Hydrogen Evolution Performance Research Articles

Covalently Linking Reduced Graphene Oxide Facilitated Electrodeposition of MoS2 on Silicon Pyramidal Photocathode To Enhance Hydrogen Evolution.

In recent years, increasing attention has been paid to photoelectrochemical (PEC) hydrogen production owing to the utilization of sustainable solar energy and its promising performance. Silicon-based composites are generally considered ideal materials for PEC hydrogen production. However, slow reaction kinetics and poor stability are still key factors hindering the development of silicon-based photoelectrocatalysts. Herein, we present an n+-p Si pyramidal photocathode assembly method to load reduced graphene oxide (rGO) onto the surface of the n+-p Si pyramid by covalently linking (Si/rGO). rGO is utilized as a conductive layer to reduce the interfacial charge-transfer resistance. Then, MoS2 can be successfully electrodeposited on the surface of Si/rGO to form the Si/rGO/MoS2 composite, which possesses excellent PEC hydrogen evolution performance with a high and stable photocurrent of -41.6 mA cm-2 and a hydrogen evolution rate of about 18.1 μmol min-1 cm-2 under 0 V (vs RHE). The covalently linking rGO layer effectively enhances the transfer of photogenerated carriers between the Si substrate and MoS2. MoS2 provides abundant hydrogen evolution active sites, which accelerate the surface reaction kinetics, as well as a protective layer for the Si pyramidal array structure. This work provides a low-cost, convenient, and efficient way of preparing silicon-based photocathodes.

Effective anaerobic digestion performance from kitchen wastewater by nanoscale zero-valent iron composite materials: Hydrogen corrosion capability and biological biogas upgrading

In this study, nanoscale zero-valent iron (nZVI) was modified by carboxymethylcellulose (CMC), extracellular polymeric substances (EPS) and sodium dodecyl sulfate (SDS), which were compared for the ability of hydrogen corrosion and then for the biogas upgrading during kitchen wastewater anaerobic digestion. The results showed that three nZVI composite materials addition could increase hydrogen evolution performance by 6.11∼10.30 % compared with nZVI. Especially, the hydrogen evolution from sodium dodecyl sulfate modified composite material reached 121.0 mL/g. The continuous release of hydrogen promoted the biogas yield to 510.96 mL/gVS in reaction group with SDS12-nZVI10 addition (N4), with CH4 content reached 93.37 %. Microbial community analysis showed that the total relative abundance of Methanothrix and Methanolinea was 43.60 % in N4, which was higher than other groups. It was indicated that H2-assisted biogas upgrading with nZVI composite materials addition was achievable, particularly in N4.

Surface cyano groups optimize the charge transfer of poly heptazine imide for enhanced photocatalytic H2 evolution

Surface functionalization has been considered as an effective strategy to manipulate charge separation of carbon nitride and therefore to largely improve the photocatalytic H2 evolution efficiency. Poly heptazine imide (PHI) is a new class of crystalline carbon nitride frameworks that exhibits remarkable photocatalytic performance for hydrogen evolution. To further improve the H2 evolution performance of PHI and explore the reaction mechanism, ammonium thiocyanate was used as a precursor for the synthesis of poly heptazine imide at elevated temperatures under molten salt conditions. The optimized PHI with an abundance of surface cyano groups shows a significantly enhanced photocatalytic performance for H2 evolution, which is 4.3 times that on pristine PCN. Most importantly, the surface cyano group adjusts the electron intensity of the polymeric framework, enhances the light absorbance, reduces the bandgap, and improves the charge separation efficiency. The synthetic technique also could be applied to other sulfur-containing precursors for the synthesis of PHI frameworks with excellent hydrogen evolution production performance.

Construction of a Dual-Function Mo-ZIS@Ti for Photocatalytic Benzyl Alcohol Oxidation and Hydrogen Evolution Performance.

The photocatalytic oxidation of benzyl alcohol and the simultaneous evolution of hydrogen from water are efficient dual-optimal routes. It is important to develop composite catalysts that combine redox properties and facilitate electron-hole separation and transport. Herein, the bimetallic-doped Mo-ZIS@Ti photocatalyst was designed and synthesized, and the selective oxidation of benzyl alcohol and hydrogen evolution by water splitting was realized at the same time. Under visible light irradiation, benzyl alcohol was completely converted with more than 99% selectivity for benzaldehyde, and the H2 production rate was 5.6 times higher than the initial ZIS. The exceptional catalytic performance was ascribed to utilizing Ti-MIL-125 as a precursor, wherein slowly releasing-doped Ti formed robust Ti-S bonds that quickly transfer electrons and reduce sites. Meanwhile, doping Mo effectively captures photogenerated holes and acts as active sites for oxidation reactions. Both experimental characterization and work function calculations demonstrate that the bimetallic synergism effectively modulates the electronic structure of ZIS, promotes the directional separation of electrons and holes, and significantly improves the photoactivity and stability of ZIS. This work contributes a route to obtain benzaldehyde and green hydrogen at the same time and also gives new insights for the construction and mechanism study of bimetallic-doping catalysts.

Unique construction of hierarchical PANI–based nanofibrous network for boosting water electrolysis through highly efficient utilization of Pt nanocatalyst

Enhancing catalytic activity of Pt and designing rational structure of catalytic layer (CL) are effective strategies for improving the performance of proton exchange membrane water electrolysis (PEMWE) with lower Pt loading. Herein, a hierarchical nanostructured CL based on co–doped carbon, sulfonated polyaniline (PANI) nanofibrous network and Pt nanoparticles is constructed on carbon cloth by layer–by–layer in–situ growth method. The N/P/S co–doped carbon interlayer derived from PANI can promote the growth of sulfonated PANI nanofibers. The in–situ grown Pt nanoparticles is anchored by sulfonated PANI, achieving uniform and stable distribution as well as altered electronic structure for improved catalytic activity. The unique CL greatly improves the electrochemical surface area and provides interconnected pathways. The as–prepared cathode exhibits an overpotential of 23 mV at 10 mA cm−2, indicating excellent hydrogen evolution performance. Furthermore, the PEMWE device with above–mentioned cathode achieves an excellent performance of 1.771 V @ 2 A cm−2 with low Pt loading of 0.07 mg cm−2, which is comparable to that of the conventional cathode with 14 times higher Pt loading of 1 mg cm−2. Our strategy of designing hierarchical nanostructured CL provides a feasible approach to lower the consumption of Pt without performance loss for further industrialization of PEMWE.

Acid etching-induced nanocutting of LaNiO3 transplanting self-assembled photodiode array-like LaNiO3/N,P-RGO nanoreactor for efficient photocatalytic hydrogen evolution

Nanoscale graphene-semiconductor composite photocatalysts with fascinating properties in the photocatalytic hydrogen evolution have inspired numerous interests in broad research fields. The architectures with efficient light response and promoting charge separation at the interface between reduced graphene oxide (RGO) and semiconductor are critical, yet synthesizing them remains a formidable challenge. Herein, the photodiode array-like LaNiO3/N,P-RGO (LNO/N,P-RGO) nanoreactor was constructed using an innovative strategy of acid etching-induced nanocutting self-assembly. Ammonium dihydrogen phosphate working as both a nitrogen phosphorus co-dopant and an acid etching reagent, cuts perovskite LaNiO3 (LNO) nanoparticles into nanorods, which are bonded evenly on the nitrogen phosphorus co-doped reduced graphene oxide (N,P-RGO) to form an n-n semiconductor heterojunction LNO/N,P-RGO as a photodiode array-like nanoreactor via hydrothermal treatment. The photodiode array-like nanostructure exposes more active sites that are conducive to light absorption. The robust Ni-C and P-O bonds promote the narrowing of space-charge region at the interface by UV irradiation, thereby improving the transport of photogenerated carriers by visible light irradiation. The LNO/N,P-RGO nanoreactor exhibits excellent photocatalytic hydrogen evolution performance with a yield of up to 354 μmol g−1 h−1 under UV–visible light, which is 50 times higher than that of pure perovskite LNO, and it also displays favorable recycling stability.

3D printed CuFe2O4 electrode with dominant facet (111) for boosting hydrogen evolution performance

The utilization of hydrogen energy is an important way to low carbon economy, and the development of active electrodes is the most critical step for efficient hydrogen evolution reaction. With the addition of KNO3 as a capping agent, the exposed crystal facet of CuFe2O4 is regulated, and the crystal facet (111) becomes dominant. Compared to CuFe2O4 (3 1 1), CuFe2O4 (111) exhibits low barrier of water dissociation and suitable *H binding strength, resulting in high intrinsic activity. Furthermore, the 3D printed electrodes show more excellent performance. At 3D printed CuFe2O4 (111) electrode, the overpotential is only 152 mV (vs. reversible hydrogen electrode) at 100 mA cm−2, and Tafel slope is as low as 33 mV dec-1. In addition, 3D printed CuFe2O4 (111) electrodes shows high stability. The superior performance of 3D printed CuFe2O4 (111) electrodes originates from high intrinsic activity and more exposed active sites. This study provides a new path for the development of efficient, stable and inexpensive monolithic catalyst electrodes for alkaline hydrogen evolution.

Enhanced photocatalytic hydrogen generation efficiency through molybdenum-sulfur dual sites synergistic catalysis

Photocatalysis has gained significant attention in recent years for water splitting, with graphitic carbon nitride (g-C3N4) emerging as a promising candidate. However, the low carrier mobility and the lack of active sites for hydrogen evolution limit photocatalytic hydrogen evolution performance. Herein, this work presents a facile approach to achieve single Mo sites with a unique local coordination structure featuring one Mo atom coordinated with two nitrogen atoms and one sulfur atom. Among the prepared photocatalysts, 6wt% Mo/SCN exhibits the highest photocatalytic hydrogen evolution activity with a yield rate of 4.05mmolg-1 h-1, which is 13 times higher than that of pure g-C3N4 and superior to most of the g-C3N4 series photocatalysts. Experimental results and density functional theory calculations confirm that the Mo single-atom and S atom have synergistic catalysis under the co-modification, and the formed Mo-S bonds will enhance the ability of the substrate to anchor the Mo single-atom to enhance the stability of the photocatalyst. This work offers insights into transition metal single-atom and synergistic catalysis design for photocatalytic hydrogen evolution.

Retraction Note: Visible light-enhanced photocatalytic dye degradation and hydrogen evolution performance of BiVO4 thin films prepared at various annealing temperatures

Retraction Note: Visible light-enhanced photocatalytic dye degradation and hydrogen evolution performance of BiVO4 thin films prepared at various annealing temperatures

Preferential heteroatom substitution into ZnIn2S4 nanosheets boosts photocatalytic hydrogen production

Interior modification through preferential substitution of heteroatoms in 2D materials can rescue surface reactive sites for enhanced charge kinetics and photo-activity. Here, Ru and Ni heteroatoms were successfully incorporated in ZnIn2S4 (ZIS) nanosheets via a simple hydrothermal technique. Ru-ZIS photocatalysts exhibited improved photo–water splitting activity (26,400 µmol. h-1g-1) and good stability than that of Ni-ZIS and pristine ZIS under simulated sunlight, which may be related to the increase in reactive sites with Ru substitution, optimized adsorption-free energy of the reaction intermediates and charge kinetics. Ru substitution influenced Zn site availability and thus coordinated bonding with surrounding S ions. Ru-ZIS showed excellent hydrogen evolution performance and minimal change in Gibbs free energy (ΔGH, ~0eV). By analyzing the density of states, both Ru and S sites had greater H* intermediate absorption abilities. This study elaborates on the effect of preferential heteroatom substitution on photocatalytic performance and has widespread applications.

Enhanced photocatalytic hydrogen evolution performance of Pd/g-C3N4 with carbon vacancies

Exploration of highly active, stable and environmentally friendly photocatalytic materials is key to address the problem for hydrogen production by photocatalytic water splitting. Among all the photocatalysts, graphitic carbon nitride (g-C3N4) has gained attention for its stable graphite-like electronic structure, appropriate band gap (∼2.7 eV), and high stability. However, the limited visible light absorption capacity and fast recombination of electron-hole pairs severely limit the photocatalytic performance of g-C3N4. In this study, Pd/g-C3N4 Schottky heterojunctions with carbon vacancies were prepared by an impregnation method. The surface plasmon resonance (SPR) effect of Pd0 nanoparticles and the incorporation of carbon vacancies synergistically reduce the band gap of g-C3N4, expanding its light response absorption capacity and increasing surface active sites, as a result of these modifications, the separation of electron-hole pairs is effectively improved, and photocatalytic water splitting for hydrogen production is greatly enhanced. Photocatalytic performance of Pd/g-C3N4 photocatalysts demonstrate outstanding hydrogen evolution efficiency under solar light irradiation. A convincing mechanism for the enhanced photocatalytic performance of the Pd/g-C3N4 Schottky heterojunctions was suggested. This investigation emphasizes a straightforward and efficient approach for fabricating of based g-C3N4 composite materials with exceptional photocatalytic efficiency.

Uniaxial Magnetization and Electrocatalytic Performance for Hydrogen Evolution on Electrodeposited Ni Nanowire Array Electrodes with Ultra-High Aspect Ratio.

Ni nanowire array electrodes with an extremely large surface area were made through an electrochemical reduction process utilizing an anodized alumina template with a pore length of 320 µm, pore diameter of 100 nm, and pore aspect ratio of 3200. The electrodeposited Ni nanowire arrays were preferentially oriented in the (111) plane regardless of the deposition potential and exhibited uniaxial magnetic anisotropy with easy magnetization in the axial direction. With respect to the magnetic properties, the squareness and coercivity of the electrodeposited Ni nanowire arrays improved up to 0.8 and 550 Oe, respectively. It was also confirmed that the magnetization reversal was suppressed by increasing the aspect ratio and the hard magnetic performance was improved. The electrocatalytic performance for hydrogen evolution on the electrodeposited Ni nanowire arrays was also investigated and the hydrogen overvoltage was reduced down to ~0.1 V, which was almost 0.2 V lower than that on the electrodeposited Ni films. Additionally, the current density for hydrogen evolution at -1.0 V and -1.5 V vs. Ag/AgCl increased up to approximately -580 A/m2 and -891 A/m2, respectively, due to the extremely large surface area of the electrodeposited Ni nanowire arrays.

Structurally disordered MoSe2 with rich 1T phase as a universal platform for enhanced photocatalytic hydrogen production

The improvement of surface reactivity in noble-metal-free cocatalysts is crucial for the development of efficient and cost-effective photocatalytic systems. However, the influence of crystallinity on catalytic efficacy has received limited attention. Herein, we report the utilization of structurally disordered MoSe2 with abundant 1T phase as a versatile cocatalyst for photocatalytic hydrogen evolution. Using MoSe2/carbon nitride (CN) hybrids as a case study, it is demonstrated that amorphous MoSe2 significantly enhances the hydrogen evolution rate of CN, achieving up to 11.37 μmol h−1, surpassing both low crystallinity (8.24 μmol h−1) and high crystallinity MoSe2 (3.86 μmol h−1). Experimental analysis indicates that the disordered structure of amorphous MoSe2, characterized by coordination-unsaturated surface sites and a rich 1T phase with abundant active sites at the basal plane, predominantly facilitates the conversion of surface-bound protons to hydrogen. Conversely, the heightened charge transfer capacity of the highly crystalline counterpart plays a minor role in enhancing practical catalytic performance. This approach is applicable for enhancing the photocatalytic hydrogen evolution performance of various semiconducting photocatalysts, including CdS, TiO2, and ZnIn2S4, thereby offering novel insights into the advancement of high-performance non-precious catalysts through phase engineering.

NiFeCo-based high entropy alloys nanoparticles coated with N-doped graphene layers as hydrogen evolution catalyst in alkaline solution

Electrochemical water splitting is an environmentally friendly technology for producing hydrogen energy. Recent studies have shown that high entropy alloys (HEAs) and N-doped graphene layers coated alloys have superior hydrogen evolution reaction (HER) performance compared to traditional alloys. This paper presents a simple method for synthesizing N-doped graphene layers coated HEAs with controllable thickness. NiFeCo-based alloy materials are prepared using this method and used as HER catalysts in alkaline conditions. Experimental results and density functional theory (DFT) calculations demonstrate that the CuNiFeCoCrTi@N-doped graphene nanoparticles (CuNiFeCoCrTi@NC NPs) with a graphene shell of 2–3 layers exhibit the best hydrogen evolution performance. The improvement of hydrogen evolution performance should be related to the unique properties of HEAs and coating the surface of alloys with thin graphene shell. This study presents a simple and efficient method for synthesizing HEA@NC NPs, which can be used as an efficient electrocatalyst in alkaline water splitting systems.

Acceleration of the electron transfer for efficient photocatalytic hydrogen evolution via regulating the surfactant around the active center in 2D MOFs

Although surfactants have been proved to be effective in controlling the size and morphology to prepare high-quality two-dimensional (2D) MOF nanosheets, the impact of surfactants remaining on the 2D MOF nanosheets on their microenvironment is rarely reported. In this paper, polyvinylpyrrolidone (PVP) was used as surfactant to synthesize Co-TCPP(Pd) (abbreviated as Co-Pd) nanosheets, and the content of PVP attached to Co-Pd nanosheets was controlled by ethanol treatment, to regulate the microenvironment around Co-Pd nanosheets. The XRD, FT-IR, XPS, TEM, and TG were used to confirm that after ethanol ultrasonic treatment, the PVP content on Co-Pd nanosheets was gradually reduced without damaging the original structure and morphology of Co-Pd nanosheets. PVP attached to Co-Pd nanosheets will slow down the electron migration rate, affecting the microenvironment around co-catalyst Pd, which has been confirmed by EIS, PL and DFT etc. The results exhibited that the Co-Pd-6 obtained by ethanol ultrasonic treatment 6 times showed the more excellent photocatalytic hydrogen evolution activity (8284.25 umol·g−1·h−1), which was 4.02 times as that of Co-Pd-0 (2059.59 umol·g−1·h−1) without ethanol ultrasonic treatment), indicating that PVP will have a negative impact on the microenvironment around the co-catalyst, thereby affecting the photocatalytic hydrogen evolution performance. This study indicates that efficient photocatalytic hydrogen evolution can be achieved via adjusting the microenvironment around the co-catalyst to promote electron transfer.

Modulation of Sulfur Vacancies in ZnIn2S4/MXene Schottky Heterojunction Photocatalyst Promotes Hydrogen Evolution

AbstractThe sustainable production of hydrogen utilizing solar energy is a pivotal strategy for reducing reliance on fossil fuels. ZnIn2S4 (ZIS), as a typical metal sulfide semiconductor, has received extensive attention in photocatalysis. Although the introduction of sulfur (S) vacancies in ZIS to enhance photocatalytic hydrogen production by creating defect energy levels has been explored, detailed studies on the control and modulation of S‐vacancies in ZIS are sparce. This study demonstrates that while moderate levels of S‐vacancies can enhance hydrogen evolution, excessive vacancies may hinder the process, underscoring the importance of S‐vacancy modulation. Guided by theoretical calculations, We have designed and synthesized ZIS with modulated S‐vacancies to realize favorable hydrogen adsorption‐free energy and integrated in a Schottky‐heterojunction with MXene co‐catalysts for enhanced hydrogen evolution. The optimized hydrogen evolution performance of ZnIn2S4/MXene (ZMX) reaches 14.82 mmol g−1 h−1 under visible light irradiation, surpassing many reported ZnIn2S4‐based photocatalysts. The enhanced performance is ascribed to widened light absorption and enhanced carrier transportation realized by S‐vacancy modulation and the co‐catalytic effect. Femtosecond ultrafast absorption (fs‐TA) spectra and other in‐situ/ex‐situ characterizations further prove an efficient separation and transfer in an as‐prepared ZMX catalyst. These findings open up new perspectives for designing catalysts with vacancy modulation.

Cocreation of photogenerated electron and hole collectors on polymeric carbon nitride synergistically promotes carrier separation and reaction kinetics towards propelling photocatalytic hydrogen evolution

It is a challenging issue for the creation of photogenerated carrier collectors on the photocatalyst to drive charge separation and promote reaction kinetics in the photocatalytic reaction. Herein, based on one-step dual-modulation strategy, IrO2 nanodots are modified at the edge of polymeric carbon nitride (PCN) nanosheets and atomically dispersed Ir atoms are implanted in the skeleton of PCN to obtain a unique Ir-PCN/IrO2 photocatalyst. IrO2 nanodots and atomically dispersed Ir atoms act as hole and electron collectors to synergistically promote the carrier separation and reaction kinetics, respectively, thereby greatly improving the photocatalytic hydrogen evolution (PHE) performance. As a result, without adding additional cocatalyst, the PHE rate over the optimal Ir-PCN/IrO2-2% sample reaches up to 1564.4 μmol h−1 g−1 under the visible light irradiation, with achieving an apparent quantum yield (AQY) of 15.7% at 420 nm.

Synthesis of rare earth MOF/CZS materials derived from aromatic tetracarboxylic acids and photocatalytic hydrogen production

With the increasing urgency of clean energy, photocatalytic hydrogen production serves as a sustainable hydrogen manufacturing method to improve the increasing scarcity of fossil fuels and environmental pollution. Herein, Cd0.2Zn0.8S (CZS)-modified Metal-Organic Framework (MOF) composites Pr–NO2–TPTC/CZS were successfully prepared through the reaction of Pr3+, aromatic tetracarboxylic acid, and Cd0.2Zn0.8S nanoparticles. Pr–NO2–TPTC/CZS composite materials exhibited enhanced photolysis performance compared to pure Pr–NO2–TPTC and Cd0.2Zn0.8S materials. With the decrease of Cd0.2Zn0.8S in Pr–NO2–TPTC/CZS composites, the photocatalytic performance of the synthesized composites is constantly improved. Pr–NO2–TPTC/CZS (1:1) photocatalyst exhibited excellent hydrogen evolution performance, with a hydrogen production capacity of 6321 μmol g−1 h−1. Photoluminescence spectroscopy (PL), photocurrent-time test (I-t), and electrochemical impedance spectroscopy (EIS) confirmed that the heterojunction interface formed between Pr–NO2–TPTC and CZS promoted electron-hole separation and transfer. Electron paramagnetic resonance (EPR) indicated that CZS-modified Pr–NO2–TPTC can promote the production of ·OH and ·O2− in the system, thereby increasing the photocatalytic hydrogen production performance. This work provides an effective solution for photocatalytic hydrogen production and a potential method for solving the energy crisis and environmental pollution.

Topological insulator Bi2Te3 and graphene oxide synergistically enhance the photothermal effect and photocatalytic hydrogen evolution activity

Photothermal co-catalysis with the partial conversion of solar energy to thermal energy has the potential to overcome the current bottleneck of realizing efficient photocatalytic hydrogen production with zero artificial energy consumption. However, it is still challenging to design highly efficient photocatalysts that can make use of light and thermal energy synergistically. In this work, we successfully improved the photothermal effect and visible-light-catalyzed hydrogen evolution performance by constructing a novel heterojunction based on the topological insulator Bi2Te3 and graphene oxide (GO) synergistically modified with Zn0.67Cd0.33S. The photocatalytic hydrogen evolution rate of the 1.1 wt% Bi2Te3@0.05% GO@Zn0.67Cd0.33S heterojunctions reached 11.52 mmol/h/g (Apparent Quantum Yield of 21.7%), which was 12.9 times higher than that of pure Zn0.67Cd0.33S. Furthermore, the hydrogen production rate reached 71.79 mmol/h/g without cooling. The improved photocatalytic activity originated from the synergistic enhancement of visible-light absorption and the systematic enhancement of the photothermal effect by the Bi2Te3 and GO. In addition, the high electrical conductivity of Bi2Te3 and the high proton conductivity of GO not only increased the electron transfer rate but also synergistically mediated the acceleration of the hydrogen generation reaction. A strong built-in electric field is formed between Bi2Te3 and Zn0.67Cd0.33S, which greatly facilitates the efficient separation of photogenerated carriers. The obtained results illustrate a promising strategy for the development of efficient new photothermal catalysts.

Preparation of Flower-like Copper Foam Supported Co3O4 Electrocatalyst and Its Hydrogen Evolution Performance

Preparation of Flower-like Copper Foam Supported Co3O4 Electrocatalyst and Its Hydrogen Evolution Performance