Available online at website: https://journal. id/index. php/bcrec Bulletin of Chemical Reaction Engineering & Catalysis, 21 . 2026, x-x Original Research Article Effect of Equimolar Sodium Borohydride-Ferric Chloride Concentrations on Nano Zero-Valent Iron/Palm Shell Composites for Simultaneous Nanogold Recovery and Hydrogen Generation Puteri Nur Syakinah Nordin1. Aina Syamimi Noor Helmy1. Chan Juinn Chieh Derek2. Mohd Fariz Rajuli3. Siu Hua Chang1* 1Waste Management and Resource Recovery (WeResCu. Group. Faculty of Chemical Engineering. Universiti Teknologi MARA. Cawangan Pulau Pinang, 13500 Permatang Pauh. Penang. Malaysia 2School of Chemical Engineering. Engineering Campus. Universiti Sains Malaysia. Seri Ampangan, 14300 Nibong Tebal. Seberang Perai Selatan. Pulau Pinang. Malaysia 3Petronas Gas Berhad Level 49-50. Tower 1. Petronas Twin Towers, 50088 Kuala Lumpur. Malaysia. Received: 13th January 2026. Revised: 19th February 2026. Accepted: 20th February 2026 Available online: 30th February 2026. Published regularly: August 2026 Abstract Gold-containing waste solutions represent both an environmental liability and a valuable secondary resource, yet few existing technologies integrate nanogold recovery with sustainable hydrogen generation from these streams. In this study, the effect of equimolar sodium borohydrideAeferric chloride (NaBHCEAeFeClCE) concentrations on the synthesis and performance of nanoscale zero-valent iron . ZVI)/palm shell composites was systematically investigated for the simultaneous recovery of nanogold and generation of hydrogen from gold-containing aqueous solutions. The composites were synthesized at different equimolar NaBHCEAeFeClCE concentrations . 5Ae2. 0 M), while maintaining a fixed overall molar ratio, with palm shell biomass employed as a support to suppress particle aggregation and preserve reactive surface area. Nanogold formation was evaluated using UVAeVis spectroscopy via localized surface plasmon resonance, while hydrogen evolution was quantified by a water-displacement method. Surface properties were characterized by BET analysis. Nanogold recovery increased progressively with increasing equimolar precursor concentration, whereas hydrogen production exhibited a non-linear dependence, reaching a maximum of 29. 02 mL at 1. 5 M, which also corresponded to the highest BET surface area . 57 mA/. Further increasing the equimolar NaBHCEAeFeClCE concentration to 2. 0 M led to surface passivation and diminished reactivity. These results demonstrate that equimolar precursor concentration plays a critical role in governing nZVI/palm shell composite structure and functionality. The optimized composite exhibits strong potential as a multifunctional material for integrated precious metal recovery and green hydrogen production, thereby contributing to sustainable circular resource utilization and clean energy Copyright A 2026 by Authors. Published by BCREC Publishing Group. This is an open access article under the CC BY-SA License . ttps://creativecommons. org/licenses/by-sa/4. Keywords: Nano zero-valent iron. Equimolar precursor concentrations. Nanogold recovery. Hydrogen Palm shell composites How to Cite: Nordin. Helmy. Derek. Rajuli. Chang. Effect of Equimolar Sodium Borohydride-Ferric Chloride Concentrations on Nano Zero-Valent Iron/Palm Shell Composites for Simultaneous Nanogold Recovery and Hydrogen Generation. Bulletin of Chemical Reaction Engineering & Catalysis, 21 . , x-x. (DOI: 10. 9767/bcrec. Permalink/DOI: https://doi. org/10. 9767/bcrec. Introduction Nanogold, valued for its size-dependent electrical, catalytic, and surface properties, is widely used in electronics, catalysis, sensing, and biomedicine . Although electronic waste and * Corresponding Author. Email: shchang@uitm. my (S. Chan. industrial effluents contain abundant goldbearing precursors . , the recovery and controlled synthesis of nanogold from these complex matrices remain challenging due to inefficiencies in existing extraction and reduction approaches . Conventional nanogold synthesis methods also often depend on strong chemical reductants, energy-intensive bcrec_20636_2025 Copyright A 2026. ISSN 1978-2993. CODEN: BCRECO Bulletin of Chemical Reaction Engineering & Catalysis, 21 . , 2026, 404 environmental concerns . Ae. In parallel, hydrogen has emerged as a clean and efficient energy carrier critical to achieving global carbon neutrality . Although hydrogen can be produced via routes such as steam methane reforming, electrolysis, and biomass conversion . , most conventional techniques are energyintensive and generate substantial greenhouse gas emissions . These challenges have intensified the search for cost-effective and ecofriendly nanogold recovery and hydrogen production technologies. Recently, nanoscale zero-valent iron . ZVI) has attracted increasing attention as a multifunctional material for both nanogold recovery and hydrogen generation from aqueous systems, owing to its high reactivity, large specific surface area, cost effectiveness, and ability to function simultaneously as a reductant and an adsorbent . Its characteristic coreAeshell structure, featuring a metallic FeA core and an iron oxide shell, is widely proposed to support Specifically, the FeA core generally electron-transfer reactions, while the oxide shell provides accessibility and stabilize reaction intermediates . In nanogold recovery, nZVI has been reported to be capable of simultaneously reducing and adsorbing AuAA ions from chloroauric acid (HAuCl. solutions to form elemental nanogold (AuA), accompanied by oxidation of FeA to FeAA, as described in Equation . Fe0 AuCl4Oe Ie Fe3 Au0 4ClOe This coupled redoxAesorption mechanism is commonly proposed as a simplified explanation for the efficient removal and immobilization of gold species on the nZVI surface without the use of toxic chemical reductants. Studies such as Li et . have reported high nanogold recovery efficiencies from industrial wastewater using nZVI, demonstrating its potential for sustainable resource reclamation. A similar redoxAesorption interplay has also been proposed to contribute to hydrogen generation via water decomposition. this process, the FeA core is suggested to donate electrons to water molecules, producing hydrogen gas (H. , while the oxide shell adsorbs and facilitates the dissociation of water at the solidAe liquid interface, enhancing reaction kinetics . The overall reaction is expressed in Equation . 3yayce 0 4ya2 ycC Ie yayce3 ycC4 4ya2 This pathway offers a conceptual route for hydrogen production without emitting greenhouse gases, unlike conventional thermochemical methods . Although nZVI has been independently employed for nanogold recovery (Equation . and hydrogen production (Equation . ), the integration of both processes within a single system has not been reported yet. The nZVI is typically synthesized through chemical reduction of ferric salts . FeCl . using strong reductants such as sodium borohydride (NaBH . , as shown in Equation . 2yayceyayco3 6ycAycayaAya4 18ya2 ycC Ie 2yayce 0 6ycAycayayco cCy. 3 21ya2 In this reaction. Fe0 represents the reactive metallic core of nZVI responsible for reductive Theoretically, a NaBHCE:FeClCE molar ratio of 3:1 is required for complete reduction of FeAA to FeA. In practice. NaBHCE is often used in excess to compensate for its rapid hydrolysis and other competing side reactions, thereby ensuring complete FeAA reduction . However, excessively high NaBHCE:FeClCE ratios may induce uncontrolled hydrogen evolution, over-reduction, and the formation of boron-rich byproducts, which promote particle aggregation and surface passivation . While the NaBHCE:FeClCE stoichiometric balance of the redox reaction, the absolute concentrations of both reagents play a critical role in influencing FeAA reduction kinetics, as well as nZVI nucleation, particle growth, and colloidal stability . Our previous work identified a NaBH4:FeCl3 molar ratio of 4:1, slightly above the stoichiometric 3:1 requirement, as optimal for efficient and controlled nZVI formation . Nevertheless, the influence of absolute reagent concentrations at this fixed optimal ratio remains unexplored. Importantly, varying reagent concentrations while maintaining equimolar NaBHCE and FeClCE solutions and a constant overall 4:1 molar ratio enables isolation of concentration-dependent effects on FeAA reduction efficiency and nZVI yield, without interference from changes in molar ratio or total reagent volume. Such effects cannot be captured through molar-ratio adjustments alone, which primarily alter reaction stoichiometry rather than the physicochemical environment governing nZVI Accordingly, this study investigated the effect of varying the absolute concentrations of equimolar NaBHCE-FeClCE solutions, combined to maintain an overall NaBHCE:FeClCE molar ratio of 4:1, on nZVI yield and its performance in simultaneous nanogold recovery and hydrogen generation from gold-containing aqueous media. Palm shell, an abundant biomass in Malaysia . , was employed as a support material to fabricate nZVI/palm shell composites, mitigating nZVI aggregation and preserving its reactive surface area. Nanogold recovery was quantified by Copyright A 2026. ISSN 1978-2993 Bulletin of Chemical Reaction Engineering & Catalysis, 21 . , 2026, 405 UVAeVis spectroscopy based on localized surface plasmon resonance (LSPR) intensity. Hydrogen production was measured via the waterdisplacement method, while the purity of the generated hydrogen gas was analysed using gas chromatography equipped with a flame ionisation detector (GC-FID). The surface properties and reactivity of the synthesized composites were further evaluated via BrunauerAeEmmettAeTeller (BET) analysis. Overall, this work provides fundamental insights into the role of reagent concentration in governing nZVI formation and offers enhanced control over nZVI composite reactivity for sustainable metal recovery and green hydrogen production. Materials and Method 1 Materials Iron. chloride hexahydrate (FeClCEA6HCCO. Ou99%), ethanol (C2H5OH, 99. 7%v/. , and poly. inyl alcoho. (PVA. Ou99%, fully hydrolyzed, 6Ae15. 4 cp. were purchased from R&M Chemicals. Sodium borohydride (NaBHCE. Ou98%) was obtained from Bellamy Precision, while chloroauric acid (HAuClCEA3HCCO. Ou99. 9%) was supplied by Sigma-Aldrich. Deionized water . 2 MAc. was used throughout all Palm shells were collected from a local palm oil mill, thoroughly washed with deionized water, dried at 80 AC for 24 h, and ground to a fine powder before use. All chemicals were used as received without further Fabrication of nZVI/Palm Shell Composites The nZVI/palm shell composites were fabricated using a modified co-precipitationreduction method under an inert nitrogen atmosphere, adapted from a previously reported method . The raw palm shell biomass was washed, dried in an oven, ground, and sieved to a powder size of <65 AAm. For each experiment, equimolar solutions of FeClCEand NaBHCEwith final concentrations of 0. 5, 1. 0, 1. 25, and 1. 5 M were prepared by dissolving the corresponding masses of ferric chloride hexahydrate (FeClCEA6HCCO) and sodium borohydride (NaBH. directly into their respective solvents, while maintaining consistent solution volumes and molar ratios across all The reagents (FeClCE. 6HCCO) were premixed with a 4:1 ethanol-water mixture . mL ethanol 2. 5 mL deionized wate. This solution was mixed with 0. 01 g of the palm shell powder in a round-bottom flask and stirred magnetically for 30 minutes to ensure uniform Subsequently, 55 mL of the corresponding equimolar concentration NaBHCE solution was added to the suspension dropwise . drops/mi. to the FeClCE/palm shell suspension under continuous stirring at 700 rpm. The addition of NaBHCE initiated an immediate reduction reaction, evidenced by the appearance of a black precipitate upon the first drop. The reaction was allowed to proceed for 1 hour at room temperature to ensure complete reduction. Following the reaction, the black iron nanoparticles were separated from the solution using the centrifuge at 6000 rpm for 7 Thereafter, the collected precipitate was washed three times with ethanol and dried for 4 hours in a freeze dryer for further use and Preparation of Gold-containing Solutions A gold-containing solution was prepared to evaluate the nanogold recovery and concurrent hydrogen production performance of the nZVI/palm Specifically, a 0. 8 mM HAuClCE solution was prepared by appropriately diluting the liquid HAuClCE stock in 45 mL of deionized water under Subsequently, 5 mL of 2% . polyvinyl alcohol (PVA) solution was added as a stabilizing agent and mixed thoroughly. The pH of the goldcontaining solution was then adjusted to 2. 0 using 1 M HCl or 1 M NaOH, added dropwise with continuous stirring to ensure homogeneity, and the pH was monitored using a calibrated pH Once the desired pH was attained, the solution was used immediately in the nanogold recovery and hydrogen generation experiments with nZVI/palm shell composites. Recovery of Nanogold and Hydrogen Gas Collection The procedure for simultaneous nanogold recovery and hydrogen generation was conducted following modified protocols reported in the literature . Figure 1 schematically depicts the experimental setup used. All reactions were performed in a 50 mL three-neck round-bottom flask immersed in a thermostatic water bath maintained at 37 AC. The flask was equipped with a thermometer and connected via rubber tubing to a pneumatic trough for hydrogen collection using the water displacement method, with an inverted 50 mL water-filled burette serving as the gasmeasuring device. Before each experiment, the gold-containing solution in the flask was purged with high-purity nitrogen . 99 %) for 20 minutes at 80 mL/min to remove dissolved oxygen and establish an inert atmosphere . Nitrogen was introduced through a submerged inlet needle while gently stirring the solution to enhance After purging, the nitrogen inlet was closed and the system was immediately sealed to form a gas-tight setup consisting of the reaction Copyright A 2026. ISSN 1978-2993 Bulletin of Chemical Reaction Engineering & Catalysis, 21 . , 2026, 406 flask, connecting tubing, and inverted burette. maintained to minimize oxygen ingress, while the water in the inverted burette served as a liquid seal to prevent back-diffusion of air. The system was allowed to stabilize until the burette water level remained constant, confirming the absence of leaks, and establishing a stable baseline. The reaction was then initiated by introducing 8 g/L of nZVI/palm shell composites synthesised using NaBHCE FeClCE concentrations . 5-2 M) and a fixed amount of palm shell powder, as described in Section 2. The suspension was stirred at 300 rpm and allowed to react for 24 hours, during which hydrogen evolution was continuously collected and analysed via gas chromatography (GC-FID. Agilent Technologie. with nitrogen gas as a carrier gas to ascertain the hydrogen concentration in the gas mixture. After 1 minute of reaction, aliquots were withdrawn, and the magnetic nZVI/palm shell composites were separated using a magnet. The resulting supernatant containing nanogold colloids was filtered, rinsed, and analysed by UV-Vis spectroscopy to detect the LSPR peak in the 530 nm - 550 nm range. reduction dominated initially due to its higher redox potential . , while hydrogen generation occurred gradually over 24 hours, as discussed in the following sections with supporting UV-Vis and BET analyses. Effect on Nanogold Recovery Figure 2 shows the UVAeVis spectra of nanogold generated using nZVI/palm shell composites synthesised at varying equimolar NaBHCEAeFeClCE concentrations . 5Ae2. 0 M). All spectra exhibit a well-defined localized surface plasmon resonance (LSPR) peak centered around Results and Discussion This study examined how varying equimolar NaBHCE-FeClCE concentrations . 5Ae2. 0 M) influence the dual performance of nZVI/palm shell composites in simultaneous nanogold recovery and hydrogen generation. Although both Figure 2. UVAeVis absorption spectra of nanogold recovered using nZVI/palm shell composites synthesized at varying equimolar NaBHCEAeFeClCE Figure 1. Experimental setup for simultaneous nanogold recovery and hydrogen generation using nZVI/palm shell composites. Copyright A 2026. ISSN 1978-2993 Bulletin of Chemical Reaction Engineering & Catalysis, 21 . , 2026, 407 530 nm, confirming the successful reduction of AuAA to AuA by nZVI. The presence of a single, symmetrical LSPR peak indicates that the resulting AuNPs were predominantly spherical with a relatively narrow size distribution, consistent with typical spherical AuNPs absorbing in the 520Ae550 nm region . The visible colour transition of the solution from light yellow to purple-red further corroborates AuNPs Notably, the intensity of the LSPR peak increased systematically with precursor concentration, suggesting that the amount of nanogold produced is highly sensitive to the NaBHCEAeFeClCE molarity used in composite This concentration-dependent behaviour is further quantified in Figure 3, which plots the average absorbance . sed as a proxy for nanogold yiel. as a function of the equimolar NaBHCEAeFeClCE Absorbance values rose nearly linearly from 0. 2227 A at 0. 5 M to 1. 0175 A at 2. M, demonstrating that higher precursor concentrations result in significantly greater nanogold recovery. This enhancement is likely associated with the increased availability of reactive FeA sites generated in the composites at higher molarities, which may facilitate more rapid and extensive reduction of AuAA to AuA. The favourable redox potential gradient between FeA/FeAA ( 0. 33 V) and AuAA/AuA ( 1. 50 V) further promotes efficient electron transfer . , accelerating nanogold nucleation. As FeA availability increases, a greater proportion of AuAA ions undergo reduction, leading to higher LSPR intensities and greater nanogold formation. This trend is consistent with previous findings, such as those reported in a prior study . , which also demonstrated improved AuAA reduction efficiency with increasing iron precursor concentrations. Figure 3. Average UV-Vis absorbance . roxy of nanogold yiel. versus equimolar NaBH4-FeCl3 concentration for nZVI/palm shell composite Effect on Hydrogen Volume In this system, hydrogen generation occurs as nZVI within the nZVI/palm shell composites undergoes corrosion in aqueous environments, releasing electrons that reduce protons (HA) or water molecules to produce hydrogen gas. The quantity and reactivity of the nZVI formed, both governed by the NaBHCE and FeClCE concentrations used during composite synthesis, play a central role in determining the overall hydrogen output. As shown in Figure 4, the hydrogen volume exhibits a distinctly non-linear dependence on the equimolar NaBHCEAeFeClCE concentrations, contrasting with the more linear trend observed for nanogold recovery profile (Figure . At lower concentrations . 5Ae1. 0 M), hydrogen volume remained relatively stable . 08Ae19. mL). Hydrogen increased substantially at 1. 5 M, reaching 29. mL, before dropping sharply to 12. 20 mL at 2. These results contrast with the continuous upward trend observed for nanogold recovery (Figure . The divergence arises from the different kinetics of the two redox processes: AuAA reduction is rapid and dominates the early reaction period, whereas corrosion-driven hydrogen evolution proceeds more slowly over 24 At 1. 5 M, sufficient FeA is available not only to fully reduce AuAA but also to sustain longterm hydrogen evolution, resulting in the highest hydrogen volume. However, beyond 2. 0 M, excessive precursor amounts produce larger quantities of nZVI, which accelerates AuAA reduction but simultaneously leads to the rapid consumption of reactive FeA. Based on the observed reduction in hydrogen volume at higher nZVI availability, we infer that passivating layers of Figure 4. Average hydrogen volume versus NaBH4-FeCl3 nZVI/palm shell composite synthesis. Copyright A 2026. ISSN 1978-2993 Bulletin of Chemical Reaction Engineering & Catalysis, 21 . , 2026, 408 iron oxides/hydroxides may build on the transfer and suppressing long-term hydrogen Although characterisation of passivation layers was conducted out in this study, this interpretation is compatible with the observed kinetic behaviour and with mechanistic models reported in the Similar behaviour has been reported in the literature . , where reduced long-term hydrogen generation was observed at higher nZVI Comparable trends were also reported in other studies . , which attributed that hydrogen evolution decreased exponentially over time, consistent with progressive surface passivation by oxide/hydroxide layers that block access to the underlying FeA and impede electron transfer, thereby reducing overall reactivity. Although nanogold recovery continued to increase up to 2 M (Figure . , hydrogen generation peaked at 1. 5 M (Figure . This difference shows a fundamental trade-off in the system: increasing equimolar NaBH4-FeCl3 concentration speeds up the reduction of AuAA ions, but it also slows down the long-term corrosion needed for hydrogen evolution. The reaction condition of 1. 5 M therefore represents an optimal balance where both nanogold recovery and hydrogen production are jointly maximized, confirming the synergistic dual-function nature of the nZVI/palm shell composites. 3 Hydrogen Purity and Gas Composition The evolved gas mixture was characterised by GC-FID to determine hydrogen purity and quantify the composition of gaseous products generated from the nZVI/palm shell system. Table 1 shows the concentrations of the gaseous species detected in the collected samples. As summarised in Table 1, hydrogen accounted for 99. 88 mol% of the total detected gas, indicating that the nZVI/palm shell system predominantly produces hydrogen with negligible interference from other gaseous species. Only trace amounts of COCC . mol%) and CO . 03 mol%) were detected, confirming minimal side reactions following correction for the blank response. This level of hydrogen purity is consistent with prior results from nZVI-based hydrogen production systems. For instance, hydrogen produced from a Bi/FeA water system was reported to contain negligible levels of common gaseous impurities such as COCC and CHCE, highlighting its potential as a clean energy carrier . Similarly, hydrogen formation arising from nZVI dissolution has been shown to correlate with minimal COCC generation under anaerobic conditions, indicating that nZVI itself can serve as a direct source of hydrogen in biomass-based systems . Compared to previous findings, the present system has a high hydrogen purity, showing that the palm shellsupported nZVI promotes selective iron corrosion while inhibiting competing side reactions. This indicates that the nZVI/palm shell composites can produce high-purity hydrogen with little gaseous byproducts, highlighting their potential for clean and sustainable energy applications. BET Surface Area and Pore Size Analysis of nZVI/Palm Shell Composites The specific surface area and pore size distribution of the nZVI/palm shell composites were evaluated using BET analysis, with the results shown in Figure 5. The composites exhibited the highest BET surface area . mA/. at an equimolar NaBH4-FeCl3 concentration 5 M, while the largest pore size . 77 yI) was observed at a concentration of 2. 0 M. The increase in specific surface area from 8. 69 mA/g . 5 M) to 57 mA/g . 5 M) is significant, as increased surface area enhances adsorptive interactions and redox activity of FeA nanoparticles. This is consistent with the improved nanogold recovery and hydrogen production observed at 1. (Figures 3 and . , implying that this concentration generated an optimum composite microstructure with a high density of active FeA Table 1. Concentration of gases collected from nZVI/palm shell composites. Gas concentration (%mol. Total gas (%mol. CO2 Figure 5. Specific surface area and pore size of nZVI/palm shell composites synthesized at NaBHCEAeFeClCE Copyright A 2026. ISSN 1978-2993 Bulletin of Chemical Reaction Engineering & Catalysis, 21 . , 2026, 409 At 2. 0 M, however, although the pore size was the highest, the specific surface area decreased to 33 mA/g. This suggests that excessively high NaBH4 and FeCl3 concentrations may cause pore coalescence or partial structural collapse, weakening the internal pore network. Under these conditions, the accelerated nucleation and growth of nZVI can produce larger agglomerates that combine and block nearby pores within the composites . Although no direct microscopic or spectroscopic evidence of pore collapse or surface passivation was determined in this study, the reduction in BET surface area, together with the decrease in hydrogen evolution at 2. 0 M (Figure . , provides indirect evidence that structural densification and surface deactivation may occur at higher precursor concentrations. These structural alterations may limit prolonged redox activity by reducing the accessibility of Feo surface sites and impeding effective electron transfer . Similarly, the structural instability in nZVI composites at high precursor concentrations has been reported to result in poor textural properties and the formation of a passivating oxide layer that inhibits electron transfer and increased aggregation . Overall, the BET results highlight those textural properties play a crucial role in determining AuAA reduction and hydrogen generation efficiency. The nZVI/palm shell composites synthesized at 1. 5 M exhibited a welldeveloped mesoporous structure that balances surface area for rapid nanogold recovery and structural stability for long-term hydrogen These findings emphasize the importance of NaBH4 and FeCl3 concentration optimization to engineer surface characteristics that enhance multifunctional nanocomposite Future research should utilize direct surface characterization techniques . , and explore kinetics and thermodynamics of the sequential redox reactions between FeA. AuAA, and water to identify rate-limiting steps and optimize nanocomposite systems . Using palm shell biomass as the support further enhanced the economic and environmental sustainability of the material. Overall, the findings highlight the potential of nZVI/palm shell composites as a multifunctional platform for wastewater treatment, precious metal recovery, and hydrogen-based energy Acknowledgment The authors gratefully acknowledge the Ministry of Higher Education (MOHE). Malaysia, for financial support through the Fundamental Research Grant Scheme (FRGS/1/2023/TK08/UITM/02/5. FRGS/1/2022/TK08/UITM/02/. , as well as Universiti Teknologi MARA (UiTM) for additional support through the UiTM Conference Support Fund. CRedit Author Statement Author Contributions: P. Nordin: Conceptualization. Methodology. Investigation. Resources. Writing. Review and Editing. Visualization. Helmy: Methodology. Investigation. Resources. Derek: Resources. Funding acquisition. Rajuli: Resources. Funding acquisition. Chang: Validation. Review and Editing. Supervision. Project administration. All authors have read and agreed to the published version of the manuscript. References