Investigating the performance of biodiesel-diesel blend coupled with green-synthesized CaO nanorods for compression ignition engines

Kiran Chaudhari; Nilesh P. Salunke; Shakeelur Raheman; Khursheed B. Ansari; Vijay R. Diware; Mumtaj Shah; Mohd Shariq Khan

doi:10.25259/JKSUS_439_2025

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Research Article

2025

:37;

4392024

doi:

10.25259/JKSUS_439_2025

Investigating the performance of biodiesel-diesel blend coupled with green-synthesized CaO nanorods for compression ignition engines

Kiran Chaudhari^a, Nilesh P. Salunke^b,*, Shakeelur Raheman^c, Khursheed B. Ansari^d,*, Vijay R. Diware^e, Mumtaj Shah^d, Mohd Shariq Khan^f,

aDepartment of Mechanical Engineering, R. C. Patel Institute of Technology, Shirpur, 425405, India

bDepartment of Mechanical Engineering, Shri Vile Parle Kelavani Mandal’s Institute of Technology, Dhule, 424001, India

cDepartment of Applied Sciences & Humanities, SVKM’s Institute of Technology, Dhule, 424001, India

dDepartment of Chemical Engineering, King Khalid University, Al Faara Campus, Abha, 61411, Saudi Arabia

eDepartment of Chemical Engineering, Shram Sadhana Bombay Trust College of Engineering & Technology, Post Box No. 94, Jalgaon, 425001, India

fDepartment of Chemical Engineering, College of Engineering, Dhofar University, Salalah, 211, Oman

* Corresponding author E-mail address: khansari@kku.edu.sa (K.B. Ansari); Nilesh.Salunke@svkm.ac.in (N. P. Salunke)

Received: 2025-02-27, Accepted: 2025-05-04, Published: 2025-05-31

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This is an open-access article distributed under the terms of the Creative Commons Attribution-Non Commercial-Share Alike 4.0 License, which allows others to remix, transform, and build upon the work non-commercially, as long as the author is credited and the new creations are licensed under the identical terms.

Abstract

Present research shows that green preparation and application of calcium oxide nanorods (CaO NRs) boost the competence of the compression ignition (CI) engine and reduce detrimental emissions. CaO NRs were synthesized in an aqueous solution using the extract from Murraya Koenigii leaves and thoroughly analyzed with UV-Vis, Fourier transform infrared (FTIR), X-ray diffraction (XRD), scanning electron microscopy-energy dispersive X-ray (SEM-EDX), and high-resolution transmission electron microscopy (TEM) analyses. The CaO NRs were uniformly distributed within biodiesel-diesel blends (BDs) and evaluated for brake thermal efficiency (BTE), brake specific fuel consumption (BSFC), exhaust gas temperature (EGT), smoke emissions, carbon monoxide, hydrocarbons in the exhaust, and blend fuel stability. The performance of CaO NRs embedded BDs, i.e., BDC50 and BDC100 (BD blended with 50 ppm and 100 ppm CaO NRs, respectively), was related to diesel (B0), biodiesel-diesel blends. The BDC100 showed improved BTE (3.32%) and minimized CO, HCs, and smoke emissions (25%, 24%, and 43.9%, respectively) than BD fuel. Further, the BSFC of BDC100 was 21.54% and 27.45% higher than BD and diesel, respectively. Moreover, BDC100 showed lower EGT (by 5.01%) and brake-specific CO emission (by 25%) than BD. The NOx emissions of BDC100 fuels were the lowest compared to pure diesel and BD. Thus, the CaO NRs embedded biodiesel-diesel blend indicated the potential for boosting CI engine fuel efficiency and reducing the environmental impact.

Keywords

Biodiesel-diesel blend

CaO Nanorods

CI engine Performance parameters

Compression Ignition Engine

Emission parameters

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1. Introduction

A major portion of the global energy demand is satisfied by petroleum oil/gas, leading to two-thirds of CO₂ emissions in the environment. However, fossil fuel resources are scarce, non-renewable, and rapidly depleting against growing demand. Health and environmental issues, supply chain disruptions, and geopolitical events have prompted researchers to explore alternative liquid fuels. One of the major utilizers of liquid fuel viz. diesel engines, remain essential for transportation, industries, agriculture, and small power plants; however, a shift towards renewable and eco-friendly fuels is necessary (Liu et al., 2022). In this context, biofuels derived from biomass (i.e., sugarcane, beet, sweet sorghum, etc.) and oils (palm oil, soybeans oil, etc.) have gained considerable interest in fulfilling the shortage of conventional fuel (Ansari et al., 2021; Kumar Prajapati et al., 2025). Among biomass-derived fuels, biodiesel and bioethanol are the two most commonly used biofuels. Biodiesels have first-, second-, and third-generation categories (Fayad et al., 2023; M.A. Fayad et al., 2022). The edible materials or vegetal oils are feed for the first generation of biodiesel (Datta and Mandal, 2016; Mohiddin et al., 2021). Second generation biodiesel is sourced from non-edible oil plants, viz. Mahua, Pongamia, and Jatropha. Third-generation biodiesel is produced using several biomass feedstocks (Leong et al., 2018; Stančin et al., 2020).

The primary drawback associated with first-generation biodiesel manufacturing lies in the competition for edible oil with the food industry. Further, it contains lower energy than petroleum diesel (Pandey et al., 2015). The arable land exploitation for biodiesel-generating crops may lead to augmented food prices (because of food shortages), creating food insecurity (Rezania et al., 2019). Hence, the focus on producing biodiesel has shifted to non-edible sources. The biodiesel is generated through a transesterification utilizing methanol and oil under a catalytic environment and mild conditions. Acid and alkali are utilized as catalysts (Bashir et al., 2022). Homogeneously catalyzed transesterification is extensively utilized for commercial biodiesel production, despite other methods being less established due to high operating costs (Neag et al., 2023). Heterogeneous transesterification, though not commercially established, eliminates catalysts and reduces reagent requirements and energy spent in biodiesel production (Chen et al., 2021; Neupane, 2023).

The unique advantage offered by biodiesel as engine fuel over petroleum diesel is the carbon neutrality inherent in its life cycle (Wu et al., 2023). This is because the CO₂ emissions generated by the combustion of biodiesel fuel are balanced with the quantity of CO₂ consumed in plantation (Fankhauser et al., 2022). Biodiesel’s high O₂ concentration (∼11% by weight) allows for full combustion, unlike petroleum diesel. When burned, it emits reduced unburned hydrocarbons, carbon monoxide, and particulate substances into the atmosphere. Furthermore, it does not emit hazardous oxides of sulfur because it has little sulfur content, making it ecologically beneficial (Sorate and Bhale, 2015). The biodiesel’s higher cetane number is ascribed to more number of fatty acids as well as saturation. It has a higher density (∼ 1.05 times) (Guo et al., 2016) and a higher flash point (by 50°C) than petroleum diesel, which makes it safe for transport, handling, and storage (Riyadi et al., 2023). Biodiesel is recognized as a lucrative engine fuel with good lubrication properties, increasing engine life, reducing friction loss, and improving brake thermal efficiency (BTE) (Kale et al., 2014; Ogunkunle and Ahmed, 2019; Tran et al., 2021).

The Indian government has sanctioned amendments to the National Policy on Biofuels, 2018, allowing the production of biofuels from numerous feedstocks. This move aimed to reduce petroleum imports through increased biofuel production and promote the Make in India drive (Roy and Chandra, 2019). Further, FSSAI has initiated the Repurpose Waste Cooking Oil (RWCO) program for converting used cooking oil into biodiesel. Despite studies showing biodiesel can be blended up to 20% without significant engine modifications, only 5% of biodiesel blends are permitted in India (Babji et al., 2024; Chaudhari et al., 2023; Jayabal et al., 2022; Tan et al., 2023). Waste cooking oil finds usage as a cheap and secondary domestic fuel, and as a source to produce plastics, lubricants, soaps, detergents, and aromatherapy (Frota de Albuquerque Landi et al., 2022; Hwang et al., 2016). The used cooking oil (UCO) is often disposed of without any treatment, causing significant environmental, societal, and health consequences (Degfie et al., 2019). WCO may be recycled to make biodiesel, like mobile fuel. This reduces pollution emissions and costs associated with waste management, and partly interchanges the import of petrochemical oil (Mahmood Khan et al., 2020). Biodiesel fuels can address issues like reduced BTE, higher brake specific fuel consumption (BSFC), and higher tailpipe emissions by using fuel additives (Konur, 2021).

Despite benefits, biodiesel includes enhanced NOx emissions, demonstrates poor cold flow properties, and heating values (Yaqoob et al., 2021). It often requires higher fuel injection pressure (Ramarao et al., 2015). The presence of fatty acid chains and saturation (or double bonds) also decreases the shelf life and oxidation capability of biodiesel (Chandran, 2020). Biodiesel alone shows lower BTE than petroleum diesel (An et al., 2013); however, when mixed with fuel additives, it can address issues of lower BTE, provide higher BSFC, and minimize higher tailpipe emissions (i.e., CO and HCs); hence, it is suitable for the effective performance of compression ignition (CI) engine (Konur, 2021). Further, adding nanoparticles to a biodiesel-diesel blend is anticipated to boost engine working (Soudagar et al., 2018). Nanoparticles in a BD provide enhanced surface-to-volume ratio and additional reactive surface for fuel oxidation, resulting in less ignition delay, greater combustion, and higher heat discharge (Ansari et al., 2023; Modi et al., 2024).

Producing nanoparticles could be tedious, time-consuming, and costly. Regulating nanoparticle’s dimensions, texture, and porosity remains difficult during synthesis, and its uniform dispersion in the fuel is desirable. In this context, several authors have enabled the control of nanoparticle size, shape, and porosity, thereby enhancing stability and dispersion of nanofluids in the fuel (Catauro et al., 2018; Suryawanshi et al., 2023; Venkatesan et al., 2017). Nanofluids are typically generated in one or two processes, with some developing synthesis techniques (Harish et al., 2023; Lee et al., 2021). In a one-step process, nanoparticles and base liquid are added together, making it cost-effective and stable over time. Current one-step synthesis processes encompass direct evaporation, laser ablation, vapor deposition, and submerged arc welding, eliminating the requirement for drying, preservation, and dispersion (Harish et al., 2022; Janakiraman et al., 2020; Yogesh et al., 2021). The two-step synthesis, a widely accepted method for nanofluids synthesis, involves separate steps for nanoparticle preparation and addition to the base liquid, offering enhanced distribution and consistency than the one-step method. Further, nanoparticle synthesis with the top-down route contains mechanical grinding, thermal decomposition, nanolithography, and laser ablation, reducing larger particles into nanoparticles. Bottom-up processes, such as the sol-gel technique, pyrolysis, chemical vapor deposition, and biosynthesis, accumulate atoms to form nanosized particles (Altammar, 2023; Baig et al., 2021). Green synthesis is a one-step route for synthesizing nanoparticles using a bottom-up approach. It utilizes biological substrates like bacteria, plant extracts, algae, or fungi to reduce a metal salt, which serves as a precursor to its metal oxide (Kuppusamy et al., 2016). The substrate is prepared through the plant extract (like leaves, flowers, stems, fruit peels, seeds, and roots), containing biomolecules like amines, sterols, enzymes, and phenols (Arun et al., 2023; Bilgiç Tüzemen, 2024; Yatish et al., 2021). These biomolecules prevent the growth and clustering of metal oxide nanoparticles. The metal oxide nanoparticles, once formed, are further reduced through NaOH or KOH, followed by filtration, drying, and calcination steps to achieve uniform grain size and desired morphology (Bitire and Jen, 2022; Doğan et al., 2024; Murugesan et al., 2021). The utilization of biomolecules in nanoparticle synthesis eliminates the harmful chemicals, and hence, the approach can be environmentally attractive.

Various additives like oxygenated additives, graphene, acetylene black, carbon nanotubes, metals, and metallic oxides have been investigated for biodiesel-fuelled CI engines (Manigandan et al., 2020). Metal oxides (MOs) nanoparticles, such as oxides of aluminum (Al₂O₃), cerium (CeO₂), titanium (TiO₂), and copper (CuO), among others, are better suited for enhancing engine performance because of their extra oxygen content. The MOs generate a large quantity of oxygen within the combustion chamber, which reacts with products of incomplete combustion, i.e., CO, HC, and C atoms in soot particles, and helps in complete combustion. This increases the overall heat release and reduces harmful greenhouse gas emissions. Hao et al. demonstrate that aluminum nano-additives have robust oxygen extraction capabilities and can decrease energy and induction time for catalytic combustion reactions (Hao et al., 2019). Carbon-based nanotubes can improve ignition rate and total combustion period. Numerous works revealed that the addition of nanoparticles to BD substantially enhanced engine performance (Ghanbari et al., 2017; Kegl et al., 2021; Kiran et al., 2021). This is credited to a higher surface area-to-volume ratio, higher energy density, catalytic performance, and additional reaction activation sites in nanoparticles (Contreras et al., 2017; Eroglu et al., 2013). Soudagar et al. revealed that adding alumina to BD (i.e., 80% diesel and 20% biodiesel) augmented peak cylinder pressure and heat release, causing faster ignition and combustion for engines operating at maximum load (Soudagar et al., 2020). The study revealed an 11.27% increase in NOx, but a 26.72% decrease in unburnt HCs and a 48.43% decrease in CO emissions. The carbon nanotubes in biodiesel augmented the power (by 3.67%), BTE (by 8.12%), and BSFC (by 7.12%) of the diesel engine, while causing a 27.49% higher NOx release (Hosseini et al., 2017). Muruganantham et al. showed that adding cerium oxide nanoparticles (50 ppm) in biodiesel improved BTE (34.7%) and lessened unburnt HCs emissions (20.8%) (Muruganantham et al., 2021). Despite numerous MO nanoparticles explored as fuel additives to increase engine working, the use of CaO nanoadditives (as nanorods) in the biodiesel-diesel blend for assessing the CI engine working and emissions is rarely studied. The present study investigates the enhancement of CI engine performance by incorporating Calcium oxide nanorods (CaO NRs) embedded biodiesel-diesel blend. The CaO NRs are synthesized in an aqueous solution (a green route) using the extract of Murraya Koenigii leaves. This green synthesis with Murraya Koenigii leaves promised a steady and homogenous distribution of CaO nanoparticles in BD. The blend was tested for BTE, BSFC, exhaust gas temperature (EGT), combustion efficiency, smoke emissions, and stability.

2. Material and Methods

2.1 CI engine performance testing system

The experimental setup investigating CI engine performance with CaO NRs biodiesel-diesel blend has been shown in Fig. 1(a). The Kirloskar CI engine, possessing 3.5 kW rated power at 1500 RPM, was tested using a dynamometer. The setup had features such as dual fuel capability, PC synchronization (using EngineSoft software), and variable compression ratio adjustment. Parameters investigated include brake torque, thermal efficiency, and BSFC, all at a constant engine speed and variable engine load, in steps of 25% up to 100%.

(a) CI Engine assembly and accessories, and (b) Schematic of diesel engine test rig with mass and data flow.

Fig. 1(b) shows the schematic of the CI engine along with mass flow and data flow. An AVL Di Gas 444N five-gas analyzer was utilized to calculate CO, HC, NOx, O₂, and CO₂ emissions. AVL 437C smoke meter was used for the measurement of smoke. The measurements were calibrated using the zero calibration setting of the instrument before each trial (Chand, 2024). Further, the test rig specifications have been reported elsewhere (Chaudhari and Salunke, 2023).

2.2 Uncertainty analysis of measurements

The uncertainty analysis in measurements remains important to maintain measured data quality, compliance, and decision-making for real applications. The measured results or data measured from different instruments cannot be reliably compared without quantifying uncertainties. The lower value of uncertainty suggests that the measuring instruments do not require regular recalibration and maintenance, or vice versa. The uncertainties determined for the IC engine performance and emissions ensure that the CaO NRs mixed fuel blend can consistently meet the required combustion quality. The study used regular calibration of measuring tools to improve precision. Analytical approaches were used to calculate random and fixed errors, which can arise during experimental research due to factors like instrument selection, calibration, individual observation, working conditions, and analytic methods (Yu and Zhao, 2020). Experiments with test fuels were repeated thrice to ensure accuracy. The measuring range, accuracy, and uncertainty for each measured parameter have been provided in Table 1. Table 1 shows percentage uncertainties for braking power, engine speed, BSFC, BTE, EGT, emissions, and smoke opacity. The square root technique used to quantify the overall uncertainty of the experimental test was calculated by combining the individual uncertainties of the measured parameters using the root-sum-square (RSS) method (Eq. 1).

(1)

\begin{matrix} Uncertainty = \sqrt{B P^{2} + B S F C^{2} + N^{2} + B T E^{2} + E G T^{2} + H C^{2} + C O^{2} + C O_{2}^{2} + N O x^{2} + S M O K E^{2}} \\ = \sqrt{{0.1}^{2} + 2^{2} + {0.5}^{2} + 2^{2} + {0.2}^{2} + {0.04}^{2} + {0.07}^{2} + {0.47}^{2} + {0.48}^{2} + {0.07}^{2}} \\ = \pm 2.96 % \end{matrix}

Table 1. Instruments range, accuracy, and % uncertainty.

Instrument used	Measured parameter	Measuring range	Resolution	Uncertainy
Eddy current dynamometer	Brake power	0-50 kW	± 0.5 kW	± 0.1%
Inductive pickup tachometer	Engine speed	0-10000 rpm	± 5 rpm	± 0.5%
Stopwatch and burette	Fuel consumption	0-200 g/s	0.5 g/s	± 2.0%
Thermocouple (K-type)	EGT	0-1200^oC	± 1^oC	± 0.2%
AVL Di Gas 444N five gas analyzer	CO	(0-10% vol.)	0.01% vol.	± 0.04
	CO₂	(0-20% vol.)	0.1% vol.	± 0.07
	HCs	(0-20000 ppm)	1 ppm/10 ppm	± 0.047
	O₂	(0-25% vol.)	0.01% vol.	± 0.01
	NOx	(0-5000 ppm)	1 ppm	± 0.048
AVL 437°C smoke meter	Smoke opacity	(0-100 in %)	0.01%	± 0.07

2.3 Murraya Koenigii leaves extract and synthesis of CaO NRs

Murraya Koenigii leaves extract was synthesized using 98% calcium nitrate (CaNO₃)₂, NaOH, and DI water (Loba Chemie). The Murraya Koenigii leaves were sourced from a local farm in India. The equipment and glassware used for leaf extract included an electric oven and muffle furnace, a magnetic stirrer with a thermostat-controlled heating plate, a weighing balance, a measuring flask, burettes, crucibles, Whatman No. 1 filter paper, Petri dishes, etc. Fig. 2(a) shows the preparation of an aqueous extract of Murraya Koenigii leaves. The leaves underwent a dual washing using DI water, subsequent oven-drying at 80°C for 2 hrs. Dry leaves were cut into pieces and heated with DI water up to 30 mins to get an extract (light brown solution). The solution underwent filtration to eliminate impurities, and the leaf extract was subsequently preserved at 4°C. Several studies have shown the use of Murraya koenigii leaves as a biological substrate for nanoparticle biosynthesis (Balakrishnan et al., 2020; Devatha et al., 2016; Goel and Tomar, 2022; Pratim Sarma et al., 2023; Sharma et al., 2023).

(a) Murraya Koenigii leaves extract and (b) synthesis of CaO nanoparticles.

Further to synthesize CaO NRs, a mixture containing 0.5 M calcium nitrate solution and Murraya Koenigii leaves extract was stirred at a stable 60°C. Then, 0.5 M NaOH was added dropwise to it. The solution, which was initially semi-white, turned yellow due to the development of Ca(OH)₂ particles as shown in Fig. 2(b). The suspension was kept for settling, and the precipitate was filtered using a Whatman paper and then washed using water, and oven-dried at 110°C for 2 hrs. Calcium oxide nanoparticles were acquired through calcination at 400°C for 3 hrs using a muffle furnace. It was then cooled overnight (Bano and Pillai, 2020; Khine et al., 2022). The possible reactions for the formation of CaO NRs are shown below:

(2)

C a {(N O_{3})}_{2} + 2 N a O H \to C a {(O H)}_{2} + 2 N a N O_{3}

(3)

C a {(O H)}_{2} \to C a O + H_{2} O

2.4 Preparation of fuel blends

The WCO-derived BD was used as test fuel. The properties of blends (B0 and BD) viz. density and calorific value, were determined. Performance characteristics of the CI engine were obtained through engine testing. The diesel and biodiesel-diesel blend were named B0 and BD, respectively. The different proportions of CaO NRs used in the BD were named BDC50 and BDC100. Table 2 shows that the lower calorific value and specific gravity of BD, BDC50, and BDC100 blends agreed with B0. The experimental investigations were carried out under varied loading conditions (0%-100%), with each reading recorded under steady-state conditions. The working of the engine and emission parameters of synthesized fuel samples (mentioned in Table 1) were evaluated in the CI engine against the standard diesel fuel (B0).

Table 2. Specifications of the fuel blends.

Test fuels	Pure diesel, % volume	Biodiesel, % volume	CaO NRs concentration, ppm (mg/liter)	Lower calorific value (kJ/kg)	Sp. Gravity, (kg/m³) at 15°C
B0 (pure diesel)	100	0	0	42.93	0.833
BD	80	20	0	41.64	0.847
BDC50	80	20	50	41.42	0.852
BDC100	80	20	100	41.30	0.857

3. Characterization of CaO particles

The structural characteristics of the synthesized CaO NRs were examined with a scanning electron microscope (SEM), model JEOL JSM-7600F, and a transmission electron microscope (TEM), model Tecnai G2 F30, functioning at an operational voltage of 300 kV. The optical absorption properties of synthesized CaO NRs were examined utilizing a UV-Vis spectrophotometer. The absorbance spectra were attained with a Cary 60 UV-Vis spectrophotometer, allowing for accurate and reliable studies of their optical characteristics. Fourier transform infrared (FTIR) spectroscopy was used for characterizing and examining functional groups (FGs) over the surfaces of CaO. A Bruker Alpha-II spectrometer was used for FTIR analysis, which provided high-resolution spectrum data to establish the presence and type of certain FGs on CaO NRs. The structural features of the CaO, including their crystalline phases and lattice constants, were investigated using X-ray diffraction (XRD).

4. Results and Discussion

4.1 Surface morphology and composition of CaO NRs

The surface morphology of the synthesized CaO NRs, thoroughly inspected using SEM. Fig. 3(a) revealed the formation of CaO NRs, which appeared as groups of aggregated NRs of 50 to 100 nm and a length of approximately 500 nm. These dimensions were consistent with the expected size range for nanorods and demonstrated their elongated structure. Fig. 3(b) shows the HR-TEM image of CaO NRs, which shows a diameter of approximately 60 nm. This observation aligned and confirmed with the SEM results, further validating the successful synthesis of CaO NRs with consistent dimensions. Fig. 3(c) shows energy dispersive X-ray (EDX) analysis of CaO NRs. EDX analysis revealed the peaks of Ca and O elements. The Ca and O were found to be 45.77 wt% and 54.23 wt%, respectively, indicating the synthesis of a highly pure material. Fig. 3(d) shows the SAED pattern of CaO NRs, which exhibited distinct diffraction spots confirming the crystalline nature of the NRs. The SAED pattern confirmed the highly ordered crystal nature of the synthesized CaO NRs, corroborating the findings from both the XRD and SEM analyses. The stability of CaO NRs in BDs (BDC50 and BDC100) was assessed through visual inspection and sedimentation test over 48 hrs. No significant agglomeration or sedimentation was observed for NRs, indicating uniform dispersion facilitated by the organic capping agents from Murraya Koenigii leaf extract, which was also confirmed by FTIR analysis.

Characterization of CaO NRs: (a) SEM micrographs showing CaO NRs morphology, (b) HR-TEM image confirming rod shape, (c) EDX analysis verifying elemental composition, and (d) SAED pattern indicating crystalline structure.

4.2 UV-Vis diffuse reflectance (DRS) spectroscopy and surface functionalities of CaO NRs

The UV-Vis DRS of CaO NRs exhibited substantial absorption in the visible light spectrum (Fig. 4a). This indicates that CaO NRs exhibit strong absorption in the visible region, suggesting potential for light-assisted catalytic processes. The optical bandgap (Eg) of CaO NRs was calculated by extrapolating the curve’s tangent to the x-intercept (hv). Fig. 4(b) shows the Tauc plot analysis of the UV-Vis DRS data, revealing an optical band gap of CaO NRs of about 3 eV. This direct band gap energy corresponds to the visible range, suggesting that CaO NRs can efficiently absorb visible photons and generate electron-hole pairs. This property indicates their potential for applications for driving photocatalytic reactions and light-emitting processes (Menezes et al., 2023; Tabrizi Hafez Moghaddas et al., 2024). The narrow bandgap is particularly advantageous for the sustainable performance of BDs, as it enables efficient light absorption to activate catalytic processes, causing better oxidation of fuel molecules, thus improving combustion efficiency and minimizing emissions of soot carbon, CO, and HCs (Mofijur et al., 2024). CaO NRs, when added to BDs, can act as effective combustion catalysts. The visible-light interaction of CaO NRs, driven by their bandgap, promotes pre-ignition oxidation reactions, enhancing combustion kinetics and reducing emissions. These characteristics address key challenges in CI engines, such as incomplete combustion and excessive emissions, making CaO NRs a sustainable additive for cleaner and more efficient fuel combustion. The optical properties of CaO NRs align with recent findings that emphasize the role of bandgap-engineered metal oxide nanoparticles in energy and environmental research (Chen et al., 2020).

(a) UV-Vis absorption spectra of CaO NRs (b) Tauc plot for optical bandgap estimation of CaO NRs (c) FTIR spectra of CaO NRs.

The surface functionalities of CaO NRs were analyzed through FTIR, providing information about chemical groups on nanoparticle surfaces. Fig. 4(c) confirmed the presence of organic capping agents derived from the leaf extract, which were instrumental in stabilizing the CaO NRs during the green synthesis process. Distinct absorption peaks were detected spectrum at 1407, 872, and 712 cm⁻¹, corresponding to specific FGs. The peak at 1407 cm⁻¹, credited to O-H bending vibrations, signified the occurrence of hydroxyl groups on the CaO NRs surface. These hydroxyl groups were likely to originate from phenolic and alcohol compounds in the Murraya Koenigii leaves extract, which acted as both reducing and stabilizing agents during CaO NRs synthesis. This observation aligned with earlier studies highlighting the role of plant-derived biomolecules in capping and stabilizing nanoparticles through green synthesis approaches (Liu et al., 2018; Naveed et al., 2017). The band at 872 cm⁻¹ was related to C-H bending vibrations, indicating the adsorption of organic molecules from the plant extract onto the nanoparticle surface. The absorption at 712 cm⁻¹ corresponded to bending vibrations linked to interactions with other organic FGs present in the plant extract. Together, these FGs, primarily hydroxyls and amines, enhanced the stabilization and dispersion of the CaO NRs in the biodiesel-diesel blends, preventing nanoparticle aggregation and improving their catalytic potential. Such surface modifications have been shown to contribute significantly to the catalytic efficiency and stability of nanoparticles (Aigbe and Osibote, 2024; Gao and Bei, 2016). The successful capping of CaO NRs by organic biomolecules confirmed the effectiveness of the Murraya Koenigii-mediated green synthesis. This process aligned with prior studies that emphasized the role of plant-based biomolecules in nanoparticle stabilization and functionalization, thus validating the approach’s eco-friendliness and sustainability (Mazher et al., 2023; Nazir et al., 2022). These results corroborated findings from previous research on biofunctionalized nanoparticles and their improved chemical stability (Rani et al., 2023; Su et al., 2020).

4.3 Crystalline structures of CaO NRs

The crystalline arrangement of CaO NRs was examined using an XRD device, the Bruker D8. The samples were scanned at a rate of 2° per minute across a 2θ range of 5° to 50°, using a nickel-filtered CuKα radiation source (λ = 1.54 Å). The XRD spectrum, presented in Fig. 5, showed a sharp peak pattern, confirming crystalline CaO NRs. The notable diffraction peaks were identified at 18.3°, 32.18°, 37.34°, and 42.8°, corresponding to the (001), (011), (002), and (012) crystal planes of CaO, respectively. The presence of a particular crystallographic plane inside the face-centered cubic (FCC) structure of CaO is shown by the (002) peak. The sharpness and peak intensity indicated the formation of a well-ordered crystalline structure, containing a little amorphous material or defects. The XRD result confirmed that the green synthesis method using Murraya Koenigii leaves extract effectively produced highly crystalline CaO NRs (Jadhav et al., 2022).

4.4 CI Engine performance with CaO NRs biodiesel-diesel blend

4.4.1 BTE

The BTE represents the ratio between braking power at the output shaft to fuel energy, which specifies how much fuel energy is transformed into mechanical energy at the engine shaft. It is determined by the fuel’s rate of consumption and calorific value. Fig. 6 depicts the deviation in % BTE with engine loads for CaO NRs biodiesel-diesel blends (BDC50 and BDC100), B0, and BD fuels. BTE was observed to increase with engine load, owing to higher fuel rate and output (see Fig. 6). Diesel fuel showed a greater BTE than BD due to its higher energy content. However, adding CaO NRs to BD (i.e., BDC50 and BDC100 fuels) at various doses (50 ppm and 100 ppm) increased BTE considerably than pure and 20% biodiesel blends. At peak engine load, the BDC100 fuel indicated a maximum BTE of 24.9%, which was 3.32% greater than BD and BDC50, as shown in Table 3.

Table 3. Summary of engine performance and emission parameters concerning pure diesel, BD, BDC50, and BDC100 fuels.

Parameter	Pure Diesel	BD	BDC50	BDC100
BTE (%)	26.8	24.1	24.68	24.9
BSFC (kg/kWh)	0.3072	0.3289	0.3241	0.3212
EGT (^oC)	386	419	392	398
CO (g/kWh)	6.5	4.3	3.6	3.2
HC (g/kWh)	0.1561	0.1401	0.1121	0.1061
NOx (g/kWh)	6.7289	6.8483	6.6094	6.5298
Smoke Intensity (%)	82	78	54	46

The increase in BTE occurred because of enriched atomization, fuel evaporation, and superior air-fuel mixing, which results in complete combustion (Fayad et al., 2024a; Hameed and Muralidharan, 2023). BDs with CaO NRs functioned as fuel catalysts and oxygen buffers during combustion (Sudarsanam and Jayaprabakar, 2024). Further, the higher O₂ percentage in CaO NRs increased combustion efficiency, causing higher BTE (Jegan et al., 2023). Similar observations were reported by Reddy et al. (Reddy et al., 2021), suggesting that NPs may show a catalytic nature and enhance engine working by improving atomization, evaporation, and mixing rates (Reddy et al., 2021; Soudagar et al., 2020).

4.4.2 Brake-specific fuel consumption (BSFC)

BSFC signifies a measure of fuel quantity used by the engine to generate one unit of brake power. It is primarily determined by its calorific value, density, and viscosity. Fig. 7 shows the BSFC of B0, BD, BDC50, and BDC100 fuels at various engine loads. Fig. 7 indicates that the BSFC of the evaluated biodiesels declined with increasing engine loads. BSFC at full load conditions for pure diesel, BD, BDC50, and BDC100 were 0.233, 0.252, 0.3, and 0.3212 kg/kW h, respectively. B0 showed a lower BSFC value than the BD blend at all engine loads because of biodiesel’s inferior calorific value and higher density. The BD blend with greater viscosity also resulted in poor atomization and reduced combustion efficiency. However, adding CaO NRs to the BD (i.e., BDC50 and BDC100) lowered fuel usage while providing the same power output. The CaO NRs-doped fuel also had lower BSFC values than BD due to its greater oxygen content, which promoted oxidation reactions and reduced the BSFC. The current investigation outcomes were comparable with the literature on nanoparticles with biodiesel (EL-Seesy et al., 2023).

4.4.3 Exhaust gas temperature (EGT)

The EGTS of B0, BD, BDC50, and BDC100 fuels at diverse engine loads were examined. For the same engine load, the higher value of EGT indicates that the engine rejects more heat to the surroundings and lowers the BTE. Fig. 8 shows the increasing nature of EGT with higher engine loads due to the greater engine cylinder temperature, causing more fuel combustion. However, adding CaO NRs to the BD blend decreased the EGT. At peak engine load, BDC50 fuel produced 6.44% lower, and BDC100 fuel produced 5.01% lower EGT than BD fuel. The augmented O₂ percentage due to CaO NRs also improved combustion and homogenization in the fuel. The minimization of EGT using CaO NRs in the fuel may benefit the environment since it lowers heat release than pure diesel. Further, incorporation of nanoparticles is reported to improve in-cylinder combustion characteristics (Das et al., 2022; Jin et al., 2023; Kumar et al., 2021).

Effect of CaO NRs on fuel exhaust gas temperature.

4.4.4 Emission parameters

Emission metrics were evaluated for all fuels. Emission components were determined based on brake-specific rates for brake power.

4.4.4.1 Brake-specific carbon monoxide

The CO is produced because of the incomplete combustion of diesel fuel and is influenced by the air-to-fuel ratio, pressure, and quality of fuel injection, timing, fuel nature, spray diffusion, and wall quenching (Tuan Hoang et al., 2022). Variations of brake-specific CO with engine load for B0, BD, BDC50, and BDC100 have been revealed (Fig. 9a). Fig. 9(a) displays that CO emissions enlarged at low engine loads but lessened with rising engine loads for all the fuels (i.e., B0, BD, BDC50, and BDC100). Notably, the lower combustion chamber temperatures resulted in higher CO emissions, while higher loading conditions led to complete combustion, converting CO to CO₂, and hence, CO must be minimized for good engine performance. It is seen in Fig. 9(a) that B0 fuel had higher CO emissions, while BD had lower CO release for all engine loads. Further, the inclusion of CaO NRs in BD or biodiesel-diesel blends (i.e., BDC50 and BDC100) showed an additional decrease in CO release for the entire engine loads, indicating the fuel’s complete combustion. CaO NRs facilitated oxidation reactions by acting as O₂ donors, guaranteeing comprehensive combustion and thus reducing the CO amount. These oxygen-buffering effects have been observed in similar studies, where nanoparticles enhanced oxidation and reduced CO formation in biodiesel blends (Hoang, 2021; Jin et al., 2023). Thus, the CaO NRs with a BD blend showed the least CO emissions across all engine loads. At the peak engine load, BDC50 and BDC100 produced 16.7% and 25% lower brake-specific CO release, respectively, than BD fuel. The synergy of oxygen content and the catalytic effects of CaO NRs reduced the CO formation. CaO NRs exhibited less CO due to their oxygen-donating nature, which promoted oxidation reactions and reduced CO formation (Hoang, 2021). The fuel combustion with reduced CO emission was also evidenced by higher BTE for CaO NRs blends. Prabu et al. (Prabu, 2018) have found that the addition of nanoparticles at 30 ppm with biodiesel (BD) reduced CO emission formation due to faster evaporation and improved fuel atomization. Further, nanorods break fuel homogeneity, ensuring an appropriate air-fuel mixture and improved combustion efficiency.

Effect of CaO NRs on emissions for B0, BD, BDC50, and BDC100 fuels: (a) brake-specific CO, (b) brake-specific unburned HC, (c) brake-specific NOx, and (d) smoke opacity at various engine loads.

4.4.4.2 Brake-specific unburned HC

Unburned hydrocarbon emissions in diesel engines result from the uneven fuel mixing with air within the combustion chamber. This incomplete mixing hampers oxidation reactions, leaving hydrocarbons unburnt. Factors such as low combustion temperatures, insufficient oxygen availability, and improper air-fuel ratios contribute significantly to unburned hydrocarbon emissions (Devarajan et al., 2018). Improper combustion chamber design, suboptimal fuel injection systems, and induction system irregularities further exacerbate these emissions (Bari et al., 2020). Fig. 9(b) displays variation in brake-specific unburned HC release for B0, BD, BDC50, and BDC100 fuels across different engine loads. The unburned hydrocarbon emissions from B0 remain high at the entire engine load, primarily because of its lower O₂ percentage and incomplete combustion characteristics (see Fig. 9b). The BD blend showed reduced unburned hydrocarbon emissions than B0, because of its higher cetane number and % O₂. Further, the BDC50 and BDC100 blends exhibited 20% and 24.3% lower unburned hydrocarbon emissions, respectively, when compared to BD fuel. Similarly, BDC50 and BDC100 fuels reduced unburned hydrocarbon emissions by 28.2% and 32.1%, respectively, than B0. The substantial reduction in unburned hydrocarbons for BDC50 and BDC100 fuels can be attributed to the catalytic activity of CaO NRs. The nanorods provided additional oxygen during combustion, improving flame propagation and ensuring complete oxidation of hydrocarbons. Their high reactivity accelerates the breakdown of hydrocarbon molecules, leading to faster ignition and lower hydrocarbon emissions in the exhaust. Moreover, the presence of CaO NRs enhanced the uniformity of the fuel-air mixture during injection, promoting complete combustion (Rathinam et al., 2020). These findings aligned with recent studies, which emphasized the role of nanoparticles in decreasing unburned HC release by enhancing combustion dynamics (Jin et al., 2023; Mofijur et al., 2024).

4.4.4.3 Brake-specific oxides of nitrogen

Nitrogen oxides (NOx) are primarily formed in diesel engines through high-temperature reactions between atmospheric nitrogen and oxygen, facilitated by the elevated in-cylinder temperatures during combustion. These thermally driven reactions follow the Zeldovich mechanism, where nitrogen species and oxygen radicals contribute to NOx formation. Fig. 9(c) illustrates the NOx release for B0, BD, BDC50, and BDC100 fuels. At full engine load, B0, BD, BDC50, and BDC100 produced NOx emissions of 6.73 g/kWh, 6.84 g/kWh, 6.61 g/kWh, and 6.53 g/kWh, respectively. Upon comparison, the BD blend exhibited slightly higher NOx emissions than B0 due to a larger O₂ percentage. This phenomenon aligns with the “oxygen paradox,” wherein biodiesel’s oxygenation, while improving combustion, inadvertently promotes NOx formation through thermal mechanisms (Masera and Hossain, 2023). The addition of CaO NRs in BD blends (i.e., BDC50 and BDC100) mitigated NOx emissions, reducing them to 6.53 g/kWh for BDC100. This reduction was primarily due to the dual role of CaO NRs as oxygen buffers and thermal regulators. The nanoparticles facilitated the formation of reactive hydroxyl radicals, which quench NOx by promoting the recombination of nitrogen species (Voinov et al., 2011). Furthermore, CaO NRs acted as heat sinks, dissipating thermal energy and minimizing hot spots within the combustion chamber, which are key sources of thermal NOx formation (Fayad et al., 2022a). The catalytic activity of CaO NRs also enhanced the in-cylinder oxidation-reduction reactions, preventing excessive oxygen availability for NOx formation (Fayad et al., 2022b). Additionally, these nanoparticles improve convective heat transfer and stabilize combustion thermodynamics, suppressing thermal NOx pathways (Fayad et al., 2024b). These findings were in agreement with the literature, which demonstrated that nanoadditives in fuel significantly reduce NOx emissions by optimizing combustion conditions and acting as reduction catalysts (Appavu et al., 2019; Devaraj et al., 2021).

4.4.4.4 Smoke opacity

Smoke development in CI engine exhaust indicates incomplete fuel combustion during operation (Gad et al., 2022). Smoke opacity is a critical metric that quantifies soot concentration in exhaust emissions, primarily influenced by the balance between soot production and oxidation reactions. The formation of smoke is predominantly observed in the rich fuel-air mixture zones, especially at higher engine loads, where increased fuel injection is required for power generation. Fig. 9(d) elucidates the variant in smoke opacity with engine loads, showing higher values during pure diesel operation, particularly under full-load conditions. At full engine load, smoke concentrations for BD, BDC50, and BDC100 fuels were 4.88%, 34.15%, and 43.9% lower than pure diesel, respectively. Furthermore, the BDC50 and BDC100 blends exhibited significantly reduced smoke opacity compared to BD. The CaO NRs mixing in BD blend (i.e., BDC50 and BDC100) played a critical role in further reducing smoke opacity. The nanorods accelerated the oxidation of soot precursors and enhanced the breakdown of hydrocarbon molecules into smaller fragments, thus promoting complete combustion (Abed et al., 2018). Additionally, NRs improved the homogeneity of the fuel-air mixture and facilitated soot oxidation by supplying reactive oxygen species during combustion. Fig. 9(d) underscores the catalytic impact of CaO NRs in reducing smoke generation, highlighting their potential as sustainable nanoadditives for improving fuel combustion in CI engines. The values of BTE, BSFC, EGT, and emission parameters at peak loads have been summarized in Table 3.

Thus, the CaO NRs embedded biodiesel-diesel blend demonstrated promising potential in booting CI engine working and diminishing destructive release to the environment.

5. Conclusions

The present work demonstrated the successful application of green-synthesized CaO NRs as fuel (or) nanoadditives to augment CI engine working and minimize its emission features. The CaO NRs synthesized using Murraya Koenigii leaves extract exhibited promising activity for combustion and oxygen-buffering properties. The BDC100 fuel outperformed BD in key parameters, with a 3.32% rise in BTE and substantial reductions in emissions. Specifically, reductions of 25%, 24%, and 43.9% were observed in CO, unburned HCs, and smoke opacity, than BD fuel. Additionally, nitrogen oxide releases were minimized by 4.7% compared to BD, highlighting the ability of CaO NRs to mitigate the trade-offs associated with biodiesel usage. These improvements were credited to a superior combustion process eased via CaO NRs, which increased atomization, evaporation rates, and air-fuel mixing while acting as a heat sink to reduce NOx formation. The eco-friendly synthesis and multifunctional properties of CaO NRs underscore their potential in addressing sustainability challenges in diesel engine operations. This study was limited to a single-cylinder CI engine, and the long-term effects of CaO NRs on engine durability and potential nanoparticle emissions were not assessed. Future research could focus on evaluating the compatibility of CaO NRs with other biofuels and hybrid additives to further enhance engine performance and emission reduction. Moreover, conducting extended durability tests and lifecycle assessments would offer deeper insights into their scalability and practical application across diverse engine systems. The green synthesis of CaO NRs using Murraya Koenigii leaves is potentially cost-effective due to the availability of plant-based precursors, though further techno-economic analysis is needed to confirm scalability for industrial fuel applications. This research paves the way for sustainable solutions in alternative fuel technologies.

Acknowledgments

The authors extend their appreciation to the Deanship of Research and Graduate Studies at King Khalid University for funding this work through Large Research Project under grant number RGP2/236/46.

CRediT authorship contribution statement

Kiran Chaudhari: Conceptualization, Data curation, Writing – original draft. Nilesh P. Salunke: Resources, Visualization, Writing – review and editing. Shakeelur Raheman: Methodology, Administration, Writing – review and editing. Khursheed B. Ansari: Formal analysis, Funding acquisition, Writing–review and editing. Vijay R. Diware: Methodology, Validation, Writing – review and editing. Mumtaj Shah and Mohd Shariq Khan: Visualization, Writing–review and editing.

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Declaration of Generative AI and AI-assisted technologies in the writing process

The authors confirm that there was no use of artificial intelligence (AI)-assisted technology for assisting in the writing or editing of the manuscript and no images were manipulated using AI.

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1. Introduction

2. Material and Methods

2.1 CI engine performance testing system
2.2 Uncertainty analysis of measurements
2.3 Murraya Koenigii leaves extract and synthesis of CaO NRs
2.4 Preparation of fuel blends

3. Characterization of CaO particles

4. Results and Discussion

4.1 Surface morphology and composition of CaO NRs
4.2 UV-Vis diffuse reflectance (DRS) spectroscopy and surface functionalities of CaO NRs
4.3 Crystalline structures of CaO NRs
4.4 CI Engine performance with CaO NRs biodiesel-diesel blend

5. Conclusions

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Investigating the performance of biodiesel-diesel blend coupled with green-synthesized CaO nanorods for compression ignition engines

Abstract

Keywords

Biodiesel-diesel blend

CaO Nanorods

CI engine Performance parameters

Compression Ignition Engine

Emission parameters

1. Introduction

2. Material and Methods

2.1 CI engine performance testing system

2.2 Uncertainty analysis of measurements

2.3 Murraya Koenigii leaves extract and synthesis of CaO NRs

2.4 Preparation of fuel blends

3. Characterization of CaO particles

4. Results and Discussion

4.1 Surface morphology and composition of CaO NRs

4.2 UV-Vis diffuse reflectance (DRS) spectroscopy and surface functionalities of CaO NRs

4.3 Crystalline structures of CaO NRs

4.4 CI Engine performance with CaO NRs biodiesel-diesel blend

4.4.1 BTE

4.4.2 Brake-specific fuel consumption (BSFC)

4.4.3 Exhaust gas temperature (EGT)

4.4.4 Emission parameters

4.4.4.1 Brake-specific carbon monoxide

4.4.4.2 Brake-specific unburned HC

4.4.4.3 Brake-specific oxides of nitrogen

4.4.4.4 Smoke opacity

5. Conclusions

Acknowledgments

CRediT authorship contribution statement

Declaration of competing interest

Declaration of Generative AI and AI-assisted technologies in the writing process

References

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