OF is revealed to successfully suppress the hydrogen evolution reaction via preventing H+ cation with large polarity from the framework of F-Cu3 -OF and in turn increasing the adsorption of other substrates with relatively small polarity like NO3 - and keto acids on the active sites. The copper atoms with short distance in the trinuclear copper clusters of F-Cu3 -OF enable simultaneous activization of NO3 - and keto acids, facilitating the following synergistic and efficient C─N coupling on the basis of in situ spectroscopic investigations together with theoretical calculation. Combination of these effects leads to efficient electroproduction of various amino acids including glycine, alanine, leucine, valine, and phenylalanine from NO3 - and keto acids with a Faraday efficiency of 42%-71% and a yield of 187-957 µmol cm-2 h-1 , representing the thus far best performance. This work shall be helpful for developing economical, eco-friendly, and high-efficiency strategy for the production of amino acids and other life substances.

Constructing homo/hetero-nuclear carbon and oxygen atoms co-doped graphitic carbon nitride assisted by ionic liquid for photothermal synergistic catalytic oxidation of cyclohexane.

The adoption of photothermal synergistic catalysis for cyclohexane oxidation can balance the advantages of high conversion of thermal catalysis and high selectivity of photocatalytic technology to achieve better catalytic performance. Here, we prepared functional carbon nitride (BCA-CN) by self-assembly strategy of ionic liquid [Bmim]CA (1-Butyl-3-methylimidazole citrate) with melamine and cyanuric acid utilizing abundant elements and anionic/cationic hydrogen bonding interactions. The introduction of [Bmim]CA embeds C-C (carbon and carbon band) and C-O-C (ether bond) structures into graphitic carbon nitride (g-C3N4) framework, significantly improving light absorption capacity and migration of photo generated charge carriers. Compared to g-C3N4, both BCA-CN increases cyclohexane conversion and KA oil (the mixture of cyclohexanol and cyclohexanone) selectivity by 1.3 times under photothermal catalysis. The surface reactions are facilitated by changing adsorption sites of cyclohexane to increase adsorption energy and obtaining more hydroxyl radicals and superoxide radicals. Furthermore, the enhanced selectivity is attributed to the difficulty in generating cyclohexanone radicals. This work offers the reference scheme for the development of efficient photothermal catalysts in the selective oxidation of cyclohexane.

Metal-Acid Interface Engineering in Pd-WOx Bifunctional Catalysts for the Hydroalkylation Tandem Reaction of Benzene.

The hydroalkylation tandem reaction of benzene to cyclohexylbenzene (CHB) provides an atom economy route for conversion and utilization of benzene; yet, it presents significant challenges in activity and selectivity control. In this work, we report a metal-support synergistic catalyst prepared via calcination of W-precursor-containing montmorillonite (MMT) followed by Pd loading (denoted as Pd-mWOx/MMT, m = 5, 15, and 25 wt %), which shows excellent catalytic performance for hydroalkylation of benzene. A combination study (X-ray diffraction (XRD), hydrogen-temperature programmed reduction (H2-TPR), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), UV-vis, Raman, and density functional theory (DFT) calculations) confirms the formation of interfacial sites Pd-(WOx)-H, whose concentration is dependent on the interaction between Pd and WOx. The optimized catalyst (Pd-15WOx/MMT) exhibits a CHB yield of up to 45.1% under a relatively low hydrogen pressure, which stands at the highest level among state-of-the-art catalysts. Investigations on the structure-property correlation based on in situ FT-IR and control experiments further verify that the Pd-(WOx)-H structure serves as the dual-active site: the interfacial Pd site accelerates benzene hydrogenation to cyclohexene (CHE), while the interfacial Bronsted (B) acid site in Pd-(WOx)-H boosts the alkylation of benzene and CHE to CHB. This study offers a new strategy for the design and preparation of metal-acid bifunctional catalysts, which shows potential application in the hydroalkylation reaction of benzene.

Room-Temperature ZnBr2 -Catalyzed Regioselective 1,6-Hydroarylation of Electron-Rich Arenes to para-Quinone Methides: Synthesis of Unsymmetrical Triarylmethanes.

A mild and efficient Zn(II)-catalyzed regioselective 1,6-hydroarylation of para-quinone methides (p-QMs) with electron-rich arenes protocol is reported. A variety of electron-rich arenes and para-quinone methides are well tolerated under mild conditions, delivering a broad range of triarylmethanes in good to excellent yields. The present method also works well for the hydroarylation of p-QMs with other nucleophiles, such as aniline, indole and phenol derivatives, offering the corresponding triarylmethanes with good yields under the standard conditions. The possible mechanism for the formation of C(sp3 )-C(sp2 ) bonds in hydroarylation reactions has been explored by step-by-step control experiments, and the reaction may follow a second-order manner in a chemical kinetic study.

Efficient depolymerization of lignin through microwave-assisted Ru/C catalyst cooperated with metal chloride in methanol/formic acid media.

Lignin, an abundant aromatic biopolymer, has the potential to produce various biofuels and chemicals through biorefinery activities and is expected to benefit the future circular economy. Microwave-assisted efficient degradation of lignin in methanol/formic acid over Ru/C catalyst cooperated with metal chloride was investigated, concerning the effect of type and dosage of metal chloride, dosage of Ru/C, reaction temperature, and reaction time on depolymerized product yield and distribution. Results showed that 91.1 wt% yield of bio-oil including 13.4 wt% monomers was obtained under the optimum condition. Yields of guaiacol-type compounds and 2,3-dihydrobenzofuran were promoted in the presence of ZnCl2. Formic acid played two roles: (1) acid-catalyzed cleavage of linkages; (2) acted as an in situ hydrogen donor for hydrodeoxygenation in the presence of Ru/C. A possible mechanism for lignin degradation was proposed. This work will provide a beneficial approach for efficient depolymerization of lignin and controllable product distribution.

Synergetic Function of the Single-Atom Ru-N4 Site and Ru Nanoparticles for Hydrogen Production in a Wide pH Range and Seawater Electrolysis.

Hydrogen production by water splitting and seawater electrolysis is a promising alternative to develop clean hydrogen energy. The construction of high-efficiency and durable electrocatalysts for the hydrogen evolution reaction (HER) in a wide pH range and seawater is critical to overcoming the sluggish kinetic process. Herein, we develop an efficient catalytic material composed of a single-atom Ru-N4 site and Ru nanoparticles anchored on nitrogen-doped carbon (Ru1+NPs/N-C) through the coordination-pyrolysis strategy of the melamine formaldehyde resin. The Ru1+NPs/N-C catalyst shows outstanding HER activity with the smallest overpotentials, the lowest Tafel slopes, the highest mass activity and turnover frequency, as well as excellent stability in both acidic and alkaline media. Moreover, Ru1+NPs/N-C shows comparable hydrogen production performance and a higher faradic efficiency to 20% Pt/C in natural seawater and artificial simulated seawater. Theoretical calculations demonstrate that the strong synergistic effects between the Ru-N4 site and Ru nanoparticles modify the electronic structure to accelerate the HER kinetics. Ru nanoparticles can effectively realize dissociation of H2O to generate adsorbed hydrogen and also promote the single-atom Ru-N4 site to combine adsorbed hydrogen to H2 and desorption. This work provides a new perspective for designing high-efficiency hydrogen production electrocatalysts for large-scale seawater electrolysis.

Metal-Acid Bifunctional Catalysts toward Tandem Reaction: One-Step Hydroalkylation of Benzene to Cyclohexylbenzene.

The one-step hydroalkylation of benzene to cyclohexylbenzene (CHB) is a technically challenging and economically interesting reaction with great industrial importance, where bifunctional catalysts play a crucial role in such a tandem reaction. In this work, we report H3PW12O40 (HPW) modified Ni nanoparticles (NPs) supported on mixed metal oxides (Ni/MMOs), which are featured by HPW species localized on the surface of Ni NPs (denoted as HPW-Ni/MMOs). The optimal catalyst (0.3HPW-Ni/MMOs) exhibits a satisfactory catalytic performance toward benzene hydroalkylation to CHB with a CHB yield of up to 41.2%, which is the highest standard among previously reported catalysts to date. A combination investigation based on HR-TEM, XPS, XANES, and in situ FT-IR verified the electron transfer from the W atom to the adjacent Ni atom, which facilitated the formation and desorption of cyclohexene (CHE) from Ni followed by the alkylation reaction of benzene and CHE at the interfacial Brønsted (B) acid sites of HPW, accounting for the significantly enhanced catalytic behavior. It is proposed that the HPW-Ni interface structure in xHPW-Ni/MMOs samples provides unique adsorption sites for benzene and CHE with a moderate adsorption strength, which serve as the intrinsic active center for this reaction: the Ni site promotes the hydrogenation of benzene to CHE, while the B acid site in HPW facilitates the alkylation of CHE and benzene to produce CHB. This work provides a fundamental understanding of the metal-acid synergistic catalysis toward the hydroalkylation reaction, which can be extended to the design and preparation of high-performance catalysts used in tandem reactions.

Split-Type Electrochemical Immunoassay System Triggering Ascorbic Acid-Mediated Signal Magnification Based on a Controlled-Release Strategy.

This research put forward a novel split-type electrochemical (EC) immunosensor which integrated the controlled-release strategy with EC detection for application in the field of biosensing. Concretely, ascorbic acid (AA) was packaged in a cadmium sulfide (CdS)-capped spherical mesoporous bioactive glass (SBG) nanocarrier (SBGCdS) on account of encapsulation technology. To reduce the complexity of the bioanalysis, the detection antibody-labeled SBGCdS-AA bioconjugate was applied in a 96-well microplate for the immunoreaction process, which is independent of the EC determination procedure. Thus, the immune interference and steric hindrance caused by the accumulation of nanomaterials on the electrode could be minimized. Subsequently, AA was released efficiently via the destruction effect of dithiothreitol on the disulfide bond. In addition, for the as-prepared FcAI/l-Cys/gold nanoparticles (GNPs)/porous BiVO4 (p-BVO)/ITO EC sensing platform in the detection solution, the synergetic catalysis of Fc and GNPs/p-BVO toward the oxidation of the released AA could be realized, which triggered AA-mediated significant signal magnification throughout this study. In particular, p-BVO with an ordered nanoarray structure could accelerate the electron transfer to assist in sensitivity improvement of this system. This novel biosensor was capable of assaying the neuron-specific enolase (NSE) biomarker sensitively, from which a linear range of 0.001-100 ng/mL was derived along with a low detection limit of 1.08 pg/mL. An innovative way could be paved in the bioanalysis of NSE and other biomarkers.

In-situ preparation of molybdenum trioxide-silver composites for the improved photothermal catalytic performance of cyclohexane oxidation.

The selective catalytic oxidation of cyclohexane has important theoretical and practical application value. However, high conversion rate and high selectivity are difficult to achieve simultaneously by conventional catalytic system. In this work, blue molybdenum trioxide (MoO3) nanorods with oxygen vacancies were prepared by hydrothermal method using hydrated molybdic acid as a precursor under the reduction of formic acid, and in-situ produced MoO3-silver (MoO3-Ag) composites were further used in the photothermal catalytic oxidation of cyclohexane with high conversion and high selectivity using dry air as oxidant. The results showed that the best conversion rate of cyclohexanone and cyclohexanol (KA oil) could reach 8.6% with the selectivity of 99.0%. The excellent catalytic performance of MoO3-Ag composites can be attributed to the significantly increased visible and near-infrared light absorption caused by the plasma resonance effect of Ag nanoparticles and oxygen vacancies, and the prevented charge recombination by MoO3-Ag Schottky heterojunction. This work provides new reference solutions for the design and preparation of high-performance photothermal catalysts for the selective oxidation of hydrocarbons.

Superb Hydrogen Evolution by a Pt Nanoparticle-Decorated Ni3S2 Microrod Array.

Ni3S2 has attracted great interest as a potential alternative catalyst for the oxygen evolution reaction; however, the formation of sulfur-hydrogen bonds on Ni3S2 suppressed the hydrogen evolution reaction (HER), which remains a significant challenge in interface engineering of Ni3S2 structures for enhancing its HER performance. Herein, we demonstrate an efficient strategy for constructing a Pt nanoparticle-decorated Ni3S2 microrod array supported on Ni foam (Pt/Ni3S2/NF) by electrodeposition of Pt nanoparticles on hydrothermally synthesized Ni3S2/NF. The Pt/Ni3S2/NF heterostructure array exhibits an extremely low overpotential of 10 mV at 10 mA cm-2, surpassing that of commercial Pt/C and representing the best alkaline HER catalysts to date. Impressively, at an overpotential of 0.15 V, Pt/Ni3S2/NF displays a Pt mass activity and a normalized current density (against the electrochemical surface area) of 5.52 A mg-1 and 1.84 mA cm-2, respectively, which are 8.8 and 15.3 times higher compared to those of Pt/C, respectively. In addition, this electrode also shows much enhanced catalytic performance and stability in neutral media. Such enhanced HER activities are attributed to the constructed interface in the Pt/Ni3S2 heterostructure array, which synergistically favor water dissociation and subsequent hydrogen evolution, which is supported by density functional theory calculations.