Biochar as heterogeneous support for immobilization of Pd as efficient and reusable biocatalyst in C–C coupling reactions

Biochar is a stable and carbon‐rich solid which has a high density of carbonyl, hydroxyl and carboxylic acid functional groups on its surface. In this work, the surface of biochar nanoparticles (BNPs) was modified with 3‐choloropropyltrimtoxysilane and further 2‐(thiophen‐2‐yl)‐1H‐benzo[d]imidazole was anchored on its surface. Then, palladium nanoparticles were fabricated on the surface of the modified BNPs and further the catalytic application was studied as recyclable biocatalyst in carbon–carbon coupling reactions such as Suzuki–Miyaura and Heck–Mizoroki cross‐coupling reactions. The structure of the catalyst was characterized using scanning electron microscopy, transmission electron microscopy, energy‐dispersive X‐ray spectroscopy, thermogravimetric analysis, X‐ray diffraction and atomic absorption spectroscopy. The catalyst can be reused several times without a decrease in its catalytic efficiency. In addition to the several advantages reported, application of biochar as catalyst support for the first time is a major novelty of the present work.     

Corncob-to-xylose residue (CCXR) derived porous biochar as an excellent adsorbent to remove organic dyes from wastewater

Biochar was prepared from corncob-to-xylose residue (CCXR) by KOH activation and anaerobic pyrolysis method. The effect of activation temperature on the microstructure of the biochar was studied. Results showed that the biochar prepared at 850°C (850NBC) possessed high specific surface area and exhibited excellent adsorption property. The maximum adsorption capacity of 2249 mg g⁻¹ was obtained when 850NBC was used for treating methylene blue (MB) solution. Adsorption isotherm fittings revealed that Langmuir and Freundlich models were applicable to 850NBC adsorption process, and the adsorption process was limited by adsorption site and the biochar surface functional groups. Furthermore, 850NBC showed good adsorption property when it was used to treat the other organic dyes of Congo red (751 mg g⁻¹), Orange II (735 mg g⁻¹), Indigo carmine (662 mg g⁻¹) and Methyl Orange (465 mg g⁻¹). Biochar 850NBC also possessed an acceptable recyclability which maintained 68.7% absorption capacity after 6 cycles when it was used to treat MB solution. These results proposed that 850NBC is expected to be a promising potential adsorbent for treating organic dyes waste water.     

Conversion of spent coffee grounds to biochar as promising TiO2 support for effective degradation of diclofenac in water

A novel composite, biochar derived from spent coffee grounds with immobilized TiO₂ (biochar–TiO₂) was prepared, characterized, and applied as an alternative, effective, and sustainable photocatalyst for degrading diclofenac from aqueous solution. Composites with different mass ratios between TiO₂ and biochar were prepared by mechanical mixing and subsequent pyrolysis in an inert atmosphere of N₂ at 650°C. The sample with biochar–TiO₂ ratio of 1:1 presented a degradation efficiency of 90% at just 120 min versus 40% for TiO₂ used as reference. This fact is associated with a set of intrinsic characteristics obtained during the formation of the composite, such as superior pore size, avoiding the recombination of the ē/h⁺ pair, bandgap reduction, and promotion of reactive oxygen species due to phenolic groups present on the biochar surface. The dominant reactive species involved during the photocatalytic degradation of diclofenac were h⁺ and ^•OH. The diclofenac degradation pathways were determined based on the identification of intermediates and nonpurgeable organic carbon (NPOC) analysis. The novel biochar–TiO₂ composite prepared in this work showed high physical–chemical stability and efficiency over five consecutive cycles of reuse, proving to be a highly promising photocatalyst for degrading diclofenac in water.     

Dechlorination of 2,4-dichlorophenoxyacetic acid using biochar-supported nano-palladium/iron: Preparation,characterization, and influencing factors

In the present study, peanut shell, a green waste raw material, was used to prepare biochar (BC) and to obtain BC-supported nano-palladium/iron (BC-nPd/Fe) composites for removing 2,4-dichlorophenoxyacetic acid (2,4-D) from water. Characterization analysis demonstrated that nPd/Fe particles were well dispersed on the BC surface with weakened magnetic properties. The average particle diameter and specific surface area of nPd/Fe were 101.3 nm and 6.7 m² g⁻¹, whereas the corresponding values of the BC-nPd/Fe materials were 88.8 nm and 14.8 m² g⁻¹, respectively. Several factors were found to influence the dechlorination of 2,4-D, including the weight ratio of BC to Fe, Pd loading ratio, initial solution pH, 2,4-D concentration, and reaction temperature. Dechlorination results indicated that the 2,4-D removal and phenoxyacetic acid (PA) generation rates were 44.1% and 20.1%, respectively, in the nPd/Fe system, and 100.0% and 92.1%, respectively, in the BC-nPd/Fe system. The dechlorination of 2,4-D was well described by the pseudo-first-order kinetic model (R² > 0.97), and the observed rate constants k_obs were 0.0042 min (nPd/Fe) and 0.0578 min (BC-nPd/Fe), respectively. The reaction mechanism indicated that the dechlorination hydrogenation was the main process to remove 2,4-D from water in the BC-nPd/Fe system. In addition, BC inhibited the formation of a passivation layer on the particle surface during the reaction, thus maintaining the high reactivity of BC-nPd/Fe. The easy preparation technique, high 2,4-D dechlorination capacity, and mild reaction conditions suggest that BC-nPd/Fe may be a promising alternative composite to remove 2,4-D from water.     

响应面法优化铁锰改性生物炭对Cd2+的吸附

以香蕉秸秆生物炭为基底,采用浸渍改性的方法,制备了一种铁锰负载生物炭用以吸附Cd2+。通过响应面法对改性生物炭制备条件进行优化,在最优制备条件下,铁锰改性生物炭对Cd2+的预测吸附量为235.64 mg·g-1,实际吸附量为221.03 mg·g-1,相对偏差为6.2%。SEM-EDS、XRD、FTIR分析结果表明,改性后的生物炭表面成功负载铁锰元素,经分析对Cd2+的吸附机理为离子交换、官能团络合、矿物沉淀和阳离子-π作用。铁锰改性生物炭对Cd2+的吸附符合Langmuir模型和准二级动力学模型,说明吸附过程是单分子层吸附和化学吸附。     

添加不同比例玉米生物炭的堆肥腐殖质光谱学表征

对于当今污泥量剧增的趋势,添加生物炭的污泥堆肥是处理污泥较好的办法。本文基于理化性质和光谱学表征来研究添加不同比例玉米生物炭的堆肥腐殖质,结果发现生物炭能延长堆肥高温期1-2天;pH、电导率（electrical conductivity,EC）、有机质含量（organic matter content,OM）等指标均表明四组堆肥效果得到提升且实验组数值优于对照组。在紫外-可见光谱和傅里叶红外光谱可以看出S2、S3组有更多的类腐殖质物质生成,芳香族化合物增多,腐殖化程度提高,说明添加10%和15%玉米生物炭有更好的堆肥效果。在三维荧光光谱分析中,经堆肥后四个处理组可溶性微生物副产品逐渐转化为类腐殖质,且添加生物炭能促进其转移效果,有更高的荧光峰值。从胡敏酸平行因子分析中可以得到添加生物炭可以使堆肥腐殖质含量增多,但各处理组胡敏酸的各组分含量变化有所差异。     

热解温度对畜禽粪便制备的生物质炭性质的影响

以猪粪和鸡粪为原料,研究了热解温度(200~700 ℃)对生物质炭物理和化学性质的影响.结果表明,生物质炭的得率随着热解温度的升高逐渐降低,猪粪生物质炭的得率较鸡粪高;猪粪和鸡粪生物质炭的灰分含量分别为41.2%~70.6%和20.3%~48.1%.生物质炭均为中性或碱性,300~700 ℃热解所制备的生物质炭的pH值不仅与灰分含量有关,还可能与Ca含量密切相关.红外光谱表明,低温热解条件下（≤300 ℃）生物质炭中的含氧官能团与原材料相比无明显变化;但是当热解温度高于400 ℃时,生物质炭中的含氧官能团明显减少.生物质炭中的矿质元素含量均随着热解温度的升高而增大,猪粪生物质炭的富集倍数平均为1.04~1.65,鸡粪生物质炭为1.08~2.26.此外,猪粪K、Cu、Zn的挥发损失较鸡粪少,300~700 ℃热解鸡粪中K的挥发损失达30%;700 ℃热解,鸡粪Cu、Zn挥发损失达14.02%和21.70%.这些结果为畜禽固废制备生物质炭提供了重要的参考依据,为畜禽固废的资源化利用提供了新的思路.     

Comparison of 17β-Estradiol Adsorption on Corn Straw- and Dewatered Sludge-Biochar in Aqueous Solutions

Removal of steroid hormones from aqueous environment is of prevailing concern because of their adverse impact on organisms. Using biochar derived from biomass as adsorbent to remove pollutants has become more popular due to its low cost, effectiveness, and sustainability. This study evaluated the feasibility of applying corn straw biochar (CSB) and dewatered sludge biochar (DSB) to reduce 17β-estradiol (E2) from aquatic solutions by adsorption. The experimental results showed that the adsorption kinetics and isotherm behavior of E2 on the two biochars were well described by the pseudo-second-order (R² > 0.93) and Langmuir models (R² > 0.97). CSB has higher E2 adsorption capacity than DSB, and the maximum adsorption capacity was 99.8 mg/g obtained from Langmuir model at 298 K, which can be attributed to the higher surface area, porosity, and hydrophobicity of this adsorbent. Higher pH levels (>10.2) decreased the adsorption capacities of biochar for E2, while the ionic strength did not significantly affect the adsorption process. The regeneration ability of CSB was slightly better than that of DSB. The possible adsorption mechanism for E2 on biochar is suggested as π–π interactions, H–bonding, and micropores filling. These results indicated that CSB has more potential and application value than DSB on reducing E2 from aqueous solutions when considering economy and removal performance.     

生物炭孔隙结构对市政污泥好氧发酵过程中甲烷释放的影响

为探究生物炭孔隙结构(孔径、孔容和比表面积)在市政污泥好氧发酵过程中对甲烷(CH₄)释放的影响,本研究分别以榉木生物炭(WB)、稻壳生物炭(RB)和玉米芯生物炭(CB)作为调理剂进行好氧发酵实验,并设置不添加生物炭的作为对照组(CK),通过比表面积测试(BET)、气相色谱法(GC)、16S rRNA高通量测序技术和冗余分析(RDA)进行测定及分析。BET结果表明,WB和RB以微孔结构为主,分别占各自总孔隙结构的87.84%和73.72%,而CB以大孔结构为主,占比为89.94%。GC结果显示,与未加生物炭的CK相比,添加WB、RB和CB的市政污泥好氧发酵组的CH₄释放量分别减少41.83%、33.59%、8.20%。高通量测序结果表明,WB和RB通过提高发酵温度抑制了甲烷菌的相对丰度,而添加CB则使堆体的甲烷菌种类更丰富。RDA结果显示,生物炭孔径与CH₄释放速率呈正相关关系。综上可知,在本研究条件下添加以微孔结构为主的WB和RB对市政污泥好氧发酵过程中的CH₄减量化效果最佳。     

低温密封法制备玉米秸秆不同部位生物炭及特性比较

针对玉米秸秆利用困难问题,探索玉米秸秆制备生物炭工艺及其理化性能,采用密封限氧法,以玉米秸秆皮、瓤、根为研究对象,分别在300 ℃/45 min、500 ℃/ 30 min、700 ℃/15 min条件下制备生物炭并分析其特性,包括炭产率、pH值、灰分含量、红外光谱和扫描电镜分析。结果表明：在300~700 ℃时,随温度升高,炭产率降低,热解失重速率先增后减,pH值均升高;相同条件下,生物炭特征吸收峰基本相同,表现为表面官能团总量减少,酸性官能团降低,碱性官能团增加。综合分析,秸秆根生物炭与秸秆瓤、秸秆皮生物炭材料功能性相近,研究结果可为玉米秸秆根部的资源化利用提供理论依据和技术支持。