【學術亮點】Sulfur-functionalized sawdust biochar for enhanced cadmium adsorption and environmental remediation: A multidisciplinary approach and density functional theory insights
Ecological Agriculture: Optimization and Validation of Soil Carbon Sequestration Prediction Models【Department of Soil Environmental Sciences / Tzou, Yu-Min / Distinguished Professor、Liu, Yu-Ting / Distinguished Professor】
生態農業：土壤碳蓄存之預測模型優化及驗證【土壤環境科學系/鄒裕民特聘教授、劉雨庭特聘教授】
| 論文篇名 | 英文：Sulfur-functionalized sawdust biochar for enhanced cadmium adsorption and environmental remediation: A multidisciplinary approach and density functional theory insights 中文：硫功能化木屑生物炭用於增強鎘吸附與環境修復：多學科方法與密度泛函理論洞察 |
| 期刊名稱 | Journal of Environmental Management |
| 發表年份,卷數,起迄頁數 | 2025, 373, no. 1123586 |
| 作者 | Ahmed, M. M. M.; Liao, Chih-Hao; Venkatesan, S.; Liu, Yu-Ting(劉雨庭); Tzou, Yu-Min(鄒裕民)*; Jien, Shih-Hao; Lin, Ming-Chang; Hsieh, Yi-Cheng; Osman, Ahmed I. |
| DOI | 10.1016/j.jenvman.2024.123586 |
| 中文摘要 | 由於孔隙發育不足與表面官能基缺乏，原始生物炭在重金屬吸附方面通常表現有限。本研究提出一種創新的化學修飾策略，利用硫基官能團（C=S、C-S、S-S、S²⁻、S-H、-SO₃²⁻、-SO₄²⁻）對鋸屑生物炭進行表面功能化，以顯著提升對鎘（Cd）的吸附能力。透過 H₂SO₄、Na₂S 與 Na₂S₂O₃ 進行硫摻雜，硫含量由原始的 0.11% 分別提高至 2.81%（H₂SO₄）、0.57%（Na₂S）以及 13.27%（Na₂S₂O₃）。SEM-EDS、FTIR 與 XPS 等表徵技術證實硫基團及額外含氧基團的成功引入，進一步改善了表面功能性。與原始生物炭相比，硫改性生物炭的 Cd 吸附容量提升了 4.8–9.0 倍，分別達到 39.38、20.84 與 34.14 mg g⁻¹（對應 H₂SO₄、Na₂S 與 Na₂S₂O₃ 修飾）。同時，平衡時間由原始生物炭的 4 小時大幅縮短至 5–10 分鐘（硫改性樣品）。Cd 吸附能力的增強歸因於靜電作用、鎘–π 電子相互作用、配位作用與離子交換等多重機制的協同效應，而這些效應受到氧與硫官能團的共同促進。密度泛函理論（DFT）計算顯示，硫摻雜改變了生物炭–Cd 系統的電子性質，縮小能隙並增強 Cd–O 鍵，進一步提升了 Cd 的吸附性能。此外，硫改性生物炭–Cd 複合物的結合能在 Cd 吸附後更加穩定。本研究證明，同時具備氧與硫官能團的鋸屑生物炭是一種高效且環保的 Cd 去除吸附劑，凸顯了表面功能化設計對提升生物炭反應性與對特定污染物親和力的重要性。所開發的材料為水體中 Cd 去除提供了一種永續且可規模化的解決方案，並有助於先進水處理技術與環境修復策略的推進。 |
| 英文摘要 | Pristine biochar typically exhibits limited capacity for heavy metal adsorption due to its inadequate pore development and insufficient surface functionality. This study introduces an innovative chemical strategy to enhance the surface of sawdust biochar with sulfur-based functional groups (C=S, C-S, S-S, S2- , S-H, -SO32-, -SO42-) to significantly improve cadmium (Cd) adsorption. Sulfur-doping using H2SO4, Na2S, and Na2S2O3 markedly increased the sulfur content from 0.11% (pristine) to 2.81% (H2SO4), 0.57% (Na2S), and 13.27% (Na2S2O3). Characterization techniques such as SEM-EDS, FTIR, and XPS confirmed the successful incorporation of sulfur moieties and additional oxygen-containing groups, improving surface functionality. The Cd adsorption capacity of S-modified biochar increased by 4.8–9.0 times compared to pristine biochar, with peak values of 39.38, 20.84, and 34.14 mg g-1 for H2SO4, Na2S, and Na2S2O3-modified biochar, respectively. The equilibrium time was significantly reduced from 4 h (pristine) to 5–10 min (S-modified). The enhanced Cd adsorption was attributed to the synergistic interplay of electrostatic attraction, cadmium-π electron interactions, complexation, and ion exchange mechanisms, facilitated by the presence of oxygen and sulfur functional groups. Density Functional Theory (DFT) calculations showed that sulfur doping modulated the electronic properties of the biochar-Cd systems, narrowing the band gap and enhancing the Cd-O bonds, thereby improving the Cd adsorption performance. Additionally, the binding energies of the S-modified biochar-Cd complex were found to be more stable compared to those before Cd adsorption. This study demonstrates that both oxygen and sulfur-functionalized sawdust biochar is an effective and eco-friendly adsorbent for Cd removal, highlighting the significance of tailored surface modifications to augment biochar’s reactivity and affinity towards specific contaminants. The developed material offers a sustainable and scalable solution for Cd removal from aqueous environments, contributing to advanced water treatment technologies and environmental remediation strategies. |
| 發表成果與本中心研究主題相關性 | 本研究在以農業剩餘資材轉變為生物炭後進行化學改質, 使其具備與重金屬鎘具高親和力的含硫官能基, 提高水體中鎘的去除, 減少其進入食物鏈的可能性, 成果與中心強調永續環境利用與健康的目標一致 |
