Promoted charge separation on 3D interconnected Ti3C2/MoS2/CdS composite for enhanced photocatalytic H2 production

The construction of heterojunction has been regarded as an effective way to promote photocatalytic H₂ evolution activity, in which an intimately interfacial contact between the materials forming heterojunction is a positive effect on enhancing activity. Herein, a ternary 3D interconnected nanocomposite Ti₃C₂/MoS₂/CdS was synthesized by a hydrothermal method. MoS₂ nanosheet with a vertically aligned structure grew on the surface of multi-layered Ti₃C₂ to form 3D Ti₃C₂/MoS₂ with tightly interfacial contact, which works as a cocatalyst for enhancing photocatalytic H₂ evolution. CdS as a photocatalyst covered the surface of Ti₃C₂/MoS₂ to absorb light energy. Benefitting to the synergistic effect between Ti₃C₂ and MoS₂, the Ti₃C₂/MoS₂ further accelerates electron transfer and inhibits the recombination of carriers. The H₂ evolution rate of Ti₃C₂/MoS₂/CdS reaches 15.2 mmol h^?1 g^?1 and the apparent quantum yield is 42.1% at λ = 420 nm. The result provides a useful insight for developing cocatalysts with new nanostructures via controlled interfacial engineering.     

Nanoflower-like Ti3CN@TiO2/CdS heterojunction photocatalyst for efficient photocatalytic water splitting

Solar energy to hydrogen production is an effective way to solve the energy crisis. Here, we report a Ti₃CN@TiO₂/CdS photocatalyst with highly efficient photocatalytic performance. Ti₃CN@TiO₂ materials with nanoflower morphology or lamellar morphology were obtained from Ti₃AlCN by controlling the etching time, and then loaded CdS nanoparticles to improve the photocatalytic efficiency. The physical and chemical properties of the catalyst were characterized by various characterization techniques. Ti₃CN@TiO₂/CdS photocatalyst shows an enhanced photocatalytic activity of 3393.4 μmol g^?1h^?1, much higher than that of CdS and Ti₃CN@TiO₂.^.     

Quasi zero-dimensional MoS2 quantum dots decorated 2D Ti3C2Tx MXene as advanced electrocatalysts for hydrogen evolution reaction

Developing advanced noble-metal-free electrocatalysts for the hydrogen evolution reaction (HER) is still a great challenge. Herein, a novel HER catalyst with quasi zero-dimensional (0D) MoS₂ quantum dots (QDs) supported on two-dimensional (2D) Ti₃C₂T_x MXene nanosheets is facilely synthesized. The MoS₂ QDs/Ti₃C₂T_x nanohybrid retains the unique layer structure, and the MoS₂ QDs are in situ formed and distributed uniformly. The obtained MoS₂ QDs/Ti₃C₂T_x catalyst exhibits superior electrocatalytic activity due to its excellent conductivity, abundant of active sites exposed and a high percentage of 1T metallic phase (～76%) of MoS₂ QDs. Remarkably, an early HER overpotential of 220 mV at 10 mA cm^?2 and a small Tafel slope of 72 mV dec^?1 of MoS₂ QDs/Ti₃C₂T_x are achieved in 0.5 M H₂SO₄ solution. In addition, the exchange current density of MoS₂ QDs/Ti₃C₂T_x is ～5 times larger compared with pure MoS₂, thus demonstrating an accelerated charge transfer during the electrocatalytic process.     

Well-designed NiS/CdS nanoparticles heterojunction for efficient visible-light photocatalytic H2 evolution

Heterojunction photocatalysts based on semiconducting nanoparticles show excellent performance in many photocatalytic reactions. In this study, 0D/0D heterojunction photocatalysts containing CdS and NiS nanoparticles (NPs) were successfully synthesized by a chemical precipitation method. The NiS NPs were grown in situ on CdS NPs, ensuring intimate contact between the semiconductors and improving the separation efficiency of hole-electron pairs. The obtained NiS/CdS composite delivered a photocatalytic H₂ evolution rate (7.49 mmol h^?1 g^?1), which was 39.42 times as high as that of pure CdS (0.19 mmol h^?1 g^?1). This study demonstrates the advantages of 0D/0D heterojunction photocatalysts for visible light-driven photocatalytic hydrogen production.     

Improvement of desorption performance of Mg(BH4)2 by two-dimensional Ti3C2 MXene addition

Magnesium borohydride (Mg(BH₄)₂) is an attractive materials for solid-state hydrogen storage due to its high hydrogen content (14.9 wt%). In the present work, the dehydrogenation performance of Mg(BH₄)₂ by adding different amounts (10, 20, 40, 60 wt%) of two-dimensional layered Ti₃C₂ MXene is studied. The Mg(BH₄)₂-40 wt% Ti₃C₂ composite releases 7.5 wt% hydrogen at 260 °C, whereas the pristine Mg(BH₄)₂ only releases 2.9 wt% hydrogen under identical conditions, and the onset desorption temperature decreases from 210 °C to a relative lower temperature of 82 °C. The special layered structure of Ti₃C₂ MXene and fluorine plays an important role in dehydrogenation process especially at temperatures below 200 °C. The main dehydrogenation reaction is divided into two steps, and activation energy of the Mg(BH₄)₂-40 wt% Ti₃C₂ composite is 151.3 kJ mol⁻¹ and 178.0 kJ mol⁻¹, respectively, which is much lower than that of pure Mg(BH₄)₂.     

A highly efficient A-site deficient perovskite interlaced within two dimensional MXene nanosheets as an active electrocatalyst for hydrogen production

We report a unique composite of La_0.4Sr_0.4Ti_0.9Ni_0.1O_3-δ (LSTN) nanoparticles interlaced with two dimensional Ti₃C₂T_x (MXene) nanosheets, providing high conductivity. LSTN heterostructure synthesized by the sol-gel method produces a large oxygen vacancy and creates a variable valence state while, MXene synthesized from Hydrofluoric acid (HF) treatment resulted in a highly hydrophilic and conductive surface, thereby enhancing the charge transferability. For OER, the LSTN/MXene 66.67% electrode exhibits a benchmark of 10 mA cm^?2 at a potential of 1.56 (V vs RHE) in 1 M KOH. It has exhibited the lowest Tafel slope of 44 mV dec^?1 and highest mass activity (60 mA g^?1 @ 1.59 V) due to quicker ions diffusion and increased available exposed area. Moreover, the efficient LSTN/MXene 66.67% electrode showed good long-term durability during a 24 h stability test at a current density of 100 mA cm^?2. The strong interfacial interaction and high charge transfer among LSTN nanoparticles and 2D MXene nanosheets not only provide good structural strength to the composite but also improves the redox activity of LSTN/MXene 66.67% catalyst towards OER. This work provides improved conductive properties of perovskite by developing a composite of perovskite and MXene, that has significantly enhanced electrochemical properties of the catalyst by undergoing fast kinetics.     

Fabrication of 1D/2D CdS/CoSx direct Z-scheme photocatalyst with enhanced photocatalytic hydrogen evolution performance

In this work, we fabricate a 1D/2D heterojunction photocatalyst composed of n-type CdS nanorods and p-type CoS_x nanoflake. This photocatalyst achieves a hydrogen evolution rate of 9.47 mmol g^?1 h^?1, which is 13.7 times higher than that of pure CdS nanorods. Scanning Kelvin Probe, Mott-Schottky plots, UV–Vis absorption spectra and surface photocarrier orienting reaction results indicate that the enhanced photocatalytic performance of CdS/CoS_x is owing to the fabrication of direct Z-Scheme heterojunction system which greatly improves the utilization, migration and separation rate of photo-generated carriers. To the best of our knowledge, this work is the first time to describe a CdS/CoS_x direct Z-scheme system with 1D/2D nanostructure, which can expedite the transfer process of photogenerated carriers with strong redox energy to participate in photocatalytic reactions.     

Facile synthesis of cobalt modified 2D titanium carbide with enhanced hydrogen evolution performance in alkaline media

2D transition metal carbides, nitrides and carbonitrides, namely the MXenes, attract more and more attentions due to their unique properties. Here, we report a simple one-step molten salt etching method to prepare Co modified MXene hybrid (Ti₃C₂T_x:Co) by the reaction of Ti₃AlC₂ with Lewis acid CoCl₂ at 750 °C. Most of Co atoms aggregates in the interlayered space of Ti₃C₂T_x. Benefitting from the improved electron charge transfer efficiency and increased active sites, the sulfuric acid treated Ti₃C₂T_x:Co-12h hybrid exhibits excellent electrocatalytical activity for hydrogen evolution reaction in alkaline media, delivering a current density of 10 mA cm⁻² at an overpotential of 103.6 mV, which is lower than most noble metal free MXene based electrocatalysts. The results illustrate that the proposed method is very facile and useful to incorporate mid-to-late transition metals into the MXene phase to prepare MXene based HER electrocatalysts.     

Efficient interfacial charge transfer of 2D/2D CoP/CdS heterojunction for extremely boosted photocatalytic H2 evolution performance

Constructing 2D/2D heterojunction photocatalysts has attracted great attentions due to their inherent advantages such as larger interfacial contact areas, short transfer distance of charges and abundant reaction active sites. Herein, 2D/2D CoP/CdS heterojunctions were successfully fabricated and employed in photocatalytic H₂ evolution using lactic acid as sacrificial reagents. The multiple characteristic techniques were adopted to investigate the crystalline phases, morphologies, optical properties and textual structures of heterojunctions. It was found that integrating 2D CoP nanosheets as cocatalysts with 2D CdS nanosheets by Co–S chemical bonds would significantly boost the photocatalytic H₂ evolution performances, and the 7 wt% 2D/2D CoP/CdS heterojunction possessed the maximal H₂ evolution rate of 92.54 mmol g^?1 h^?1, approximately 31 times higher than that of bare 2D CdS nanosheets. Photoelectrochemical, steady photoluminescence (PL) and time-resolved photoluminescence (TRPL) measurements indicated that there existed an effective charge separation and migration over 2D/2D CoP/CdS heterojunction, which then markedly lengthened the photoinduced electrons average lifetimes, retarded the recombination of charge carriers, and caused the dramatically boosted photocatalytic H₂ evolution activity. Moreover, the density functional theory (DFT) calculation further corroborated that the efficient charge transfer occurred at the interfaces of CoP/CdS heterojunction. This present research puts forward a promising strategy to engineer the 2D/2D heterojunction photocatalysts endowed with an appealing photocatalytic H₂ evolution performance.     

Synergistic effects of multiple heterojunctions significantly enhance the photocatalytic H2 evolution rate CdS/La2Ti2O7/NiS2 ternary composites

Novel CdS/La₂Ti₂O₇/NiS₂ ternary composite photocatalysts without noble metal were successfully constructed by a simple hydrothermal method. Under visible light irradiation (λ > 400 nm), the optimal CdS/La₂Ti₂O₇/NiS₂ composite produced H₂ at a rate of about 12.77 mmol g⁻¹ h⁻¹, which was 84 times as high as that of pure CdS. This performance enhancement can be attributed to the formation of multiple heterojunctions (including CdS/NiS₂, CdS/La₂Ti₂O₇ and CdS/La₂Ti₂O₇/NiS₂ interface structures) between the three components in the as-prepared CdS/La₂Ti₂O₇/NiS₂ composites. The formed multiple heterojunctions help to separate electron-hole pairs more quickly and efficiently, thus greatly increasing the photocatalytic activity of the CdS/La₂Ti₂O₇/NiS₂ composites. This is very important for the utlization of solar energy for water splitting.     

MoS2/Ti3C2 heterostructure for efficient visible-light photocatalytic hydrogen generation

The MoS₂/Ti₃C₂ catalyst with a unique sphere/sheet structure were prepared by hydrothermal method. The MoS₂/Ti₃C₂ heterostructure loading 30% Ti₃C₂ has a maximum hydrogen production rate of 6144.7  μmol g⁻¹ h⁻¹, which are 2.3 times higher than those of the pure MoS₂. The heterostructure maintains a high catalytic activity within 4 cycles. The heterostructure not only effectively reduce the recombination of photogenerated electrons and holes, but also provide more activation sites, which promotes the photocatalytic hydrogen evolution reaction (HER). These works can provide reference for the development of efficient catalysts in photocatalytic hydrogen evolution.     

Multifunctional Co3O4/Ti3C2Tx MXene nanocomposites for integrated all solid-state asymmetric supercapacitors and energy-saving electrochemical systems of H2 production by urea and alcohols electrolysis

Co₃O₄/Ti₃C₂T_x MXene nanocomposites have been fabricated by vacuum filtration and hydrothermal-annealing methods, and their electrochemical performance were investigated for energy storage and conversion, systematically. As electrode materials, Co₃O₄/Ti₃C₂T_x MXene nanocomposites in 6 M KOH solution demonstrated the specific capacitance of 240.1 F g^?1 at 0.1 A g^?1 and the long-term cycle stability. The solid-state asymmetric supercapacitors exhibited an operating potential window of 1.4 V, a specific capacitance of 97.9 F g^?1at 0.25 A g^?1, an energy density of 95.9 Wh kg^?1 at a power density of 630.4 W kg^?1, and excellent long-term durability. Furthermore, the connected solid-state asymmetric supercapacitors inseries and parallels presented the promising practical applications. Besides, Co₃O₄/Ti₃C₂T_x nanocomposites displayed outstanding catalytic behaviors for energy-saving H₂ generation by urea and alcohols electrolysis. The electrolyzer in KOH + CH₃CH₂OH electrolyte required only 1.33 V potential to deliver the current density of 0.5 A g^?1. Especially, the elctrochemical system of H₂ production by The electrolyzer and the powered solid-state asymmetric supercapacitors based on Co₃O₄/Ti₃C₂T_x nanocomposites was constructed, demonstrating outstanding properties of H₂ production. Therefore, this study not only shows enormous potential of Co₃O₄/Ti₃C₂T_x nanocomposites as a portable power supply but also indicates its great opportunities in energy-saving H₂ production in practical applications.     

Improving the hydrogen storage performance of lithium borohydride by Ti3C2 MXene

Two-dimensional layered material of Ti₃C₂ has been used to improve the hydrogen desorption properties of LiBH₄. The results of temperature-programmed dehydrogenation (TPD) and isotherm dehydrogenation (TD) demonstrate that adding the Ti₃C₂ contributes to the hydrogen storage performance of LiBH₄. The dehydrogenation temperature decreases and the dehydrogenation rate increases with increasing the adding amounts of Ti₃C₂. The onset dehydrogenation temperature of LiBH₄ + 40 wt% Ti₃C₂ composite is 120 °C and approximately 5.37 wt% hydrogen is liberated within 1 h at 350 °C. Furthermore, the activation energy of LiBH₄ + wt.% Ti₃C₂ is also greatly reduced to 70.3 kJ/mol, much lower than that of pure LiBH₄. The remarkable dehydrogenation property of the LiBH₄+ 40 wt% Ti₃C₂ may be due to the layered active Ti-containing Ti₃C₂ and the high surface area of MXene.     

In-situ synthesis of ternary heterojunctions via g-C3N4 coupling with noble-metal-free NiS and CdS with efficient visible-light-induced photocatalytic H2 evolution and mechanism insight

The two-dimensional (2D) graphitic carbon nitride (g-C₃N₄) nanosheets based composites are prepared in the form of the NiS/g-C₃N₄, CdS/g-C₃N₄ and CdS/NiS/g-C₃N₄ using a facile and reliable method of chemical deposition. The TEM and HRTEM images demonstrated a spectacular representation of the 2D lamellar microstructure of the g-C₃N₄ with adequately attached CdS and NiS nanoparticles. The changes in crystallinity and the surface elemental valence states of composites with the incorporation of two metal sulphides are studied, which confirmed the formation of composites. The photocatalytic response of the composites was estimated by photodegradation of Rhodamine B (C₂₈H₃₁ClN₂O₃–RhB), and the ternary composite CdS/NiS/g-C₃N₄ samples exhibited the superior photocatalytic performance. Further, the free radical capture and electron paramagnetic resonance (EPR) spectroscopy experiments identified the main active species that contributed to the photocatalytic reaction. Besides, the samples’ photocatalytic performance was evaluated by photocatalytic hydrogen production. The stability of the performance-optimized composite was determined by employing cyclic experiments over five cycles. The CdS/NiS/g-C₃N₄ showed the highest efficiency of hydrogen production i.e. about 423.37 μmol.g^?1.h^?1, which is 2.89 times that of the pristine g-C₃N₄. Finally, two types of heterojunction structures were proposed to interpret the enhanced photocatalytic efficiency.     

Construction of Co-decorated 3D nitrogen doped-carbon nanotube/Ti3C2Tx-MXene as efficient hydrogen evolution electrocatalyst

Rational design of transition metal catalysts with robust and durable electrocatalytic activity for hydrogen evolution reactions (HER) is extremely important for renewable energy conversion and storage, as well as water splitting. Heteroatom doping has emerged as a feasible strategy for enhancing electrocatalytic activity. Here, cobalt nanoparticles (Co-NPs) were coated with nitrogen-doped carbon nanotubes (NCNTs) prepared via an in situ growth on accordion-like Ti₃C₂T_x-MXene (Co-NCNT/Ti₃C₂T_x). Such an intriguing structure showed great features: abundant anchoring sites for NCNT in situ growth, intimate integration of Co-NPs and NCNTs, high-speed electron transfer between 1D NCNTs and 2D Ti₃C₂T_x-MXenes, and a large number of effective catalytic active sites. This Co-NCNT/Ti₃C₂T_x hybrid catalyst was demonstrated to possess excellent HER performance with low overpotential (η₁₀, 190 mV), small Tafel slope (78.4 mV dec⁻¹), large electrochemically active surface area, and good long-term stability, thus outperforming many reported electrocatalysts. The present strategy provided a facile route for the design of transition metal HER catalysts with NCNT and MXene.     

In-situ growth of CdS quantum dots on g-C3N4 nanosheets for highly efficient photocatalytic hydrogen generation under visible light irradiation

Well dispersed CdS quantum dots were successfully grown in-situ on g-C₃N₄ nanosheets through a solvothermal method involving dimethyl sulfoxide. The resultant CdS–C₃N₄ nanocomposites exhibit remarkably higher efficiency for photocatalytic hydrogen evolution under visible light irradiation as compared to pure g-C₃N₄. The optimal composite with 12 wt% CdS showed a hydrogen evolution rate of 4.494 mmol h⁻¹ g⁻¹, which is more than 115 times higher than that of pure g-C₃N₄. The enhanced photocatalytic activity induced by the in-situ grown CdS quantum dots is attributed to the interfacial transfer of photogenerated electrons and holes between g-C₃N₄ and CdS, which leads to effective charge separation on both parts.     

High-efficiency charge separation of Z-scheme 2D/2D C3N4/C3N5 nonmetal VdW heterojunction photocatalyst with enhanced hydrogen evolution activity and stability

The interfacial charge transfer control is a key and arduous issue for propelling the migration/separation of photogenerated carriers for heterojunction photocatalysts. Here, a new 2D/2D C₃N₄/C₃N₅ nonmetal van der Waals (VdW) heterojunction is fabricated by the simple self-assembly technique in acidic medium, whose charge separation efficiency is promoted dramatically, thus being endowed with the high-efficiency photocatalytic hydrogen evolution (PHE) performance. The PHE rate reaches up to 3.33 mmol h^?1 g^?1 under the visible light and the apparent quantum efficiency (AQE) of 20.6% is achieved at 420 nm on the optimal 2D/2D C₃N₄/C₃N₅-5% sample. Furthermore, the 2D/2D C₃N₄/C₃N₅ nonmetal VdW heterojunction also exhibits the desired stability because there was no significant decrease after PHE reaction of 10 cycles with total 40 h. Such outstanding PHE activity and stability originate from the impelled separation of photoinduced charge carriers and the powerful interfacial interaction through forming Z-Scheme charge transfer path and π-π coupling effect between C₃N₄ and C₃N₅ nanosheets. This work takes a significant guiding and demonstration for designing and exploiting other novel nonmetallic polymer-based VdW heterojunctions in the photocatalytic application field.     

Additional electron transfer channels of thermostable 0D Cs(Pb: Pt)Br3 perovskite quantum dots /2D accordion-like Ni-MOF nanojunction for photocatalytic H2 evolution

Overcoming the low charge transfer efficiency and poor photothermal stability of halide perovskite quantum dots (QDs) is the booster to achieve photocatalytic applications. In this paper, the Pt²⁺-doped CsPbBr₃ QDs/two-dimensional accordion-like Ni-MOF (CPPB QDs/Ni-MOF) composite was firstly synthesized by fixing the CPPB QDs into the pores of Ni-MOF. Electron separation and transfer efficiency were analyzed by PL spectra and electrochemical data. The photocatalyst exhibited outstanding photocatalytic performance in hydrogen (H₂) evolution. The optimal H₂ evolution efficiency of the composite reached 153.6 μmol h^?1, which was about 9 times than that of pure Ni-MOF and remained 134.8 μmol h^?1 after the cycle test. The splendid efficiency could be benefited from the advantages of 2D layered structure of Ni-MOF and the high charge separation and transmission efficiency of CPPB QDs. Finally, the mechanism of electron migration and additional electron transfer channels between composite interfaces was further demonstrated by density functional theory (DFT) calculations. The present work opens up a novel perspective for photocatalytic applications of doped halide perovskite QDs/Ni-MOF nanocomposites.     

The construction of 3D hierarchical CdS/NiAl-LDH photocatalyst for efficient hydrogen evolution

The development of excellent photocatalysts for hydrogen evolution is of great significance to solving the global energy crisis. In this work, a novel 3D hierarchical CdS/NiAl-LDH photocatalyst was fabricated by a facile electrostatic assembly strategy, which was composed of 1D CdS nanorods and 3D flower-like NiAl-LDH microspheres. Under the visible irradiation, the CNA-20 hierarchical photocatalyst presents the optimum hydrogen evolution rate achieved to 3.24 mmol g^?1 h^?1, which is improved 6.23-fold in comparison with the pure CdS. Through the analysis of energy band structures and first-principles calculation, the type-Ⅱ charge transfer mechanism was proposed. Driven by the built-in electric field, as well as the effect of intimate interface contact of CdS and NiAl-LDH, the photogenerated charge could be achieved rapidly separate and migrate, which effectively promotes the H₂ evolution. This well-designed synergistic 1D/3D interface interaction and provides an economic approach to rationally developing metal-free photocatalysts for hydrogen production.     

NiFe LDH/Ti3C2Tx/nickel foam as a binder-free electrode with enhanced oxygen evolution reaction performance

In this work, NiFe LDH/Ti₃C₂T_x/Nickel foam (NF) was successfully prepared as a binder-free electrode by depositing NiFe layered double hydroxide (LDH) nanosheets on Ti₃C₂T_x/NF substrate through electrodeposition approach. The strong electrostatic interactions between the negatively charged surface of MXene and positively charged NF substrate enabled the direct growth of NiFe LDH nanosheets on Ti₃C₂T_x/NF substrate. As a result, the as-prepared NiFe LDH/Ti₃C₂T_x/NF electrode exhibited an excellent OER performance, fast catalytic reaction kinetics and good chemical stability. Its overpotential reached 200 mV at a current density of 10 mA cm^?2, and the cycling tests suggested a good cycling stability.