Experimental investigation on NG dual fuel engine improvement by hydrogen enrichment

The crude oil graduate depletion, as well as aspects related to environmental pollution and global warming instigated many researches concerning alternative fuels. Natural gas (NG) is one of the most attractive available fuels. A promising technique for its use in internal combustion engines is the dual fuel concept. One of the main problems with this technique is that, at low loads, the engine efficiency decreases compared to conventional diesel. The unburned hydrocarbons and carbon monoxide emissions are also higher in dual fuel mode. An effective method to compensate the demerits of limited lean-burn ability and slow burning velocity of NG is to mix it with a fuel that possesses wide flammability limit and fast burning velocity. Hydrogen (H₂) is thought to be the best gaseous candidate for natural gas.In the present work, NG enrichment with various H₂ blends is investigated as a technique for improving dual fuel mode, especially at low loads. Impact on engine performance and emissions is experimentally examined. Total BSFC is considerably reduced. An important benefit in terms of BTE, reaching to increase a 12% with the 10%H₂ blend compared to the pure NG case, is also achieved. THC and CO emissions are in general reduced as a result of the improvement of gaseous fuel utilization. CO₂ emissions are also in general reduced. Even though a slight increase is in overall observed for NO_x emissions, it's almost insignificant.     

Hydrogen supplemented natural gas effect on a DI diesel engine operating under dual fuel mode with a biodiesel pilot fuel

In order to slow down the continuing environmental deterioration, regulations for pollutant emissions limitations are increasingly rigorous. The development of new alternative fuels for internal combustion engines is a very interesting solution not only to overcome the pollution problem but also because of the petroleum shortage. In this context, the present work investigates the improvement of a DI diesel engine operating at constant speed (1500 rpm) and under dual fuel mode with eucalyptus biodiesel and natural gas (NG) enriched by various H₂ quantities (15, 25 and 30 by v%). The eucalyptus biodiesel quantity injected into the engine cylinder is kept constant, to supply around 10% of the engine nominal power, for all examined engine loads. The engine load is further increased using only the gaseous fuel (NG+H₂), which is introduced with the intake air. The effect of H₂/NG blending ratio on the combustion parameters, performance and pollutant emissions of the engine is investigated and compared with those of pure NG case. An important benefit in terms of brake specific fuel consumption, reaching a decrease of 4–10% with the 25% H₂ blend compared to the pure NG case, is achieved. Concerning the pollutant emissions, NG enrichment with H₂ is an efficient solution to enhance the combustion process and hence reduce carbon monoxide, unburned hydrocarbon and soot emissions at high loads where they are important for pure NG. However for the nitrogen oxide emissions, NG blending with H₂ is attractive only at low and medium loads where their levels are lower than pure NG.     

Experimental investigation of the effects of simultaneous hydrogen and nitrogen addition on the emissions and combustion of a diesel engine

Overcoming diesel engine emissions trade-off effects, especially NO_x and Bosch smoke number (BSN), requires investigation of novel systems which can potentially serve the automobile industry towards further emissions reduction. Enrichment of the intake charge with H₂ + N₂ containing gas mixture, obtained from diesel fuel reforming system, can lead to new generation low polluting diesel engines.     

Study of methane enrichment in a biogas fuelled HCCI engine

Biogas has been a promising alternative fuel for IC engines. However, its CO₂ content reduces calorific value and ignitability. The CO₂ fraction of raw biogas can be separated out by various techniques, which are collectively called methane enrichment. The present study explores the effect of methane enrichment on the output parameters of a Homogeneous Charge Compression Ignition (HCCI) engine. A single cylinder CI engine is altered for this purpose. Biogas (CH₄ + CO₂) is supplied along with air. Diethyl Ether (DEE) is used as the secondary fuel to initiate auto-ignition. The effects of injecting DEE at the inlet port and upstream in the intake manifold are also compared. Performance, emission and combustion characteristics such as brake thermal efficiency, equivalence ratio, HC, CO, CO₂, NO_x and smoke emissions, start and duration of combustion, in-cylinder pressure and maximum heat release rate are compared for operation with raw biogas (50% methane) and methane enriched biogas (100% methane) for various biogas flow rates and engine torques. Results show that methane enrichment enhances brake thermal efficiency by up to 2% compared to raw biogas. Methane enrichment advances and speeds up combustion. HC, CO and CO₂ emissions, maximum cylinder pressure and maximum heat release rate are also improved with methane enrichment. Ultra-low NO_x and smoke emissions can be obtained using raw biogas as well as methane enriched biogas. Low biogas flow rates provide better brake thermal efficiency and HC emissions. Manifold injection of DEE enhances brake thermal efficiency by up to 2% compared to port injection by virtue of greater mixture homogeneity.     

Influence of hydrogen peroxide emulsification with gasoline on the emissions and performance in an MPFI engine

Spark ignition (SI) engines have been a major contributor from the transportation sector towards the increased emissions to the environment. Modifications to the SI engine like structural modifications, pre, and post-combustion treatments have been investigated in the literature. The use of oxygenated additives to gasoline fuel has been major research interest in curbing the emissions without any significant loss in engine performance. Hydrogen peroxide (H₂O₂) has not been investigated as an additive in SI engines although its effect is demonstrated for compression ignition (CI) engines. This paper aims to address this gap by ascertaining the influence of H₂O₂ concentration on SI engine emissions and performance. H₂O₂ is varied from 0 to 1.5% and the engine speed varied from 1500 to 3000 rpm by operating at a constant load. A total of 16 trials (with three replicates) is carried out. The output responses are brake thermal efficiency (BTE), brake specific fuel consumption (BSFC), emissions of CO, CO₂, HC, and NOx. Artificial neural networks are adopted to ascertain the relation between the inputs and the output responses. Emulsifying gasoline with 1.5% H₂O₂ resulted in an average reduction of CO and HC emissions by 21.1% and 28.6% respectively with an overall average of 25.3% of reduction in the NOx. The average BTE at all engine speeds increases from 21.6% for G0 to 23.8% for G1.5 and an overall average of 10.5% reduction in BSFC is obtained. The study shows that H₂O₂ can be employed as an emulsifier to gasoline fuel, however, more rigorous studies are required to ascertain its impact, volatility, and storage.     

Effect of manifold injection of hydrogen gas in producer gas and neem biodiesel fueled CRDI dual fuel engine

The high flammability of hydrogen gas gives it a steady flow without throttling in engines while operating. Such engines also include different induction/injection methods. Hydrogen fuels are encouraging fuel for applications of diesel engines in dual fuel mode operation. Engines operating with dual fuel can replace pilot injection of liquid fuel with gaseous fuels, significantly being eco-friendly. Lower particulate matter (PM) and nitrogen oxides (NO_x) emissions are the significant advantages of operating with dual fuel.Consequently, fuels used in the present work are renewable and can generate power for different applications. Hydrogen being gaseous fuel acts as an alternative and shows fascinating use along with diesel to operate the engines with lower emissions. Such engines can also be operated either by injection or induction on compression of gaseous fuels for combustion by initiating with the pilot amount of biodiesel. Present work highlights the experimental investigation conducted on dual fuel mode operation of diesel engine using Neem Oil Methyl Ester (NeOME) and producer gas with enriched hydrogen gas combination. Experiments were performed at four different manifold hydrogen gas injection timings of TDC, 5°aTDC, 10°aTDC and 15°aTDC and three injection durations of 30°CA, 60°CA, and 90°CA. Compared to baseline operation, improvement in engine performance was evaluated in combustion and its emission characteristics. Current experimental investigations revealed that the 10°aTDC hydrogen manifold injection with 60°CA injection duration showed better performance. The BTE of diesel + PG and NeOME + PG operation was found to be 28% and 23%, respectively, and the emissions level were reduced to 25.4%, 14.6%, 54.6%, and 26.8% for CO, HC, smoke, and NO_x, respectively.     

An experimental investigation of incomplete combustion of gaseous fuels of a heavy-duty diesel engine supplemented with hydrogen and natural gas

This paper investigates the emissions of the unburned gaseous fuels of a heavy-duty diesel engine converted to operate under natural gas (NG)-diesel and hydrogen (H₂)-diesel dual fuel combustion mode. The detailed effects of the addition of H₂, NG, engine load, and engine speed on the exhaust emissions of the unburned H₂, methane (CH₄), and carbon monoxide (CO) were experimentally investigated. The combustion efficiencies of CH₄ and H₂ supplemented were also examined and compared.     

Performance and emissions characteristics of Jatropha oil (preheated and blends) in a direct injection compression ignition engine

The scarce and rapidly depleting conventional petroleum resources have promoted research for alternative fuels for internal combustion engines. Among various possible options, fuels derived from triglycerides (vegetable oils/animal fats) present promising “greener” substitutes for fossil fuels. Vegetable oils, due to their agricultural origin, are able to reduce net CO₂ emissions to the atmosphere along with import substitution of petroleum products. However, several operational and durability problems of using straight vegetable oils in diesel engines reported in the literature, which are because of their higher viscosity and low volatility compared to mineral diesel fuel.In the present research, experiments were designed to study the effect of reducing Jatropha oil’s viscosity by increasing the fuel temperature (using waste heat of the exhaust gases) and thereby eliminating its effect on combustion and emission characteristics of the engine. Experiments were also conducted using various blends of Jatropha oil with mineral diesel to study the effect of reduced blend viscosity on emissions and performance of diesel engine. A single cylinder, four stroke, constant speed, water cooled, direct injection diesel engine typically used in agricultural sector was used for the experiments. The acquired data were analyzed for various parameters such as thermal efficiency, brake specific fuel consumption (BSFC), smoke opacity, CO₂, CO and HC emissions. While operating the engine on Jatropha oil (preheated and blends), performance and emission parameters were found to be very close to mineral diesel for lower blend concentrations. However, for higher blend concentrations, performance and emissions were observed to be marginally inferior.     

Exploration of engine characteristics in a CRDI diesel engine enriched with hydrogen in dual fuel mode using toroidal combustion chamber

The impact of dual fuel (diesel/hydrogen) on different performance aspects of CRDI diesel engines is investigated in this study. Amongst the fuel alternatives for IC (internal combustion) engines, the research described in this study recommended hydrogen as the least polluting and renewable in the long term. A CNG-LPG injector feeds hydrogen into the intake manifold, while diesel injectors pump pilot diesel to a DI engine adapted to hydrogen and diesel (dual-fuel mode). By maintaining 5.2 KW of consistent IP (Indicated Power) and engine speed at 1500 ± 10 rotations per minute (RPM), the hydrogen energy was varied in the dual fuel at 0% (100% diesel), 6%, 12%, 18% and 24%. With the increase in H₂ energy proportion, a decrease (5.2% decrease at 24% HES) in the BSEC (brake specific energy consumption) and the engine's BTE (brake thermal efficiency) is improved (7.85% increase at 24% HES). When emissions are considered, indicated NO_x increased (3.42%) while indicated CO₂ (3.61%), CO (2.84%), and smoke (4.85%) decreased with an increase in the proportion of hydrogen. Along with this, it was noted that the peak HRR (heat release rate) of 69.8 J/deg and in-cylinder pressure of 80.8 bar which increased significantly with the increase in hydrogen rate.     

Effect of injection timing on the exhaust emissions of a diesel engine using diesel–methanol blends

Environmental concerns and limited resource of petroleum fuels have caused interests in the development of alternative fuels for internal combustion (IC) engines. For diesel engines, alcohols are receiving increasing attention because they are oxygenated and renewable fuels. Therefore, in this study, the effect of injection timing on the exhaust emissions of a single cylinder, naturally aspirated, four-stroke, direct injection diesel engine has been experimentally investigated by using methanol-blended diesel fuel from 0% to 15% with an increment of 5%. The tests were conducted for three different injection timings (15°, 20° and 25 °CA BTDC) at four different engine loads (5 Nm, 10 Nm, 15 Nm, 20 Nm) at 2200 rpm. The experimental test results showed that Bsfc, NO_x and CO₂ emissions increased as BTE, smoke opacity, CO and UHC emissions decreased with increasing amount of methanol in the fuel mixture. When compared the results to those of original injection timing, NO_x and CO₂ emissions decreased, smoke opacity, UHC and CO emissions increased for the retarded injection timing (15 °CA BTDC). On the other hand, with the advanced injection timing (25 °CA BTDC), decreasing smoke opacity, UHC and CO emissions diminished, and NO_x and CO₂ emissions boosted at all test conditions. In terms of Bsfc and BTE, retarded and advanced injection timings gave negative results for all fuel blends in all engine loads.     

Performance and emissions characteristics of a lean-burn marine natural gas engine with the addition of hydrogen-rich reformate

The exhaust gas-fuel reforming technique known as reformed exhaust gas recirculation (REGR) can generate on-board hydrogen-rich gas mixture (i.e., reformate) by catalytic reforming of the exhaust gas and fuel added into the reformer and then recirculate the reformate into the engine cylinder, which can realize the combination of hydrogen-rich lean combustion and exhaust gas recirculation. The REGR technique can be employed to achieve efficient and stable lean-burn combustion for the marine engine fueled with natural gas (i.e., marine NG engine) and it is considered as an effective way to meet the stringent ship emissions regulations. In the present study, an experimental investigation into the effects of reformate addition ratio (R_re) and excess air ratio (λ) on the combustion and emissions characteristics of a marine NG engine under various loads was conducted, and the potential of applying the REGR technique in a marine NG engine to achieve low emissions (i.e., International Maritime Organization Tier Ⅲ emissions legislations for international ships) was discussed. The results indicate that the addition of the hydrogen-rich reformate gases can extend lean-burn limit. For a given λ, the flame development duration and rapid combustion duration decrease with the increase of R_re, and the combustion efficiency is improved. The brake specific NO_x emissions first increase and then decrease with the increase of R_re due to the competition between the combustion phase and total heat release value. The brake specific THC emissions decline with the increase of R_re, while the reverse holds for the brake specific CO emissions, and the behavior tends to be obvious under large λ. It is demonstrated that the combination of REGR and the lean-burn combustion strategy can improve the trade-off relationship between the NO_x emissions and brake specific fuel consumption of the marine NG engine to meet the IMO Tier Ⅲ NO_x emissions legislations and maintain relatively low brake specific fuel consumption.     

Flame chemiluminescence and OH LIF imaging in a hydrogen-fuelled spark-ignition engine

Research into novel internal combustion engines requires consideration of the diversity in future fuels in an attempt to reduce drastically CO₂ emissions from vehicles and promote energy sustainability. Hydrogen has been proposed as a possible fuel for future internal combustion engines. Hydrogen’s wide flammability range allows higher engine efficiency with much leaner operation than conventional fuels, for both reduced toxic emissions and no CO₂ gases. This paper presents results from an optical study of combustion in a spark-ignition research engine running with direct injection and port injection of hydrogen. Crank-angle resolved flame chemiluminescence images were acquired and post-processed for a series of consecutive cycles in order to calculate in-cylinder rates of flame growth. Laser induced fluorescence of OH was also applied on an in-cylinder plane below the spark plug to record detailed features of the flame front for a series of engine cycles. The tests were performed at various air-to-fuel ratios, typically in a range of φ = 0.50–0.83 at 1000 RPM with 0.5 bar intake pressure. The engine was also run with gasoline in direct-injection and port-injection modes to compare with the operation on hydrogen. The observed combustion characteristics were analysed with respect to laminar and turbulent burning velocities, as well as flame stretch. An attempt was also made to review relevant hydrogen work from the limited literature on the subject and make comparisons were appropriate.     

Conversion of a commercial spark ignition engine to run on hydrogen: Performance comparison using hydrogen and gasoline

The modifications performed to convert the spark ignition gasoline-fueled internal combustion engine of a Volkswagen Polo 1.4 to run with hydrogen are described. The car is representative of small vehicles widely used for both city and interurban traffic. Main changes included the inlet manifold, gas injectors, oil radiator and the electronic management unit. Injection and ignition advance timing maps were developed for lean mixtures with values of the air to hydrogen equivalence ratio (λ) between 1.6 and 3. The established engine control parameters allowed the safe operation of the hydrogen-fueled engine (H₂ICE) free of knock, backfire and pre-ignition as well with reasonably low NO_x emissions. The H₂ICE reached best brake torque of 63 Nm at 3800 rpm and maximum brake power of 32 kW at 5000 rpm. In general, the brake thermal efficiency of the H₂ICE is greater than that of gasoline-fueled engine except for the H₂ICE working at very lean conditions (λ = 2.5) and high speeds (above 4000 rpm). A significant effect of the spark advance on the NO_x emissions has been found, specially for relatively rich mixtures (λ < 2). Small changes of spark advance with respect to the optimum value for maximum brake torque give rise to an increase of pollutant emissions. It has been estimated that the hydrogen-fueled Volkswagen Polo could reach a maximum speed of 140 km/h with the adapted engine. Moreover, there is enough reserve of power for the vehicle moving on typical urban routes and routes with slopes up to 10%.     

The effects of ethanol–unleaded gasoline blends on engine performance and exhaust emissions in a spark-ignition engine

Alcohols have been used as a fuel for engines since 19th century. Among the various alcohols, ethanol is known as the most suited renewable, bio-based and ecofriendly fuel for spark-ignition (SI) engines. The most attractive properties of ethanol as an SI engine fuel are that it can be produced from renewable energy sources such as sugar, cane, cassava, many types of waste biomass materials, corn and barley. In addition, ethanol has higher evaporation heat, octane number and flammability temperature therefore it has positive influence on engine performance and reduces exhaust emissions. In this study, the effects of unleaded gasoline (E0) and unleaded gasoline–ethanol blends (E50 and E85) on engine performance and pollutant emissions were investigated experimentally in a single cylinder four-stroke spark-ignition engine at two compression ratios (10:1 and 11:1). The engine speed was changed from 1500 to 5000 rpm at wide open throttle (WOT). The results of the engine test showed that ethanol addition to unleaded gasoline increase the engine torque, power and fuel consumption and reduce carbon monoxide (CO), nitrogen oxides (NO_x) and hydrocarbon (HC) emissions. It was also found that ethanol–gasoline blends allow increasing compression ratio (CR) without knock occurrence.     

Experimental study on premixed hydrogen/air and hydrogen–methane/air mixtures explosion in 90 degree bend pipeline

Nowadays, hydrogen is being utilized massively in industries as a clean fuel. Displacing of hydrogen due to unique chemical and physical properties has adversely affect on pipeline network, hence increases the potential risk of explosion. This study was carried out to determine the flame propagation of hydrogen/air and hydrogen–methane/air mixtures in pipeline. A 90° pipeline with L/D ratio of 40 was used. Pure hydrogen/air mixture with equivalence ratio, φ = 0.13, 0.17, 0.2, 0.24, 0.27 and 0.30 were used in this work. Different composition of hydrogen–methane–air mixtures were tested in this study i.e. 3%H₂ + 97CH₄, 4%H₂ + 96CH₄, 6%H₂ + 94CH₄ and 8%H₂ + 92CH₄. All mixtures were operated at ambient condition. The results show that bending is the critical part of pipeline and higher concentration of hydrogen can affect on maximum overpressure, flame speed and temperature rise of both pure hydrogen/air and methane-hydrogen/air mixtures.     

Effect of Exhaust Gas Recirculation (EGR) on performance,emissions, deposits and durability of a constant speed compression ignition engine

To meet stringent vehicular exhaust emission norms worldwide, several exhaust pre-treatment and post-treatment techniques have been employed in modern engines. Exhaust Gas Recirculation (EGR) is a pre-treatment technique, which is being used widely to reduce and control the oxides of nitrogen (NO_x) emission from diesel engines. EGR controls the NO_x because it lowers oxygen concentration and flame temperature of the working fluid in the combustion chamber. However, the use of EGR leads to a trade-off in terms of soot emissions. Higher soot generated by EGR leads to long-term usage problems inside the engines such as higher carbon deposits, lubricating oil degradation and enhanced engine wear. Present experimental study has been carried out to investigate the effect of EGR on soot deposits, and wear of vital engine parts, especially piston rings, apart from performance and emissions in a two cylinder, air cooled, constant speed direct injection diesel engine, which is typically used in agricultural farm machinery and decentralized captive power generation. Such engines are normally not operated with EGR. The experiments were carried out to experimentally evaluate the performance and emissions for different EGR rates of the engine. Emissions of hydrocarbons (HC), NO_x, carbon monoxide (CO), exhaust gas temperature, and smoke opacity of the exhaust gas etc. were measured. Performance parameters such as thermal efficiency, brake specific fuel consumption (BSFC) were calculated. Reduction in NO_x and exhaust gas temperature were observed but emissions of particulate matter (PM), HC, and CO were found to have increased with usage of EGR. The engine was operated for 96 h in normal running conditions and the deposits on vital engine parts were assessed. The engine was again operated for 96 h with EGR and similar observations were recorded. Higher carbon deposits were observed on the engine parts operating with EGR. Higher wear of piston rings was also observed for engine operated with EGR.     

The effects of fuel-injection timing at medium injection pressure on the engine characteristics and emissions of a CNG-DI engine fueled by a small amount of hydrogen in CNG

The experiments to determine the effect of fuel-injection timings on engine characteristics and emissions of a DI engine fueled with NG-hydrogen blends (0%, 3%, 5% and 8%) at various engine speeds were conducted. Three injection timings namely 120°, 180° and 300° CA BTDC with a wide open throttle at relative air-fuel ratio, λ = 1.0 were selected. The ignition advance angle was fixed at 30° CA BTDC, while the injection pressure was fixed at 1.4 MPa for all the cases. The tests were firstly performed at low engine speed of 2000 rpm to determine the engine characteristics and emissions. The results showed that the engine performance (e.g. Brake Torque, Brake Power and BMEP), the cylinder pressure and the heat release have the highest values at the injection timing of 180° CA BTDC, followed by the 300° CA BTDC and the 120° CA BTDC. The NO_x emission was found to be highest at the injection timing of 180° CA BTDC. The THC and CO emissions were found to decrease while the CO₂ emission increased with the advancement in the injection timing. The addition of a small amount of hydrogen to the natural gas was found to increase the engine performance, enhance combustion and reduce emissions for any selected injection timings. Secondly, the tests were carried out at variable engine speeds (i.e. 2000 rpm-4000 rpm) in order to further investigate the engine performance. The injection timings of 180° and 300° CA BTDC with CNG-H₂ blends were only selected for comparisons. The injection timing of the 300° CA BTDC was discovered to yield better engine performance as compared to the 180° CA BTDC injection timing after a cutoff engine speed of approximately 2500 rpm.     

Controlled autoignition of hydrogen in a direct-injection optical engine

Research into novel internal combustion engines requires consideration of the diversity in future fuels in an attempt to reduce drastically CO₂ emissions from vehicles and promote energy sustainability. Hydrogen has been proposed as a possible fuel for future internal combustion engines and can be produced from renewable sources. Hydrogen’s wide flammability range allows higher engine efficiency than conventional fuels with both reduced toxic emissions and no CO₂ gases. Most previous work on hydrogen engines has focused on spark-ignition operation. The current paper presents results from an optical study of controlled autoignition (or homogeneous charge compression ignition) of hydrogen in an engine of latest spark-ignition pentroof combustion chamber geometry with direct injection of hydrogen (100 bar). This was achieved by a combination of inlet air preheating in the range 200–400 °C and residual gas recirculated internally by negative valve overlap. Hydrogen fuelling was set to various values of equivalence ratio, typically in the range ? = 0.40–0.63. Crank-angle resolved flame chemiluminescence images were acquired for a series of consecutive cycles at 1000 RPM in order to calculate in-cylinder rates of flame expansion and motion. Planar Laser Induced Fluorescence (LIF) of OH was also applied to record more detailed features of the autoignition pattern. Single and double (i.e. ‘split’ per cycle) hydrogen injection strategies were employed in order to identify the effect of mixture preparation on autoignition’s timing and spatial development. An attempt was also made to review relevant in-cylinder phenomena from the limited literature on hydrogen-fuelled spark-ignition optical engines and make comparisons were appropriate.     

Reducing cold-start emission from internal combustion engines by means of thermal energy storage system

Increasing environmental pollutions is an important problem appearing at cold start of internal combustion engines. Developments of new devices that solve this problem are an extremely urgent need especially for cold regions. In this study, a developed experimental sample of thermal energy storage system (TESS) for pre-heating of internal combustion engines has been designed and tested. The development thermal energy storage device (TESD) works on the effect of absorption and rejection of heat during the solid–liquid phase change of heat storage material (Na₂SO₄ · 10H₂O). The TESS has been applied to a gasoline engine at 2 °C temperature and 1 atm pressure. Charging and discharging time of the TESD are about 500 and 600 s, respectively and temperature of engine is increased 17.4 °C averagely with pre-heating. Maximum thermal efficiency of the TESS system is 57.5 % after 12 h waiting duration. CO and HC emissions decrease about 64% and 15%, respectively, with effect of pre-heating engine at cold start and warming-up period.     

2D/2D Cu-tetrahydroxyquinone MOF/N-doped graphene heterojunction as photocatalyst for overall water splitting

A novel 2D/2D heterojunction (CuTHQ/NG) has been prepared by in situ growth of the 2D CuTHQ MOF on defective N-doped graphene (NG), and its photocatalytic activity for overall water splitting studied in detail. CuTHQ/NG heterojunction has demonstrated better photocatalytic activity (480 μmol/g) than the individual components (257 and 65 μmol/g for CuTHQ and NG, respectively) for H₂ evolution. Furthermore, unlike the individual components, the as-prepared 2D/2D CuTHQ/NG heterojunction promotes overall water splitting under simulated sunlight (164 μmol of H₂/g and 80 μmol of O₂/g). We have also studied the photo-induced charge separation and recombination reactions. Photocurrent measurements and emission quenching experiments have confirmed improved charge separation in the CuTHQ/NG heterojunction. Moreover, the charge recombination kinetics have been investigated with transient absorption spectroscopy. Electron/hole recombination in the heterojunction has been determined more than one order of magnitude slower (8.9 μs) than the mechanical mixture of CuTHQ and NG (0.35 μs). Finally, the photochemical stability of the 2D/2D heterojunction has been investigated performing a long-term (96 h) experiment, demonstrating near linear H₂ evolution along the irradiation time.