Stoichiometric H2 Research Articles

Gradient pulsed transient plasma for initiation of detonation

The formation of a gradient of atomic oxygen is demonstrated by means of a nanosecond non-equilibrium plasma for a varying gap size plane-to-plane electrode. Using a flat high-voltage electrode in front of a rounded triangle a 2.9 to 5 cm gap is formed over a 9.8 cm span. ICCD imaging determined an adequate ground electrode shape and slope to create a gradient. The plasma is formed by three consecutive high voltage pulses of -30, -40 and -50 kV in 100 mbar of air. O-TALIF measurements confirm that atomic oxygen production changed with gap size within the same plasma. This setup will be used to test detonation initiation by Zel’dovich gradient mechanisms in stoichiometric H2:O2 mixtures.Novelty and Significance: A novel configuration of a nanosecond non-equilibrium discharge was developed to create a controllable gradient of atomic oxygen. This was achieved by using varying gap plane-to-plane electrodes to generate an electric field of varying strength along the length of the gap. This setup will be tested in combustible mixtures to initiate a detonation wave using a gradient mechanism of Zel’dovich.

(Invited) Polymeric Carbon Nitride for Photocatalytic Overall Water Splitting

Photocatalytic overall water splitting can be achieved using Z-scheme systems that mimic natural photosynthesis by combining dissimilar semiconductors in series. However, coupling well-suited H2- and O2-evolving components remains challenging. Here, we fabricate a Z-scheme system for photocatalytic overall water splitting based on boron-doped, nitrogen-deficient carbon nitride two-dimensional (2D) nanosheets. We prepare ultrathin carbon nitride nanosheets with varying levels of boron dopants and nitrogen defects, which leads to nanosheets that can act as either H2- or O2-evolving photocatalysts. Using an electrostatic self-assembly strategy, the nanosheets are coupled to obtain a 2D/2D polymeric heterostructure. Owing to their ultrathin nanostructures, strong interfacial interaction and staggered band alignment, a Z-scheme route for efficient charge-carrier separation and transfer is realized. The obtained heterostructure achieves stoichiometric H2 and O2 evolution in the presence of Pt and Co(OH)2 co-catalysts, and the solar-to-hydrogen efficiency reaches 1.16% under one-sun illumination.

Pore-scale resolved simulation of quenching, acceleration, and transition to detonation of hydrogen explosions by metal foams

Pore-scale simulations of quenching, acceleration, and transition to detonation of gaseous hydrogen explosions by metal foams were performed. The model solves the three dimensional compressible reactive Navier-Stokes equations with detailed chemistry in a closed square channel with a metal foam placed inside. The structures of the foam were fully resolved using an immersed boundary method. Stoichiometric mixtures of hydrogen-oxygen and hydrogen-air were considered. An explosion in the channel was initiated with a high-pressure and high-temperature spark. The simulation results show that the explosion can be quenched, accelerate, or transition to detonation depending on the foam pores-per-inch (PPI). Hydrogen-air explosions were quenched with foams of ∼39 PPI or higher due to heat losses from the flame, which is consistent with experimental observations. The explosion was not quenched by foams with low PPI. Instead the low PPI foams exacerbated the explosion by causing flame acceleration. Worse, a 78 PPI foam caused a stoichiometric H2 and O2 mixture to transition to detonation. Hydraulic resistance due to products venting away from the flame surface was found to produce strong pressure gradients within the foam. This causes a self-pressurizing effect that grows as the flame propagates further into the foam. The pressure within the foam grows and steepens into a shock. The shock initiated the detonation by a Mach reflection, which is similar to deflagration-to-detonation transition mechanisms in traditional obstacle-laden channels. Statement of SignificanceMetal foam structures are often used as devices to inhibit flames in scenarios where explosion hazards are a concern. Direct numerical simulations were performed to increase understanding of how flames and explosions interact with metal foams. The simulation results show that high pores-per-inch (PPI) foams quench the explosion by removing heat from the flame. Lower PPI foams can have the opposite effect and exacerbate the explosion by promoting flame acceleration or even transition to detonation. Flames self-pressurize as they propagate through low PPI foams due to hydrodynamic friction and gas-dynamic effects from flowing product gases. In extreme cases, the pressure waves near the flame can steepen into a shock and initiate a detonation. These results indicate that improperly selected metal foam flame arresters can exacerbate the explosion.

Valorizing the Steel Industry Off-Gases: Proof of Concept and Plantwide Design of an Electrified and Catalyst-Free Reverse Water-Gas-Shift-Based Route to Methanol.

Conversion of steel industry off-gases to value-added chemicals enabled by renewable electricity can significantly reduce the environmental burden of the steelmaking process. Herein, we demonstrate that CO2 reduction by H2, both contained in steel mill off-gases, to form syngas via the reverse water-gas-shift reaction is effectively performed by nanosecond pulsed discharges at atmospheric pressure. The experimental results suggest the following: (i) An optimum interelectrode distance exists, maximizing CO2 conversion. (ii) CO2 conversion at constant SEI follows a nonmonotonic trend with H2 excess. CO2 conversion increases with H2 excess up to H2:CO2 = 3:1 upon shifting the chemical equilibrium. At larger H2:CO2, both gas cooling, promoted by the high H2 content, and hindered CO2 collisions in a highly diluted stream hamper CO2 conversion. (iii) SEI enhances CO2 conversion, but the effect decreases with increasing SEI due to equilibrium limitations. A stoichiometric H2:CO2 feed ratio in the plasma reactor is recommended for higher energy efficiency. Intensifying MeOH productivity via SEI elevation is not advised as a 2-fold SEI increase results only in 17% higher MeOH throughput.

H2 Production from Real Wastes of Polyethylene Terephthalate and Polylactic Acid using CNx/Ni2P Nanocatalyst

In this study, H2(g) production from real wastes of polyethylene terephthalate and polylactic acid using CNx/Ni2P nanocatalyst was investigated with photoreforming process. Optimum experimental conditions were found at ultrasonicated 4.8 mg/ml CNx/Ni2P nanocatalyst, at pre-treated 20 mg/ml polyethylene terephthalate, at pre-treated 20 mg/ml polylactic acid, at 4 ml aqueous 1 M KOH, at 10 ml internal volume of sealed photoreactor under anaerobic conditions, at 1200 W Xe solar lamp, at 60 h photoreforming solar irradiation time, at AM 1.0G, at 150 mW/cm2, at 25°C, respectively. XRD, FESEM, EDX, FTIR, TEM, DRS and XPS analyzes were performed for characterization studies of microplastics. Polyethylene terephthalate and polylactic acid measurements were measured in inductively coupled plasma mass spectrometry (ICP-MS). H2(g) measurements were made in gas chromatography–mass spectrometry (GC-MS). The maximum 41.40 ± 5.10 and 48.60 ± 3.12 µmol H2 / gsub yields were measured for CNx=20 mg/ml and for Ni2P=20 mg/ml, respectively. The maximum 18.26 ± 1.18 and 52.41 ± 7.29 µmol H2 / gsub H2(g) production yields were found for non-sonicated CNx/Ni2P and ultra-sonicated CNx/Ni2P nanocatalyst, respectively, after 24 h photoreforming solar irradition time. The maximum 123.75 ± 11.92 and 267.41 ± 24.65 µmol H2 / gsub H2(g) production yield was measured for polyethylene terephthalate and polylactic acid, respectively, after 60 h photoreforming solar irradiation time. The maximum 6.57 ± 0.87Percentage and 2.43 ± 0.38Percentage stoichiometric H2 conversion yields were observed for polyethylene terephthalate and polylactic acid, respectively, after 60 h photoreforming solar irradition time. The maximum 96 and 57 μmol H2 / gsub H2(g) yields for polyethylene terephthalate were obtained over CNx/Ni2P and H2NCNx/Ni2P, respectively, after 60 h photoreforming solar irradiation time. The maximum 182 and 173 μmol H2 / gsub H2(g) yields for polylactic acid were observed over CNx/Ni2P and H2NCNx/Ni2P, respectively, after 60 h photoreforming solar irradiation time. The maximum 4.85 ± 0.62, 88.37 ± 10.74, 26.55 ± 1.95, 21.94 ± 1.86, 75.30 ± 9.34, 60.07 ± 5.11 and 14.61 ± 2.14 μmol H2 / gsub H2(g) production yields were obtained for Acetate, Ethylene glycol, Formate, Glycolate, Glyoxal, Lactate and Terephthalate oxidation intermediates, respectively, after 24 h photoreforming solar irradiation times. 126 nmol Acetate, 131 nmol Formate, 5 nmol Glycolate and 6200 nmol Glyoxal organic oxidation intermediates for polyethylene terephthalate with CNx/Ni2P nanocatalyst were found after 7 days photoreforming solar irradiation time. 67 nmol Acetate and 63 nmol Formate organic oxidation intermediates for polylactic acid with CNx/Ni2P nanocatalyst were obtained after 7 days photoreforming solar irradiation time. Photoreforming process is a very effective, easy to apply, economical and environmentally friendly method for the removal of plastic and microplastic wastes.

Modulating charge centers and vacancies in P-CoNi loaded phosphorus-doped ZnIn2S4 nanosheets for H2 and H2O2 photosynthesis from pure water

Photocatalytic water splitting has recently attracted increasing interests for solar to chemical energy conversion. Nevertheless, the high-efficiency process for photocatalytic water splitting is driven by recombination of photogenerated electron-hole pairs and the resultant low H2 productivity. Herein, we demonstrate that P-doping induced positive charge centers (Pδ+) and indium vacancies (VIn) in ZnIn2S4 (ZIS) nanosheets can significantly promote photosplitting pure water to simultaneously produce H2 and H2O2. Microstructural and spectroscopic analysis suggest that Pδ+ and VIn can trap photogenerated electrons and holes, respectively, as a result of enhanced separation of electron-hole pairs. The optimal catalyst of P-CoNi/ZIS displays a stoichiometric H2 and H2O2 productivity of 1228.7 and 1105.5 μmol h−1 g−1, respectively, with an apparent quantum efficiency of 6.2% at 365 nm. Impressively, H2 productivity of P-CoNi/ZIS has surpassed most reported catalysts for photocatalytic pure water splitting. This work provides a unique strategy to create efficient photocatalyst for pure water splitting.

Synthesis of Ilmenite Nickel Titanite-Supported Carbon Nanofibers Derived from Polyvinylpyrrolidone as Photocatalyst for H2 Production from Ammonia Borane Photohydrolysis.

The present study involves the synthesis of photocatalytic composite nanofibers (NFs) comprising ilmenite nickel titanite-supported carbon nanofibers (NiTiO3/TiO2@CNFs) using an electrospinning process. The photocatalytic composite NFs obtained were utilized in hydrogen (H2) production from the photohydrolysis of ammonia borane (AB). The experimental findings show that the photocatalytic composite NFs with a loading of 25 mg had a good catalytic performance for H2 generation, producing the stoichiometric H2 in 11 min using 1 mmol AB under visible light at 25 °C and 1000 rpm. The increase in catalyst load to 50, 75, and 100 mg leads to a corresponding reduction in the reaction time to 7, 5, and 4 min. The findings from the kinetics investigations suggest that the rate of the photohydrolysis reaction is directly proportional to the amount of catalyst in the reaction system, adhering to a first-order reaction rate. Furthermore, it was observed that the reaction rate remains unaffected by the concentration of AB, thereby suggesting a reaction of zero order. Increasing the reaction temperature results in a decrease in the duration of the photohydrolysis reaction. Furthermore, an estimated activation energy value of 35.19 kJ mol-1 was obtained. The composite nanofibers demonstrated remarkable and consistent effectiveness throughout five consecutive cycles. The results suggest that composite NFs possess the capacity to function as a feasible substitute for costly catalysts in the process of H2 generation from AB.

Enhanced Photocatalytic Activity of Hyper-Cross-Linked Polymers Toward Amines Oxidation Coupled with H2 O2 Generation through Extending Monomer's Conjugation Degree.

Visible-light-driven amines oxidation coupled with hydrogen peroxide (H2 O2 ) generation is a promising way to convert solar energy to chemical energy. Herein, a series of hyper-cross-linked polymers (HCPs) photocatalysts with different arenes monomers, including benzene (BE), diphenyl (DP), p-terphenyl (TP), or p-quaterphenyl (QP), were synthesized by simple Friedel-Crafts alkylation reaction. Owing to the maximum monomer's conjunction degree and excellent oxygen (O2 ) adsorption capacity, QP-HCPs exhibited highest photocatalytic activity for benzylamine oxidation coupled with H2 O2 generation under the irradiation of 455 nm Blue LED lamp. More than 99 % of benzylamine could be converted to N-benzylidenebenzylamine within 60 min. In addition, nearly stoichiometric H2 O2 was synchronously obtained with a high production rate of 9.3 mmol gcat -1 h-1 . Our work not only demonstrated that the photocatalytic activity of HCPs photocatalysts significantly depends on monomer's conjunction degree, but also provided a new strategy for converting solar energy to chemical energy.

Efficiently Light-Driven Nonoxidative Coupling of Methane on Ag/NaTaO3: A Case for Molecular-Level Understanding of the Coupling Mechanism

Metal-decorated oxide semiconductors are overwhelming photocatalysts for nonoxidative coupling of methane (NOCM). However, the overall NOCM mechanism remains an unopened black box, which hinders the design of high-performance catalysts. Herein, we systematically studied a series of noble metal (Ag, Au, Pt, Pd, Cu, and Ni)-decorated oxides (NaTaO3, CaTiO3, LiNbO3, and TiO2) for NOCM. We proposed that the active sites for H abstraction and C–C coupling of CH4 are spatially separated. Specifically, NaTaO3 only completes the initial H abstraction of CH4 activation, while metal nanoparticles are responsible for the final C–C coupling. Noble metals dominate NOCM by significantly decreasing the energy barrier of CH4 dissociation and promoting C–C coupling. Among various metals, Ag is preferential for the weak adsorption of ·CH3 intermediates and subsequent metal-induced C–C coupling. This contributes to Ag/NaTaO3 the highest C2H6 yield of 194 μmol g–1 h–1 and stoichiometric H2 with 11.2% quantum efficiency. This work provides a molecular-level insight into the CH4 coupling mechanism on metal-decorated photocatalysts.

Heterojunction within dual electric fields dynamically tailoring charge transfer to surface redox active sites for efficient H2 generation

Flying broom-like heterojunction photocatalysts with internal electric field synergizing polarized field has been constructed by spontaneously assembling CuO nanoparticles on polarized g-C3N4 microfibers (p-C3N4Fs) with using a facile hydrothermal method. Theoretical prediction and characterizations confirm that, photo-generated electrons and holes are dynamically transferred to reductive sites of pyridine-like N in p-C3N4Fs and oxidative sites of Cu atom in CuO for H2O splitting within the dual electric fields, respectively. Stoichiometric H2 and O2 evolution with solar energy conversion into H2 energy of 1.22 % has been achieved under AM 1.5G irradiation in photocatalytic H2O overall splitting by heterojunction photocatalytic mechanism of translation, rotation, transformation of protons and intermediates. The rational photocatalyst design on heterojunction with dual electric fields breaks the long-term thought of regulating charge carriers only by internal electric field, which will provide a unique perspective to deepen the kinetic study on the spatial separation and directional migration of photogenerated charges to the surface redox active sites for solar energy conversion.

Delocalized ferroelectric engineering of efficient photo-generated charge directional transfer for solar energy conversion into H2

Efficient transfer of photo-generated charges is a key kinetic factor of photocatalytic water (H2O) overall splitting. Herein, conversion of polypyrrole nanowire (PPyWs) insulator into delocalized ferroelectric semiconductor by transforming pyrrole into graphene structure containing azide (CNxFs) and subsequently integrating Ni2P (CNxFs/Ni2P) has been achieved for efficiently photocatalytic H2O overall splitting into hydrogen (H2) energy through a joint thermal and hydrothermal treatment. Theoretical prediction and detailed experimental results reveal that band gap of PPyWs insulator narrows from 4.63 eV to 2.36 eV of CNxFs (redox potentials: −0.85/1.51 V vs NHE), and the constructed delocalized ferroelectric CNxFs/Ni2P show efficient charge directional migration from generation sites to surface redox active sites. As a result, stoichiometric H2 and O2 evolution and a solar-to-H2 (STH) efficiency of 1.273 ± 0.051 % in photocatalytic H2O overall splitting have been completed under AM 1.5 G solar simulator irradiation along with gas bubbles under visible and even natural solar light. This research aims to solve the kinetic barrier of photocatalytic H2O splitting fundamentally through delocalized ferroelectric engineering, which will greatly boost the development of solar to H2 energy conversion.

High-performance photocatalytic nonoxidative conversion of methane to ethane and hydrogen by heteroatoms-engineered TiO2

Nonoxidative coupling of methane (NOCM) is a highly important process to simultaneously produce multicarbons and hydrogen. Although oxide-based photocatalysis opens opportunities for NOCM at mild condition, it suffers from unsatisfying selectivity and durability, due to overoxidation of CH4 with lattice oxygen. Here, we propose a heteroatom engineering strategy for highly active, selective and durable photocatalytic NOCM. Demonstrated by commonly used TiO2 photocatalyst, construction of Pd–O4 in surface reduces contribution of O sites to valence band, overcoming the limitations. In contrast to state of the art, 94.3% selectivity is achieved for C2H6 production at 0.91 mmol g–1 h–1 along with stoichiometric H2 production, approaching the level of thermocatalysis at relatively mild condition. As a benchmark, apparent quantum efficiency reaches 3.05% at 350 nm. Further elemental doping can elevate durability over 24 h by stabilizing lattice oxygen. This work provides new insights for high-performance photocatalytic NOCM by atomic engineering.

Enhanced ex-situ biomethanation of hydrogen and carbon dioxide in a trickling filter bed reactor

Ex-situ biomethanation is an emerging technology used for converting carbon dioxide (CO2) and renewable hydrogen (H2) into biomethane. The aim of this study was to investigate the influence of 4:1 and 6:1 stoichiometric H2:CO2 ratio for converting simultaneously exogenous and endogenous CO2 to natural gas quality (biomethane) in the trickling filter bed (TFB) reactor. The coupling of H2 and CO2 produced methane (CH4) content up to 75% and 98% at 4:1 and 6:1 H2:CO2 ratio, respectively. At 6:1 H2:CO2 ratio, the reactor demonstrated its potential to meet the criteria for natural gas quality biomethane and produced CH4 at a rate up to 2.65 L/LR.d with complete H2 utilization. Samples collected from the inoculum, the biofilm formed on the carrier material, and the liquid phase of the reactor showed distinct changes in the microbial community composition. The significant increase in relative abundance of Methanoculleus bourgensis upon H2 injection indicates hydrogenotrophic methanogenesis as the main pathway for enhanced biomethanation. Thus, our study provides a novel approach for simultaneous utilization of CO2 and digestate in a single-stage TFB reactor for achieving higher CH4 content in the output gas.

Ultrathin Crystalline Covalent-Triazine-Framework Nanosheets with Electron Donor Groups for Synergistically Enhanced Photocatalytic Water Splitting.

Ultrathin nanosheets have great potential for photocatalytic applications, however, suffer from enlarged band gap and narrowed visible-light-responsive range due to the quantum confinement effect. Herein, we report a novel redox strategy for efficient preparation of ultrathin crystalline amide-functionalized covalent-triazine-framework nanosheets (CTF NSs) with enhanced visible light absorption. The CTF NSs exhibited photocatalytic hydrogen (512.3 μmol h-1 ) and oxygen (12.37 μmol h-1 ) evolution rates much higher than that of pristine bulk CTF. Photocatalytic overall water splitting could be achieved with efficient stoichiometric H2 (5.13 μmol h-1 ) and O2 (2.53 μmol h-1 ) evolution rates under visible light irradiation. Experimental and theoretical analysis revealed that introduction of amide groups as electron donor optimized the band structure and improve its visible-light absorption, hydrophilicity and carrier separation efficiency, thus resulting in the enhanced photocatalytic performance. The well-dispersed CTF NSs could be easily cast onto a support as a thin film device and demonstrate excellent photocatalytic activity (25.7 mmol h-1 m-2 for hydrogen evolution).

Ultrathin Crystalline Covalent‐Triazine‐Framework Nanosheets with Electron Donor Groups for Synergistically Enhanced Photocatalytic Water Splitting

AbstractUltrathin nanosheets have great potential for photocatalytic applications, however, suffer from enlarged band gap and narrowed visible‐light‐responsive range due to the quantum confinement effect. Herein, we report a novel redox strategy for efficient preparation of ultrathin crystalline amide‐functionalized covalent‐triazine‐framework nanosheets (CTF NSs) with enhanced visible light absorption. The CTF NSs exhibited photocatalytic hydrogen (512.3 μmol h−1) and oxygen (12.37 μmol h−1) evolution rates much higher than that of pristine bulk CTF. Photocatalytic overall water splitting could be achieved with efficient stoichiometric H2 (5.13 μmol h−1) and O2 (2.53 μmol h−1) evolution rates under visible light irradiation. Experimental and theoretical analysis revealed that introduction of amide groups as electron donor optimized the band structure and improve its visible‐light absorption, hydrophilicity and carrier separation efficiency, thus resulting in the enhanced photocatalytic performance. The well‐dispersed CTF NSs could be easily cast onto a support as a thin film device and demonstrate excellent photocatalytic activity (25.7 mmol h−1 m−2 for hydrogen evolution).

LaTaON2 Mesoporous Single Crystals for Efficient Photocatalytic Water Oxidation and Z-Scheme Overall Water Splitting.

LaTaON2 porous single crystals (PSCs), integrating structural coherence and porous microstructures, will warrant promising photocatalytic performance. The absence of grain boundaries in PSCs ensures rapid photocarrier transportation from bulk to the surface, thereby mitigating photocarriers' recombination. Porous microstructures not only provide ample reachable surface to host photochemical reactions but also reinforce photon-matter interactions by additional photon reflection/scattering. Here, we have synthesized LaTaON2 PSCs via a topotactic route and show significantly improved photocatalytic performance. Efficient water oxidation into O2 has been realized by LaTaON2 PSCs with an apparent quantum efficiency as high as 5.7% at 420 ± 20 nm. Stable overall water splitting into stoichiometric H2 and O2 has also been achieved in a Z-scheme setup using LaTaON2 PSCs as the O2 evolution photocatalyst. These results not only prove that PSCs facilitate photocarrier migrations, which in turn deliver exceptional photocatalytic performance, but also imply that PSCs are useful to reinvigorate conventional semiconductor photocatalysts toward efficient solar energy conversions.

Syngas biomethanation: effect of biomass-gas ratio, syngas composition and pH buffer

The concept of syngas biomethanation is attractive, however, it still needs improvement in optimizing the operational conditions. In the present study, syngas fermentations under different carbon monoxide (CO), carbon dioxide (CO2) and hydrogen (H2) compositions were conducted under two different biomass-gas ratio (BGR) systems. The results showed that high BGR enhanced the CO consumption rate, achieving a 60% enhancement with CO as the sole substrate. Stoichiometric H2 addition could successfully convert all the CO and CO2 to pure methane, however, higher H2 partial pressure might decline the CO consumption due to pH inhibition from consumption of bicarbonate. Microbial analysis showed different syngas composition could affect the bacteria community, while, archaea community was only slightly affected with Methanothermobacter as the dominant methanogen. This study provided strategy for efficient syngas biomethanation and deeper insight into effect of H2 addition on CO conversion under different BGR systems.

Light-Induced Nonoxidative Coupling of Methane Using Stable Solid Solutions.

Achieving efficient and direct conversion of methane under mild conditions is of great significance for innovations in the chemical industry. However, the efficiency and lifetime of most catalysts remain too far from practical requirements, since it is difficult to break the first C-H bond of methane as well as to suppress the following complete dehydrogenation (or overoxidation) and the resulting carbonaceous deposition (or CO2 ). Here, we report that wurtzite GaN:ZnO solid solutions exhibit unique and unprecedented photocatalytic performances for the nonoxidative coupling of methane at room temperature, exclusively generating ethane with nearly stoichiometric H2 . High conversion rate (>330 μmol g-1 h-1 ), long-term stability (>70 h), and superior coke-resistance were achieved. At 293 K, the methane conversion exceeds 7 %, comparable to the equilibrium conversion of thermal catalysis at 910 K. Mechanistic studies revealed that the N-ZnGa -ON units and the absence of acid sites on the surface played crucial roles in reactivity and coke resistance, respectively.

Light‐Induced Nonoxidative Coupling of Methane Using Stable Solid Solutions

AbstractAchieving efficient and direct conversion of methane under mild conditions is of great significance for innovations in the chemical industry. However, the efficiency and lifetime of most catalysts remain too far from practical requirements, since it is difficult to break the first C−H bond of methane as well as to suppress the following complete dehydrogenation (or overoxidation) and the resulting carbonaceous deposition (or CO2). Here, we report that wurtzite GaN:ZnO solid solutions exhibit unique and unprecedented photocatalytic performances for the nonoxidative coupling of methane at room temperature, exclusively generating ethane with nearly stoichiometric H2. High conversion rate (>330 μmol g−1 h−1), long‐term stability (>70 h), and superior coke‐resistance were achieved. At 293 K, the methane conversion exceeds 7 %, comparable to the equilibrium conversion of thermal catalysis at 910 K. Mechanistic studies revealed that the N‐ZnGa‐ON units and the absence of acid sites on the surface played crucial roles in reactivity and coke resistance, respectively.

Photocatalytic overall water splitting without noble-metal: Decorating CoP on Al-doped SrTiO3

CoP, a noble-metal-free cocatalyst, was first introduced onto the surface of Al-doped SrTiO3 (Al:STO) via an in situ photodeposition-phosphorization method for photocatalytic overall water splitting (POWS) into stoichiometric H2 and O2. Compared with pure Al:STO, the POWS activity was enhanced by a factor of ~ 421 over 1.0%CoP/Al:STO, with the highest evolution rates of 2106 and 1002 μmol h−1 g−1 for H2 and O2, respectively. The mechanism for the remarkably boosted POWS activity was systematically analyzed based on the comprehensive characterization. On the one hand, benefiting from the in situ photodeposition process, CoP with metallic character were intimately decorated onto the surface of Al:STO and accelerated the separation and migration of photoinduced charge carriers. On the other hand, CoP, serving as reactive sites for H2 evolution reaction, lowered the overpotential and facilitated the surface reduction reaction, thereby enhancing the POWS activity. Furthermore, Cr2O3 was photodeposited on the surface of 1.0%CoP/Al:STO composite to suppress the undesired reverse reaction and the POWS activity was further enhanced up to 3558 and 1722 μmol h−1 g−1 for H2 and O2, respectively, with apparent quantum yield of 7.1% at 350 ± 10 nm. This work presents a new avenue for designing POWS system without noble-metal cocatalyst.