Improved Hydrogen Evolution Research Articles

In-situ engineering of 3D amorphous/crystalline NiFeP/NiMoP/NF composite for improved hydrogen evolution

Developing High-performance, low-cost, and non-noble-metal hydrogen evolution reaction (HER) electrocatalysts are one of the particularly significant elements to triumph over the slow kinetics of water dissociation. However, utilizing non-noble metal electrocatalysts at large-scale applications remains a significant challenge. This work informs the fabrication of porous amorphous NiFeP nanostructures on crystalline NiMoP/NF nanoflakes morphology via straightforward two-step electrodeposition and hydrothermal processes as a binder-free 3D hetero-structured composite catalyst for reliable HER. Based on experimental characterizations and density functional theory (DFT) calculations, the optimized NiFeP@NiMoP@NF electrocatalyst exhibits a favorable amorphous/crystalline morphology and an intrinsic metallic phase. This structure facilitates efficient charge transport and exposes abundant active sites with strong electronic interactions between NiFeP and NiMoP, significantly optimizing the adsorption and desorption energy of H2O and thus leading to easy adsorption of H and OH− on NiFeP@NiMoP and promoting the bubble release, finally improving electrocatalytic HER performance in alkaline media (only need an overpotential of 40 mV to conduct a current density of 10 mA cm−2). The rational and affordable developing technique in this study not only implies the importance of interface engineering in catalyst construction but also opens a new route for synthesizing high-efficiency Ni-based electrocatalysts for a variety of water electrolysis applications.

Pt Single Atoms and Clusters Supported on N-Doped Porous Carbon for Improved Hydrogen Evolution Reaction

Pt Single Atoms and Clusters Supported on N-Doped Porous Carbon for Improved Hydrogen Evolution Reaction

Rational Design of Mesoporous ZnFe2O4@g-C3N4 Heterojunctions for Environmental Remediation and Hydrogen Evolution.

Mesoporous catalysts with a high specific surface area, accessible pore structures, and appropriate band edges are desirable for optimal charge transfer across the interfaces, suppress electron-hole recombination, and promote redox reactions at the active sites. The present study demonstrates the rational design of mesoporous ZnFe2O4@g-C3N4 magnetic nanocomposites (MNCs) with different pore sizes and pore volumes following a combination of facile thermal itching and thermal impregnation methods. The MNCs preserve the structural, morphological, and physical attributes of their counterparts while ensuring their effectiveness and superior catalytic capabilities. The morphological analysis confirms the successful grafting and confinement of ZnFe2O4 nanoparticles with the polymeric g-C3N4 nanosheets to form heterojunctions with numerous interfaces. The MNCs possess uniformly distributed small mesopores (pore size <4 nm), ample active sites, and a high specific surface area of 62.50 m2/g. The mesoporous ZnFe2O4@g-C3N4 notably improve hydrogen evolution rate and methylene blue dye degradation. The optimal loading weight of ZnFe2O4 is 20 %, in which the MNCs display the highest hydrogen evolution rate of 1752 μmol g-1 h-1 and photo-Fenton dye degradation rate constants of 0.147 min-1, upon solar-light illumination. Furthermore, the photocatalysts demonstrate recyclability over five consecutive cycles, confirming their stability, while easy separation using a simple magnet underscores practical utility.

Enhanced Photocatalytic Hydrogen Evolution Activity Driven by the Synergy Between Surface Vacancies and Cocatalysts: Surface Reaction Matters.

The incorporation of defects and cocatalysts is known to be effective in improving photocatalytic activity, yet their coupled contribution to the photocatalytic hydrogen evolution process has not been well-explored. In this study, We demonstrate that the incorporation of S vacancies and NiSe can contribute to the improvement of charge separation efficiency via the formation of a strong electric field within the bulk ZnIn2S4 (ZIS) and on its surface. More importantly, We also demonstrate that the synergy of S vacancies and NiSe benefits the overall hydrogen evolution activity by facilitating the H2O adsorption and dissociation process. This is particularly important for hydrogen evolution taking place under alkaline conditions where the proton concentration is low, allowing ZISv-NiSe (containing abundant S vacancies) to outperform ZIS-NiSe under alkaline conditions. In contrast, under acid conditions, since there are already sufficient amounts of protons available for reaction, the hydrogen evolution activity became governed by the hydrogen adsorption/desorption process rather than the H2O dissociation process. This leads to ZIS-NiSe exhibiting higher activity than ZISv-NiSe due to its more favorable hydrogen adsorption energy. The findings thus provide insights into how defect and cocatalyst modification strategies can be tailor-made to improve hydrogen evolution activity under different pH conditions.

Green hydrogen and acetaldehyde production via photo-induced thermal dehydrogenation of bioethanol over a highly dispersed CuS/ TiO2 catalyst

The emergence of global warming issues has triggered the interest in producing carbon-neutral energy sources and fossil-based chemicals from affordable and renewable feedstocks (e.g., bio-ethanol). Herein, the synthesis of highly dispersed CuS/TiO2 photothermal catalysts is reported for simultaneously converting ethanol into hydrogen and acetaldehyde under simulated sunlight. The catalyst achieved a hydrogen evolution rate of 51.61 mmol g−1 h−1 and an acetaldehyde production rate of 48.63 mmol g−1 h−1, with a maximal acetaldehyde selectivity of 97% among carbon-containing products. Compared to pristine TiO2, the introduction of plasmonic CuS largely extended the light adsorption range and enhanced the photothermal performance, whilst the formation of heterojunction structure improved the charge transfer and separation efficiency. The density functional theory calculation results demonstrate that CuS/TiO2 composite interfaces could significantly lower the activation energy of ethanol dehydrogenation reaction and improve hydrogen evolution reaction ability. This study provides deep insight into understanding and optimizing hot carrier dynamics in photothermal catalytic systems.

Photocatalyst Au@Ni-MOFs with Different Plasmonic Coverages for Improved Hydrogen Evolution from Water.

Plasmonic materials are fundamental photosensitizer materials for photocatalytic reactions. Various structures, including core-shell types, satellite types, and distribution types, have been designed and prepared for the optimization of photocatalytic reactions. However, understanding the profound enhancement mechanism of various structures is still challenging. Thus, the plasmonic coverage is considered to be an index for analyzing the influence mechanism. Here, Au@Ni-MOF core-shell flower sphere-like photocatalysts are prepared, and the size of the flower sphere can be precisely regulated by varying the amount of Au. Thus, different plasmonic coverages are realized through the tuning of spheres of different sizes. The high plasmonic coverage of catalysts can enhance visible light absorption, facilitate the generation of photogenerated electron-hole pairs, and shorten the photogenerated carrier transport distance. Moreover, the exponential relationship between the photocatalytic hydrogen production performance and the plasmonic coverage can also be used as a guide for material design. As a result, a photocatalytic hydrogen production rate of 3389 μmol·g-1·h-1 is achieved in the Au@Ni-MOF sample with high plasmonic coverage, which will advance the plasmonic application in photocatalytic reactions.

Precursor-reforming protocol to hierarchical porous g-C3N4 with N defects for remarkable visible-light-driven hydrogen evolution

The photocatalytic activity of g-C3N4 can be enhanced through precise defect engineering. In this study, hierarchical porous g–C3N4–containing cyano groups and N vacancies was synthesized by thermally polymerizing dicyandiamide precursor in a hydrochloric acid solution of magnesium chloride. The resulting structure comprised crosslinked rod-shaped units with a high aspect ratio, facilitating efficient light transmission and absorption within the material. Furthermore, introducing N defects reduced the bandgap and optimized the electronic structure, thereby enhancing light absorption and exposing active sites effectively. The synergistic effects of N defects and the hierarchical porous structure disrupted the original electronic distribution of g-C3N4, leading to directional separation of photogenerated charge carriers and considerably enhancing hydrogen evolution performance. Consequently, the optimized hpCNX-0.05 sample exhibited markedly improved hydrogen evolution rates, achieving 1703.67 μmol g−1 h−1 under visible light irradiation, approximately 3.16 times higher than that of bulk g-C3N4. Overall, this paper presents a promising strategy for synthesizing hierarchical porous g-C3N4 with N defects to achieve highly efficient H2 production.

Intramolecular Quaternary Carbon Nitride Homojunction for Enhanced Visible Light Hydrogen Production.

In this work, an intramolecular carbon nitride (CN)-based quaternary homojunction functionalized with pyridine rings is prepared via an in situ alkali-assisted copolymerization strategy of bulk CN and 2-aminopyridine for efficient visible light hydrogen generation. In the obtained structure, triazine-based CN (TCN), heptazine-based CN (HCN), pyridine unit incorporated TCN, and pyridine ring inserted HCN constitute a special multicomponent system and form a built-in electric field between the crystalline semiconductors by the arrangement of energy band levels. The electron-withdrawing function of the conjugated heterocycle can trigger the skeleton delocalization and edge induction effect. Highly accelerated photoelectron-hole transfer rates via multi-stepwise charge migration pathways are achieved by the synergistic effect of the functional group modification and molecular quaternary homojunction. Under the addition of 5mg 2-aminopyridine, the resulting homojunction framework exhibits a significantly improved hydrogen evolution rate of 6.64mmol g-1 h-1 with an apparent quantum efficiency of 12.27% at 420nm. Further, the catalyst verifies its potential commercial value since it can produce hydrogen from various real water environments. This study provides a reliable way for the rational design and fabrication of intramolecular multi-homojunction to obtain high-efficient photocatalytic reactions.

Maximizing biofuel production from algal biomass: A study on biohydrogen and bioethanol production using Mg[sbnd]Zn ferrite nanoparticles

Algal biomass is a promising renewable feedstock for biofuel production that does not compete with food crops or require complex pretreatment like lignocellulosic biomass. This study examined biofuel production from two algae: Alkalinema pantanalense (cyanobacteria) and Chlorella vulgaris (green alga). Although there was no significant difference in their biomass, A. pantanalense showed a higher carbohydrate content (204.96 mg L−1) than C. vulgaris (156.07 mg L−1). To maximize reducing sugar release, three pretreatments were tested: thermotacidic, biological using the new fungal isolate Trichoderma longibrachiatum, and biological with nanoparticles. Biological pretreatment with MgZn ferrite nanoparticles (MZF-nps) at 60 mg L−1 concentration gave the best results, significantly enhancing cellulase, β-glucosidase and filter paper cellulase activities by 20.94 % (A. pantanalense) and 18.63 % (C. vulgaris). For biohydrogen production, the co-culture of Klebsiella pneumoniae and Enterobacter cloacae resulted in faster fermentation and improved hydrogen evolution compared to individual cultures. A. pantanalense and C. vulgaris yields were 35.1 mL g−1 and 26.6 mL g−1 dry weight, with maximal cumulative production of 2478 mL L−1 and 1845 mL L−1, respectively. Optimized Saccharomyces cerevisiae bioethanol fermentation conditions included 72 h incubation, 5 % inoculum, 30 °C, pH 5 under shaking condition, yielded 11.2 g L−1 (A. pantanalense) and 7.2 g L−1 (C. vulgaris). Furthermore, MZF-nps hydrolysate significantly increased bioethanol production, by 4.2-fold (A. pantanalense) to 32.45 g L−1 and 3.48-fold (C. vulgaris) to 28.6 g L−1, compared to thermoacidic pretreatment. In summary, biological pretreatment demonstrates the potential of algal biomass as a renewable feedstock for sustainable biofuel production.

Improving NiFe Electrocatalysts through Fluorination-Driven Rearrangements for Neutral Water Electrolysis.

Neutral electrolysis to produce hydrogen is prime challenging owing to the sluggish kinetics of water dissociation for the electrochemical reduction of water to molecular hydrogen. An ion-enriched electrode/electrolyte interface for electrocatalytic reactions can efficiently obtain a stable electrolysis system. Herein, we found that interfacial accumulated fluoride ions and the anchored Pt single atoms/nanoparticles in catalysts can improve hydrogen evolution reaction (HER) activity of NiFe-based hydroxide catalysts, prolonging the operating stability at high current density in neutral conditions. NiFe hydroxide electrode obtains an outstanding performance of 1000mA cm-2 at low overpotential of 218mV with 1000 h operation at 100mA cm-2. Electrochemical experiments and theoretical calculations have demonstrated that the interfacial fluoride contributes to promote the adsorption of Pt to proton for sustaining a large current density at low potential, while the Pt single atoms/nanoparticles provide H adsorption sites. The synergy effect of F and Pt species promotes the formation of Pt─H and F─H bonds, which accelerate the adsorption and dissociation process of H2O and promote the HER reaction with a long-term durability in neutral conditions.

Understanding Performance Limitation of Liquid Alkaline Water Electrolyzers

Liquid alkaline water electrolyzers (LAWEs), being the most commercially mature electrolysis technology, play a pivotal role in large-scale hydrogen production. However, LAWEs suffer from low operational efficiency, primarily due to un-optimized electrode structure and chemical compositions. Thus, we investigated how various electrode configurations could impact LAWE performance. Our results show that Ni felt electrodes outperform the conventional Ni foam thanks to improved electrochemical active surface area (ECSA) and preferred electrode surface structure that minimizes the micro-gaps in between the electrode and separator. By comparing the stainless steel (SS) felt electrodes with Ni felt electrodes, SS not only shows better oxygen evolution reaction activity but also improved hydrogen evolution reaction activity, which is less studied in the literature. We also show that a bilayer structure with small pore radius facing the separator could further improve LAWE performance by further optimizing interfacial contact between electrode and separator. These findings enable LAWEs to sustain 2 A cm−2 at 2.2 V and operate steadily at 1 A cm−2 for nearly 600 h with negligible performance decay. Our studies establish criteria for selecting electrodes to achieve high-performance LAWE and, in turn, expedite the adoption of LAWEs in hydrogen production and the transition towards low-carbon economies.

Efficient Visible Light Photocatalytic Hydrogen Evolution by Boosting the Interfacial Electron Transfer in Mesoporous Mott-Schottky Heterojunctions of Co2P-Modified CdIn2S4 Nanocrystals.

Photocatalytic water splitting for hydrogen generation is an appealing means of sustainable solar energy storage. In the past few years, mesoporous semiconductors have been at the forefront of investigations in low-cost chemical fuel production and energy conversion technologies. Mesoporosity combined with the tunable electronic properties of semiconducting nanocrystals offers the desired large accessible surface and electronic connectivity throughout the framework, thus enhancing photocatalytic activity. In this work, we present the construction of rationally designed 3D mesoporous networks of Co2P-modified CdIn2S4 nanoscale crystals (ca. 5-6 nm in size) through an effective soft-templating synthetic route and demonstrate their impressive performance for visible-light-irradiated catalytic hydrogen production. Spectroscopic characterizations combined with electrochemical studies unravel the multipathway electron transfer dynamics across the interface of Co2P/CdIn2S4 Mott-Schottky nanoheterojunctions and shed light on their impact on the photocatalytic hydrogen evolution chemistry. The strong Mott-Schottky interaction occurring at the heterointerface can regulate the charge transport toward greatly improved hydrogen evolution performance. The hybrid catalyst with 10 wt % Co2P content unveils a H2 evolution rate of 20.9 mmol gcat -1 h-1 under visible light irradiation with an apparent quantum efficiency (AQE) up to 56.1% at 420 nm, which is among the highest reported activities. The understanding of interfacial charge-transfer mechanism could provide valuable insights into the rational development of highly efficient catalysts for clean energy applications.

Hydrogen Spillover Effect in Electrocatalysis: Delving into the Mysteries of the Atomic Migration

Hydrogen spillover effect has recently garnered a lot of attention in the field of electrocatalytic hydrogen evolution reactions. A new avenue for understanding the dynamic behavior of atomic migration in which hydrogen atoms moving on a catalyst surface was opened up by the setup of the word “hydrogen spillover.” However, there is currently a dearth of thorough knowledge regarding the hydrogen spillover effect. Currently, the advancement of sophisticated characterization procedures offers progressively useful information to enhance our grasp of the hydrogen spillover effect. The understanding of material fabrication for hydrogen spillover effect has erupted. Considering these factors, we made an effort to review most of the articles published on the hydrogen spillover effect and carefully analyzed the aspect of material fabrication. All of our attention has been directed toward the molecular pathway that leads to improve hydrogen evolution reactions performance. In addition, we have attempted to elucidate the spillover paths through the utilization of DFT calculations. Furthermore, we provide some preliminary research suggestions and highlight the opportunities and obstacles that are still to be confronted in this study area.

MoS2 supported Ruthenium nanoparticles with abundant sulfur vacancies significantly improved hydrogen evolution reaction

The electrochemical hydrogen evolution reaction (HER) has become one of effective ways to produce hydrogen. MoS2 is a promising electrocatalyst for the HER, and loading noble metal atoms on MoS2 support can further enhance its HER activity. In present work, the CO was employed as a structure-directing agent to in situ synthesize MoS2-n (n = 0, 0.5, 1.0, 1.4 and 2.0 MPa, representing the CO pressure). Among them, the MoS2-1.4 with highest amounts of sulfur vacancies and superior alkaline HER performance was selected as the support for Ru loadings. Sulfur vacancies can stabilize Ru nanoparticles, prevent nanoparticles from aggregating, and facilitate the formation of small-sized nanoparticles. By optimizing the loading amounts of Ru, the 5Ru@MoS2-1.4 with the Ru loading of 5 wt.% and nanoparticle size of 2 nm exhibits the best alkaline HER activity by displaying a low overpotential of 55 mV and Tafel slope of 68.6 mV dec−1 at a current density of 10 mA cm−2 in 1.0 M KOH medium. This can be majorly related to the synergistic effect of MoS2-1.4 support and small-sized Ru nanoparticles, wherein the CO plays a significant role in regulating the structure of MoS2-1.4 support that favors dispersion of Ru nanoparticles. Generally, present work provides a strategy to enhance the HER catalytic performance of MoS2, which is favorable for other highly-efficient catalyst design.

Improving hydrogen evolution reaction efficiency through lattice tuning

Improving hydrogen evolution reaction efficiency through lattice tuning

Fabricating highly active Pt atomically dispersed catalysts with the co-existence of Pt-O1Ni1 single atoms and Pt sub-nanoclusters for improved hydrogen evolution

Atomically dispersed catalysts (ADCs), including single atoms and sub-nanoclusters, simultaneously, are considered as the most promising candidate to boost the reaction kinetics of hydrogen evolution reaction (HER). However, the correlation between the coordination environment of single atoms and catalytic activity has not been clearly discussed in ADCs system. Herein, Pt ADCs with the different coordination structures were fabricated by a facile sulfurate route coupling deposition strategy. Importantly, Pt ADCs, including Pt-O1Ni1 single atoms and Pt sub-nanoclusters (Pt1+n/Ni3S2), show good basic HER activity, which just need 17 mV at 10 mA cm−2. Meanwhile, the turnover frequency for Pt1+n/Ni3S2 is 0.49 H2 s−1 under the overpotential of 100 mV, which is 8.6 times higher than Pt/C. Besides, the assembled RuO2 || Pt1+n/Ni3S2 system could get 100 mA cm−2 current density under 1.7 V cell voltage in alkaline water electrolyzer. Notably, in-situ Raman and attenuated total reflection-surface enhanced infrared absorption spectroscopy reveal that Pt-O1Ni1 coordination is conducive to promoting the fracture of H-O-H bond, realizing the rapid transform of Pt-H* intermediates. Further, density functional theory calculations confirm Pt single atoms with Pt-O1Ni1 coordination environment in Pt1+n/Ni3S2 serves as the main role for HER because Pt-O1Ni1 are more likely to accelerate the production of Pt-H* at the Pt sites, extremely achieving the rapid HER progress. This work discloses the structure-activity relationship in ADCs system, which is essential for the development of highly active electrocatalysts.

Atomically Precise Mo2Cu17 Bimetallic Nanocluster: Synergistic Mo2O4-Coupled Copper Alkynyl Cluster for the Improved Hydrogen Evolution Reaction Performance.

Electrolytic hydrogen production via water splitting holds significant promise for the future of the energy revolution. The design of efficient and abundant catalysts, coupled with a comprehensive understanding of the hydrogen evolution reaction (HER) mechanism, is of paramount importance. In this study, we propose a strategy to craft an atomically precise cluster catalyst with superior HER performance by cocoupling a Mo2O4 structural unit and a Cu(I) alkynyl cluster into a structured framework. The resulting bimetallic cluster, Mo2Cu17, encapsulates a distinctive structure [Mo2O4Cu17(TC4A)4(PhC≡C)6], comprising a binuclear Mo2O4 subunit and a {Cu17(TC4A)2(PhC≡C)6} cluster, both shielded by thiacalix[4]arene (TC4A) and phenylacetylene (PhC≡CH). Expanding our exploration, we synthesized two homoleptic CuI alkynyl clusters coprotected by the TC4A and PhC≡C- ligands: Cu13 and Cu22. Remarkably, Mo2Cu17 demonstrates superior HER efficiency compared to its counterparts, achieving a current density of 10 mA cm-2 in alkaline solution with an overpotential as low as 120 mV, significantly outperforming Cu13 (178 mV) and Cu22 (214 mV) nanoclusters. DFT calculations illuminate the catalytic mechanism and indicate that the intrinsically higher activity of Mo2Cu17 may be attributed to the synergistic Mo2O4-Cu(I) coupling.

Effect of Intrinsic Ferroelectric Phase Transition on Hydrogen Evolution Electrocatalysis

AbstractHeterogeneous electrocatalysis closely relies on the electronic structure of the catalytic materials. The ferroelectric‐to‐paraelectric phase transition of the materials also involves a change in the state of electrons that could impact the electrocatalytic activity, but such correlation remains unexplored. Here, we demonstrate experimentally and theoretically that the intrinsic electrocatalytic activity could be regulated as exampled by hydrogen evolution reaction catalysis over two‐dimensional ferroelectric CuInP2S6. The obvious discontinuity in the overpotential and apparent activation energy values for CuInP2S6 electrode are illustrated during the ferroelectric‐to‐paraelectric phase transition caused by copper displacement around Tc point (318 K), revealing the ferroelectro‐catalytic effect on thermodynamics and kinetics of electrocatalysis. When loading Pt single atom on the CuInP2S6, the paraelectric phase one showed an improved hydrogen evolution activity with smaller apparent activation energy over the ferroelectric phase counterpart. This is attributed to the copper hopping between two sulfur planes, which alternate between strong and weak H adsorption at the Pt sites to simultaneously promote H+ reactant adsorption and H2 product desorption.

Mechanism insight into the N-C polar bond and Pd-Co heterojunction for improved hydrogen evolution activity

Constructing platinum-like materials with excellent catalytic activity and low cost has great significance for hydrogen evolution reaction (HER) during electrolysis of water. Herein, palladium nanoparticles (NPs) deposition on the surface of Co NPs using nitrogen-doped carbon (NC) as substrate, denoted as N-ZIFC/CoPd-30, are manufactured and served as HER electrocatalysts. Characterization results and density functional theory calculations validate that Pd-Co heterojunctions with NC acting as "electron donators" promote the Pd species transiting to the electron-rich state based on an efficient electron transfer mechanism, namely the N-C polar bonds induced strong metal-support interaction effect. The electron-rich Pd sites are beneficial to HER. Satisfactorily, N-ZIFC/CoPd-30 have only low overpotentials of 16, 162, and 13mV@-10 mA cm-2 with the small Tafel slopes of 98mV/decade, 126mV/decade, and 72mV/decade in pH of 13, 7, and 0, respectively. The success in fabricating N-ZIFC/CoPd opens a promising path to constructing other platinum-like electrocatalysts with high HER activity.

Effect of Intrinsic Ferroelectric Phase Transition on Hydrogen Evolution Electrocatalysis.

Heterogeneous electrocatalysis closely relies on the electronic structure of the catalytic materials. The ferroelectric-to-paraelectric phase transition of the materials also involves a change in the state of electrons that could impact the electrocatalytic activity, but such correlation remains unexplored. Here, we demonstrate experimentally and theoretically that the intrinsic electrocatalytic activity could be regulated as exampled by hydrogen evolution reaction catalysis over two-dimensional ferroelectric CuInP2S6. The obvious discontinuity in the overpotential and apparent activation energy values for CuInP2S6 electrode are illustrated during the ferroelectric-to-paraelectric phase transition caused by copper displacement around Tc point (318 K), revealing the ferroelectro-catalytic effect on thermodynamics and kinetics of electrocatalysis. When loading Pt single atom on the CuInP2S6, the paraelectric phase one showed an improved hydrogen evolution activity with smaller apparent activation energy over the ferroelectric phase counterpart. This is attributed to the copper hopping between two sulfur planes, which alternate between strong and weak H adsorption at the Pt sites to simultaneously promote H+ reactant adsorption and H2 product desorption.