Algae-based carbons: Design, preparation and recent advances in their use in energy storage, catalysis and adsorption
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摘要: 能源危机和环境恶化是人类社会面临的两大难题。多孔炭材料因孔隙发达、结构易调和化学性质稳定等特点在能源存储和生态环境治理等领域具有重要作用，其应用性能高度依赖碳源的选择及其合成方法和条件优化。生物质富含有机碳元素且具有成本低、可再生等优点，以生物质为碳源构建多孔炭材料符合绿色化学理念、具备实现大规模工业化应用前景，特别是藻类生物质因富含杂原子纤维组分被认为是构建杂原子掺杂多孔炭材料的优良前驱体。通过有效调控合成方法和工艺过程，设计具有孔径结构和表面化学性质可控的藻类生物炭材料并在能源存储和生态环境治理等应用领域表现出优异性能，有效实现能源资源与生态环境和谐共存，特别是有研究报道海带基多孔炭的比表面积高达4000 m2/g。本文系统评述了藻类生物炭材料的制备方法及其孔径结构形成机理，并着重介绍这类多孔炭材料在电化学储能和吸附等方面的研究进展及其性能调控策略。提出藻类生物质衍生多孔炭材料面临的新趋势与挑战，并对未来开发低成本、高效率的高性能生物质基多孔炭材料的探索方向进行了展望。Abstract: Porous carbons with well-developed pores, tunable microstructures and stable chemistry play a significant role in energy storage and environmental pollution control. Biomass is a carbon precursor that is abundant, low cost, sustainable and carbon neutral, and is promising for the large-scale production of porous carbons. Among the various types of biomass, algae usually contain abundant cellulose and heteroatoms, which are suitable precursors for heteroatom-doped carbons. Recent advances in synthesis methods for algae-based porous carbons are reviewed and their pore formation mechanisms discussed. Their potential applications in adsorption, catalysis and energy storage are highlighted, and strategies for improving their performance are proposed. Future research trends and challenges for algae-based carbons are discussed, especially as they relate to their low-cost production and performance improvement.
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Key words:
- Algae biomass /
- Porous carbons /
- Green chemistry /
- Energy storage /
- Adsorption
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Figure 1. Publication of porous carbons from various biomass across globe in recent year with data collected from ISI Web of Thomson Reuters (Oct. 2020).
Figure 2. Top represents photos for typical macroalgae (a, prolifera; b, kelp; c, laver; d, gelidium; e, hypnea; and f, undaria), and Bottom represents micrographs of several types of microalgae (g, scenedesmus obliquus; h, ankistrodesmus sp.; i, tetraedron sp.; j, chlorella sp.; and k, mesotaenium sp.)
Figure 3. (a) Thermal decomposition of seaweeds to produce carbons, (b) yields of biochar, (c) gas compositions under different temperatures and (d-f) the normalized distribution of typical phenolics and N-containing organics in bio-oil produced from carbonization of seaweeds. Reproduced with permission from ref.[54]. Copyright 2020 Elsevier.
Figure 4. (a) Possible mechanism for HTC fromation from cellulose, SEM images of HTCs from (b) fructose, (c) xylose, and (d) furfural (Reproduced with permission from ref.[58]. Copyright 2012 RSC), and SEM images of HTCs from (e) starch, (f) cellulose and (g) sawdust.Reproduced with permission from ref.[61]. Copyright 2011 RSC.
Figure 5. (a) SEM images of AR material and carbons from carbonization and CO2 etching with increasing holding time: (b) 20, (c) 40, and (d) 60 min. Reproduced with permission from ref.[70]. Copyright 2015 Elsevier.
Figure 6. Schematic of N-doped carbon production from a mixture of microalgae and glucose, XPS results of N-species, and pore size distributions (PSDs) of carbons with various activation temperatures. Reproduced with permission from ref.[77]. Copyright 2014 Elsevier.
Figure 7. SEM images of carbons: (a) KC-700, (b) NC-900, and (c) KNC-650-900 using Chlorococcum sp. as a precursor, (d) PSDs of carbons, (e) CO2 uptake at 25 °C and 1 bar, (f) kinetics and (g) isotherms of CO2 and N2 for KC-700 at 25 °C up to 1 bar and (h) CO2 adsorption/desorption cycles for KC-700. Reproduced with permission from ref.[83]. Copyright 2016 RSC.
Figure 8. (a) Scheme for kelp carbons, (b-d) CV and GCD curves, and cycling of a symmetric cell in 6 mol L−1KOH (Reproduced with permission from ref.[98]. Copyright 2019 ACS), (e) scheme for a ‘all-kelp’ solid-state cell, (f) GCD curves, (g) capacitance variation, and (h) cycling and constant voltage hold test. Inset was GCD curve of the first and 10 000th cycles. The performance in 1 mol L−1 H2SO4 (KAC-A) was also tested. Reproduced with permission from ref.[101]. Copyright 2017 RSC.
Figure 9. (a) Scheme for carbon aerogels, (b-e) SEM and TEM images of HPCA-700-800, (f) GCD curves at 0.1 A g−1 up to 3.0 V (vs. Li+/Li), (g) CV curves at 0.1 mV/s and (h) stability and Coulombic efficiency of carbons at 0.5 A g−1. Reproduced with permission from ref.[95]. Copyright 2016 WILEY-VCH Verlag GmbH & Co. KGaA.
Figure 10. (a) Scheme for S-doped carbons, (b) N2 isotherms, (c-e) SEM images and EDS mapping for C, O and S, (f) CV curves of S/HPSCA-400 at 0.1 mV s−1 between 1.7−2.8 V (vs. Li+/Li), (g) GCD profiles and (h) cycling performance and Coulombic efficiency at 1 C rate, (1 C=1675 mAh g−1). Reproduced with permission from ref.[73]. Copyright 2019 Elsevier.
Figure 11. (a) Scheme for a N, S-doped carbon from Undaria pinnatifida, (b, c) TEM images for the carbon carbonized at 1000 °C, (d) N2 isotherms, (e) LSV curves at 1600 r min−1 and 10 mV s−1, (f, g) XPS for S, N-species, (h, i) CV curves at 50 mV s−1 in 0.1 mol L−1 KOH and (j) durability performance at ORR peak potential in the O2-saturated 0.1 mol L−1 KOH at 1600 r min−1. Reproduced with permission from ref.[50]. Copyright 2014 Wiley-VCH Verlag GmbH & Co. KGaA.
Figure 12. Scheme of carbons from direct carbonization of Spirulina sp.and SEM images for carbons obtained at various temperatures and possible mechanism for tetracycline removal. Reproduced with permission from ref.[119]. Copyright 2020 Elsevier.
Table 1. Different conditions for the carbonization of biomass and their effects on the yield of solid carbons. Reproduced with permission from ref.[4] Copyright 2020 Elsevier.
Types of carbonization Temperature (°C) Heating rate
(°C min−1)Yields of solid carbons (%) Slow 300−800 <10 ~30−35 Fast 400−600 >10 ~10−12 Flash <650 ~1000 ~10 Gasification 700-1500 ~1000 ~10 
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