NiCoP nanoparticles anchored on CdS nanorods for enhanced hydrogen production by visible light-driven formic acid dehydrogenation

Photocatalytic dehydrogenation of formic acid (FA), HCOOH→H₂+CO₂, is a promising strategy for hydrogen production. Although tremendous efforts have been made, developing efficient and robust system driven by visible light without noble metal still remains a huge challenge. Herein, we report for the first time the use of NiCoP nanoparticles anchored on CdS nanorods (NiCoP@CdS NRs) as a highly efficient and robust catalyst for photocatalytic FA dehydrogenation. NiCoP nanoparticles as cocatalyst can effectively separate the electron-hole pairs generated by CdS NRs. The H₂ production rate of the NiCoP@CdS nanorods reached ~354 μmol mg⁻¹ h⁻¹ under visible light irradiation (λ > 420 nm) and the apparent quantum yield (AQY) was ~45.5 % at 420 nm which are among the best values ever reported in photocatalytic FA dehydrogenation systems. This work provides a prospective strategy for developing noble-metal-free photocatalytic FA dehydrogenation systems and hydrogen-based energy applications.     

A DFT study on production of hydrogen from biomass-derived formic acid catalyzed by Pt–TiO2

Production and storage of hydrogen from biomass component by using efficient catalysts, it can finely maintain the future energy of the world and reduce human dependence on fossil fuels. Hydrogen production mechanism via formic acid decomposition on the TiO₂ anatase (101) and Pt–TiO₂ surfaces in the solvent (water) and gaseous conditions performed by density functional theory (DFT) calculation. Regarding to the proposed routes, decomposition reaction of formic acid on TiO₂ surface incline to be followed by second route in the water which is acceptable in terms of energy. Decomposition reaction of formic acid on Pt–TiO₂ surface prefers to do it via first route (rotation around CO bond of formic acid) in solvent conditions. Furthermore, adsorption energy and geometric changes of formic acid on TiO₂ anatase (101) and Pt–TiO₂ surface in gaseous and solvent conditions were clearly studied.     

Recent progress in hydrogen production from formic acid decomposition

Formic acid, as the simplest carboxylic acid which can be obtained as an industrial by-product, is colorless, low toxicity, and easy to transport and storage at room temperature. Recently, Formic acid has aroused wide-spread interest as a promising material for hydrogen storage. Compared to other organic small molecules, the temperature for formic acid decomposition to produce hydrogen is lower, resulting in less CO toxicant species. Lots of catalysts on both homogeneous catalysts and heterogeneous were reported for the decomposition of formic acid to yield hydrogen and carbon dioxide at mild condition. In this paper, the recent development of mechanism and the material study for both homogeneous catalysts and heterogeneous catalysts are reviewed in detail.     

Co/multi-walled carbon nanotubes as highly efficient catalytic nanoreactor for hydrogen production from formic acid

Formic acid is well-recognized as safe and convenient hydrogen carrier. Development of active and cost-effective catalysts for formic acid to hydrogen conversion is important problem of hydrogen energy field. Herein, we report on new Co catalysts supported on oxidized multi-walled carbon nanotubes (MWCNTs), which demonstrate high efficiency in the gas-phase formic acid decomposition affording molecular hydrogen. Various parameters of the catalysts, Co loading, MWCNTs structure, and nanotubes treatment conditions, have been investigated in terms of their influence on the catalytic properties. The catalysts morphology has been characterized with a set of physicochemical methods. It is found that the catalytic activity of Co particles depends on their electronic state and location on the support. Co species located inside the MWCNTs channels are less active than Co species stabilized on the outer surface. An increase in the content of Co nanoparticles on the MWCNT outer surface leads to a higher catalytic activity.     

ZnIn2S4 modified CaTiO3 nanocubes with enhanced photocatalytic hydrogen performance

Novel ZnIn₂S₄/CaTiO₃ nanocubes were prepared by a two-step method and used as a visible light photocatalyst for efficient hydrogen production. The control of the content of CaTiO₃ could effectively change the photocatalytic H₂ production activity of ZnIn₂S₄/CaTiO₃ nanocubes, and the maximum H₂ evolution amount reached to 133116.43 μmol g⁻¹ in 6 h. The photocatalytic hydrogen production efficiency of ZnIn₂S₄/CaTiO₃ nanocubes was almost 4.5 times higher than that of pure ZnIn₂S₄. The electrochemical impedance spectrum of ZnIn₂S₄/CaTiO₃ exhibited the smallest arc radius, time-resolved PL spectrum showed that the carrier lifetime of ZnIn₂S₄/CaTiO₃ nanocubes was 3.29 ns, and the photocurrent density of ZnIn₂S₄/CaTiO₃ reached to 0.81 μA cm⁻². The prepared ZnIn₂S₄/CaTiO₃ nanocubes increased visible light absorption, improved the separation and transfer of photo-generated electrons and holes, and inhibited the recombination of photo-generated electron-hole pairs. ZnIn₂S₄/CaTiO₃ nanocubes exhibited the enhanced photocatalytic activity and high stability, and could be used as promising photocatalyst for hydrogen production application.     

Photocatalytic degradation of butyric acid over Cu2O/Bi2WO6 composites for simultaneous production of alkanes and hydrogen gas under UV irradiation

In present study, photocatalytic production of alkanes and hydrogen gas from butyric acid solution over Cu₂O/Bi₂WO₆ composites has been investigated under UV irradiation. The Cu₂O/Bi₂WO₆ heterojunction composites were synthesized by a two-step method, first by a hydrothermal method, and then by a simple reduction precipitation method. The as-prepared samples were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), ultraviolet–visible diffuse reflection spectroscopy (DRS) and photoluminescence spectroscopy (PL). In Cu₂O/Bi₂WO₆ composites, the larger spherical Cu₂O were covered by smaller Bi₂WO₆ nanosheets. The 24.36 wt%Cu₂O/Bi₂WO₆ composite showed the highest photocatalytic activity for production of alkanes and hydrogen gas. The enhancement in photocatalytic activity can be ascribed to increment in light absorption and effective inhibition of recombination of photogenerated carriers at the heterostructure interface. Based on distributions of gaseous products and intermediates in liquid, a possible mechanism for photocatalytic decomposition of butyric acid over Cu₂O/Bi₂WO₆ composites is proposed. Our results provide a method for pollutants removal with simultaneous production of alkanes and hydrogen.     

Fast hydrogen evolution by formic acid decomposition over AuPd/TiO2-NC with enhanced stability

Well-dispersed AuPd nanoparticles were immobilized on TiO₂-NC supports derived from NH₂-MIL-125(Ti) and used as highly active, stable catalysts for hydrogen production from formic acid under mild conditions. The highest total turnover frequency, i.e., 3207 h⁻¹, for formic acid dehydrogenation was achieved with Au₂Pd₈/TiO₂-NC-800 as the catalyst at 60 °C; this is 1.4 times that achieved with Au₂Pd₈/TiO₂–C-800 under the same conditions. The excellent performance of the Au₂Pd₈/TiO₂-NC-800 catalyst originates from the high anatase TiO₂ content, pyridinic N and oxygen vacancies in the support, the small size and alloying effect of the AuPd nanoparticles, and the metal–support synergistic effect. Doping the support with N improves the catalyst stability because N prevents metal particle aggregation to some extent. These results provide guidelines for the future development and applications of catalysts based on TiO₂ and metal–organic-framework-derived carbon-based materials.     

Hollow In2O3 nanotubes decorated with Cd0.67Mo0.33Se QDs for enhanced photocatalytic hydrogen production performance

Novel Cd_0.67Mo_0.33Se/In₂O₃ hollow nanotubes were prepared for photocatalytic hydrogen production application. Under visible light irradiation, Cd_0.67Mo_0.33Se/In₂O₃ hollow nanotubes showed enhanced photocatalytic performance. And the apparent quantum efficiency of 34.86% was obtained when irradiated with 420 nm monochromatic light. The modification of Cd_0.67Mo_0.33Se QDs on the surface of In₂O₃ hollow nanotubes effectively improved the utilization rate of light absorption, increased the separation and migration rate of electrons, inhibited the recombination of photo-generated electron and hole pairs, thus enhancing the photocatalytic activity of water splitting to produce hydrogen. It would be an efficient photocatalyst for hydrogen production application in future.     

Facile fabrication of CdSe/CuInS2 microflowers with efficient photocatalytic hydrogen production activity

Photocatalytic water splitting to produce hydrogen has attracted extensive attention and exhibited broad development prospects. In this work, CuInS₂ microflowers were fabricated through the solvothermal method, and decorated with CdSe quantum dots on the surface. As-prepared CdSe/CuInS₂ microflowers exhibited high photocatalytic hydrogen production activity (10610.37 μmol g^?1 h^?1) and high AQE of 48.97% at 420 nm. The enhanced photocatalytic hydrogen production activity owing to the construction of p-n heterostructure improved light absorption ability, increased electrons transfer efficiency and reduced recombination of photo-induced electrons and holes. Moreover, high stability and cyclic utilization of CdSe/CuInS₂ microflowers were beneficial to photocatalytic hydrogen production application.     

Janus Ga2SeTe and In2SeTe nanosheets: Excellent photocatalysts for hydrogen production under neutral pH

In the past few years, Janus nanosheets have attracted much interest according to their specific structure and considerable potential to address the energy and environmental issues. Herein, the electronic, optical and photocatalytic properties of two-dimensional Janus Ga₂SeTe and In₂SeTe have been studied using ab-initio computations based on the density functional theory. The obtained results show that these nanomaterials exhibit a semiconductor behavior with direct and moderate bandgaps using hybrid HSE06 functional. Subsequently, the understudied compounds present suitable optical conductivity, absorption, transmission and reflectivity for water splitting under the ultraviolet–visible light irradiation. Interestingly, the band edge positions of Janus Ga₂SeTe and In₂SeTe excellently straddle the redox potentials of water under neutral pH. Additionally, the free energy values for the formation of H₂ from H adsorbed on the Ga₂SeTe and In₂SeTe compounds are respectively 1.304eV and 0.976eV at pH = 7. More excitingly, the present study proposes strain engineering approach to improve the photocatalytic performance of the Janus Ga₂SeTe and In₂SeTe monolayers. Specifically, the investigated semiconductors show more appropriate band edge alignment and better hydrogen evolution reaction activity under biaxial tensile strain, which fulfil the water splitting requirements at neutral pH conditions. Our findings conclude that the Janus Ga₂SeTe and In₂SeTe nanosheets are promising candidates for photocatalytic hydrogen production.     

Efficient photocatalytic hydrogen evolution on amorphous MoSx-modified CdS/KTaO3 heterojunctions under visible light irradiation

Constructing heterostructures with efficient charge separation is a promising route to improve photocatalytic hydrogen production. In this paper, MoS_x/CdS/KTaO₃ ternary heterojunction photocatalysts were successfully prepared by a two-step method (hydrothermal method and photo deposition method), which improved the photocatalytic hydrogen evolution activity. The results show that the rate of hydrogen evolution for the optimized photocatalyst is 2.697 mmol g^?1·h^?1under visible light, which is 17 times and 2.6 times of the original CdS (0.159 mmol g^?1 h^?1) and the optimal CdS/KTaO₃(1.033 mmol g^?1 h^?1), respectively, and the ternary photocatalyst also shows good stability. The improvement on photocatalytic hydrogen evolution performance can be attributed to the formation of heterojunction between the prepared composite materials, which effectively promotes the separation and migration of photo-generated carriers. Amorphous MoS_x acts as an electron trap to capture photogenerated electrons, providing active sites for proton reduction. This provides beneficial enlightenment for hydrogen production by efficiently utilizing sunlight to decompose water.     

Z-scheme MoO3-2D SnS nanosheets heterojunction assisted g-C3N4 composite for enhanced photocatalytic hydrogen evolutions

In this work, the 2D SnS/g-C₃N₄ nanosheets have been successfully prepared by a facile ultrasonic and microwave heating approach, which formed intimate interfacial contact and suitable energy band structure. The optimized sample displayed enhanced photocatalytic hydrogen evolution from water assisted with Pt co-catalyst, which is much higher than that of pure g-C₃N₄. After loaded with MoO₃ particles, the stability of photocatalysts displayed significate improvement due to the formed Z-scheme heterojunction. With the characterization, the enhanced hydrogen evolution reaction (HER) performance might be ascribed to the improved light-harvesting capability of the composite, lowered charge-transfer resistance, increased electrical conductivity and the co-catalyst effect of SnS. This study provides insights about SnS assisted HER photocatalysts and a new strategy to improve the stability of metal sulfides photocatalysts.     

Engineering of the N-doped carbon support for improved performance of supported Pd catalysts in hydrogen production from gas-phase formic acid

Development of N-doped Pd/C catalysts for hydrogen production from gas-phase formic acid is a challenge. To elucidate the efficient routes of nitrogen insertion on the surface of a mesoporous carbon support, the latter was treated with melamine (Mel), dicyandiamide or NH₃ at 673 and 823 K. Pyrolysis of the melamine/carbon mixture taken in a 1:2 ratio provides an increase in the reaction rate by a factor of 5. The inserted N-sites strongly interact with Pd leading to the formation of highly dispersed Pd nanoparticles (∼1.6 nm) and active atomically dispersed Pd²⁺ species. With a further increase of the Mel/C ratio, the number of surface N-sites decreases due to occupation of carbon support pores with a g–C₃N₄–type residue. This provides a decrease in the Pd dispersion leading to lower reaction rates. Therefore, melamine is an efficient N precursor. The considered synthesis of N-doped catalysts could be scaled.     

Efficient decomposition of formic acid into hydrogen on Pd nanoparticles anchored in amine-pyridine polymer networks without extra additives at ambient condition

Palladium (Pd) is considered as the most promising catalyst for hydrogen production from formic acid decomposition (FAD), but pristine Pd catalysts are less active and readily to perform activity decay by CO poisoning. Thus the modulation of Pd is critical for its application in H₂ production from FAD. Here a Pd/APPNs catalysts by anchoring ca. 2.1 ± 0.3 nm Pd nanoparticles in the amino-pyridine polymer networks (designated as APPNs) was designed based on so-called metal-support interaction. The strong interaction between Pd and N of amine-pyridine unites was demonstrated by the X-ray photoelectron spectroscopic (XPS) analysis. It suggests the electron transfer between N and Pd, which could lower the d-band center of Pd and further effectively enhance the FAD catalysis performance. The initial FAD TOF value of 512 h^?1 and the activation energy (E_a) of ca. 22.1 kJ mol^?1 give a proper proof for the catalysis enhancement. And the third time FAD run still show a 442 h^?1 TOF, indicating an excellent catalysis stability. In addition, the production analysis by Gas chromatography (GC) show that no CO was detected. This CO-free production was also confirmed through no observation of Surface-enhanced Adsorption Infrared Spectral (SEIRAS) band at 1700-2100 cm^?1 (i.e. the CO_ad species) on Pd/ANNPs surface. This work indicates that direct modification of Pd by the functionalized support (metal-support interaction) could effective enhance the FAD catalysis performance, although further work combined with other tuning means should be push forward.     

Prickly Ni3S2 nanowires modified CdS nanoparticles for highly enhanced visible-light photocatalytic H2 production

The photocatalytic water splitting strategy is one of the most promising ways to achieve clean and renewable solar-to-hydrogen energy conversion. In this study, a highly enhanced photocatalytic H₂ production system has been achieved, using CdS nanoparticles (NPs) decorated on prickly Ni₃S₂ nanowires (NWs) as the light-driven photocatalyst. The photocatalyst was prepared by a co-precipitated method in which spiky Ni NWs were employed as starting material for prickly Ni₃S₂ NWs. Characterization analysis (XRD, TEM, XPS, etc.) show the high purity of Ni₃S₂/CdS hybrid structures and the well deposition of CdS NPs on prickly Ni₃S₂ NWs. Besides, the as synthesized Ni₃S₂/CdS photocatalyst exhibit reduced photoluminescence peak intensity, which means the Ni₃S₂ NWs functions as electron collector and transporter to quench the photoluminescence of CdS. This prickly Ni₃S₂/CdS nanocomposite demonstrates a 70 times higher H₂ production rate than that of pure CdS and a quantum efficiency of 12.3% at the wavelength of 400 nm in the absence of noble metals. This enhanced H₂ production activity is better than the one of CdS loaded with 0.5 wt% Pt. Our findings highlight the potential application of Ni₃S₂/CdS hybrid structures for visible light photocatalytic hydrogen yielding in the energy conversion field.     

Noble metal-free cobalt oxide (CoOx) nanoparticles loaded on titanium dioxide/cadmium sulfide composite for enhanced photocatalytic hydrogen production from water

In this present paper, cobalt oxide (CoO_x) is studied as an effective cocatalyst in a photocatalytic hydrogen production system. CoO_x-loaded titanium dioxide/cadmium sulfide (TiO₂/CdS) semiconductor composites were prepared by a simple solvothermal method and characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), ultraviolet–visible diffuse reflectance spectroscopy (UV–Vis DRS), and X-ray photoelectron spectroscopy (XPS). Photocatalytic hydrogen production was studied using the as-synthesized photocatalysts in aqueous solution containing sodium sulfide (Na₂S)/sodium sulfite (Na₂SO₃) as hole scavengers under visible light irradiation (λ > 400 nm). The optimal cobalt content in CoO_x-loaded TiO₂/CdS composite is determined to be 2.1 wt% and the corresponding rate of hydrogen evolution is 660 μmol g⁻¹ h⁻¹, which is about 7 times higher than TiO₂/CdS and CdS photocatalysts under the same condition. Visible light-driven photocurrents of the semiconductor composites were further measured on a photoelectrochemical electrode, revealing that the photocorrosion of CdS can be prevented due to the presence of TiO₂–CoO_x.     

New insights in the performance and reuse of rGO/TiO2 composites for the photocatalytic hydrogen production

The viability of the photocatalytic hydrogen production is closely related to the performance and long term stability of the photocatalyst. In this work rGO/TiO₂ composites have been synthetized with graphene oxide (GO) ratios from 1% to 10% and experimentally assessed towards hydrogen generation from methanol solutions. The performance of the composite with 2% of rGO (2 GT) has been compared to bare TiO₂ working with 20% volume methanol solution. The hydrogen production initial rate showed similar values with both photocatalysts decreasing after about 24 h. Further analysis of the photocatalytic process at longer times showed the negative influence of hydrogen accumulation in the reaction system. Thus, an experimental procedure with argon purge was developed and the behavior of TiO₂ and 2 GT photocatalysts was compared. It is concluded that TiO₂ keeps its activity after 8 operation cycles while 2 GT performance reduces progressively. This can be attributed to the further reduction of GO and the increase of defects in its structure.     

2-Dimensional metal-organic framework derived N-doped carbon immobilized Pd nanoparticles for hydrogen release from formic acid

Hydrogen release from formic acid is a significant energy supply route. However, the current catalysts suffer from low catalytic efficiency and stability. Herein, a porous N-doped carbon material with high N content (16.87%) and a large surface area (1544 m²·g^?1) were designed using a 2-dimensional metal-organic framework and etching agent potassium chloride. Due to its high N content and large surface area, ultrafine Pd particles are uniformly distributed on the porous N-doped carbon support, which effectively enhances excellent reactivity and enables a TOF value of 2365 h^?1 under additive-free conditions. The research also revealed that the strong interaction between Pd particles and pyridinic-N species can significantly slow metal agglomeration. Hence, the Pd/NC_ZIF-L (KCl) displayed good activity even after 10 cycling experiments, and it is a particularly competitive catalyst for hydrogen release from formic acid.     

In2Se3/CdS nanocomposites as high efficiency photocatalysts for hydrogen production under visible light irradiation

Hydrogen energy is an important clean energy. Using visible light to produce hydrogen by semiconductor photocatalysts is one of the current research hotspots. In this work, In₂Se₃/CdS nanocomposite photocatalysts with different mass content of CdS are prepared. The In₂Se₃/CdS photocatalyst with 85.25% CdS mass content exhibits the optimal photocatalytic hydrogen evolution activity (1.632 mmol g^?1 h^?1), which is much higher than that of CdS (0.715 mmol g^?1 h^?1) and In₂Se₃ (trace). Moreover, the In₂Se₃/CdS photocatalyst still maintains a high hydrogen evolution rate after five cycles. The high photocatalytic activity and stability of the In₂Se₃/CdS nanocomposite is due to the formation of heterojunction between In₂Se₃ and CdS. The existence of heterojunction is confirmed by high resolution transmission electron microscopy image and X-ray photoelectron spectra. Theoretical calculations and experimental results indicate that the electron transfer route at the heterojunction is step-scheme. The step-scheme helps the separation of photogenerated electrons and holes, and maximize the hydrogen evolution activity. This work provides a high efficiency step-scheme photocatalyst for hydrogen production.     

One-step water splitting and NaHCO3 reduction into hydrogen storage material of formate with Fe as the reductant under hydrothermal conditions

In this paper, we give an overview of recent advances in the production of formic acid, as a hydrogen carrier, from CO₂ and water by using the earth-abundant metal of Fe as the reductant under hydrothermal conditions, which mainly includes: 1) hydrogen production from water with Fe; 2) reduction of HCO₃^– to formic acid in the presence and absence of catalysts; 3) proposed reaction mechanisms. The novel options under this study are mainly the use of water as a hydrogen source with metal Fe as a reductant, and the formed Fe_xO_y as an auto-catalyst. Such a process possesses several benefits: (i) water acts not only as a hydrogen source but also as an environmentally benign solvent; (ii) there are no hydrogen requirements, including pumps or storage, because hydrogen is derived from water and reacts with CO₂in situ; (iii) no exotic catalysts or harsh reagents are used; and (iv) the method is simple and highly efficient. This technology can provide a one-step, sustainable and highly efficient way to reduce CO₂ into formic acid using the hydrogen directly from water.