植物生物质的热化学液化及其应用

热化学液化是植物生物质利用的一条较好途径.本文综述了植物生物质热化学液化的工艺、机理,同时概述了液化产物在高分子材料方面的应用.     

Co-pyrolysis of biomass and waste plastics for production of chemicals and liquid fuel: A review on the role of plastics and catalyst types

The increasing global fuel consumption and growing environmental concerns are the impetuses to explore alternative energy that is clean and renewable for fuel production. Converting biomass and plastic waste into high-value fuel and chemicals via co-pyrolysis technique may provide a sustainable remediation to this problem. This review critically discussed the influence of various types of plastic wastes as co-reactant in co-pyrolysis with biomass on the product distribution, synergistic effect, and quality of bio-oil. The outcome of this review revealed that the addition of plastic enhanced the yield and quality of bio-oil and inhibited the production of oxygenated compound and coke formation. Next, the critical role of zeolite-based catalyst (microporous, mesoporous, hierarchical, and metal modified zeolite) and low-cost mineral-based catalyst in upgrading the yield and quality of liquid fuel were compared and discussed. The characteristic, synthesis method, strength, and limitation of each catalyst in upgrading the products were summarized. Hierarchical zeolites can resolve the problems of mass transfer, and diffusion limitation of large molecules into active sites associated with conventional zeolite due to the combination of two levels of porosity. Finally, the potential challenges and future directions for this technique were also suggested.     

Identification of Active Sites Formed on Cobalt Oxyhydroxide in Glucose Electrooxidation

Transition-metal-based oxyhydroxides are efficient catalysts in biomass electrooxidation towards fossil-fuel-free production of valuable chemicals. However, identification of active sites remains elusive. Herein, using cobalt oxyhydroxide (CoOOH) as the archetype and the electrocatalyzed glucose oxidation reaction (GOR) as the model reaction, we track dynamic transformation of the electronic and atomic structure of the catalyst using a suite of operando and ex situ techniques. We reveal that two types of reducible Co³⁺-oxo species are afforded for the GOR, including adsorbed hydroxyl on Co³⁺ ion (μ₁-OH−Co³⁺) and di-Co³⁺-bridged lattice oxygen (μ₂-O−Co³⁺). Moreover, theoretical calculations unveil that μ₁-OH−Co³⁺ is responsible for oxygenation, while μ₂-O−Co³⁺ mainly contributes to dehydrogenation, both as key oxidative steps in glucose-to-formate transformation. This work provides a framework for mechanistic understanding of the complex near-surface chemistry of metal oxyhydroxides in biomass electrorefining.     

Analysis of biomass sugars using a novel HPLC method

The precise quantitative analysis of biomass sugars is a very important step in the conversion of biomass feedstocks to fuels and chemicals. However, the most accurate method of biomass sugar analysis is based on the gas chromatography analysis of derivatized sugars either as alditol acetates or trimethylsilanes. The derivatization method is time consuming but the alternative high-performance liquid chromatography (HPLC) method cannot resolve most sugars found in biomass hydrolysates. We have demonstrated for the first time that by careful manipulation of the HPLC mobile phase, biomass monomeric sugars (arabinose, xylose, fructose, glucose, mannose, and galactose) can be analyzed quantitatively and there is excellent baseline resolution of all the sugars. This method was demonstrated for standard sugars, pretreated corn stover liquid and solid fractions. Our method can also be used to analyze dimeric sugars (cellobiose and sucrose).     

Hydrothermal Synthesis of NiCo-layered Double Hydroxide Nanosheets Decorated on Biomass Carbon Skeleton for High Performance Supercapacitor

Afacile hydrothermal strategy is adopted to synthesize the composite of NiCo-layered double hydroxide(NiCo-LDH) with biomass carbon as substrate for supercapacitor electrodes. The prepared NiCo@BC was characterized by means of X-ray diffraction(XRD), scanning electronic microscopy(SEM), Fourier transform infrared spectroscopy(FTIR) and Raman spectroscopy, and electrochemical tests. The SEM images demonstrated that numerous NiCo-LDH nanosheets directly grew on the surface of biomass carbon uniformly. Electrochemical tests indicated that the NiCo@BC electrode exhibited good capacitive behavior with a specific capacitance of 606.4 F/g at the current density of 0.5 A/g. In addition, the composite electrode showed excellent cyclic stability of 87.1% even after 1000 cycles. These results manifest that NiCo@BC nanocomposite is a promising candidate for the electrode material for future supercapacitor practical applications.     

直接合成Beta沸石封装Pt纳米粒子用于5-羟甲基糠醛合成2,5-呋喃二甲酸

生物质是唯一的碳基可再生资源,具有种类丰富、廉价易得、来源广泛等特点,将生物质资源转化为高附加值化学品对于可持续生产,缓解全球性能源和环境危机具有重要意义.5-羟甲基糠醛(HMF)是广泛研究的生物质平台分子,可以转化为多种高附加值化学品,其中氧化产物2,5-呋喃二甲酸(FDCA)有望作为对苯二甲酸的潜在替代物生产聚酯,因而备受关注.然而如何设计合成高性能的多相催化剂一直是个挑战.以氧气为氧化剂,负载型贵金属纳米粒子作为多相催化剂是目前广为研究的体系,但是面临贵金属利用率低,稳定性不佳等不足.将贵金属纳米粒子封装于沸石骨架,不仅能通过沸石孔壁的物理隔离效应增加纳米粒子的稳定性,同时基于沸石孔道对于底物、中间生成物、产物等特有的传质限域效应,可能会进一步提高活性和选择性.由于沸石晶体一般在碱性水热条件下晶化得到,易导致贵金属物种的快速沉积而难以获得高分散贵金属纳米粒子的沸石催化剂.因此这类催化剂的直接水热合成以及在生物质平台分子转化中的应用至今少有报道.本文设计合成了一种封装铂(Pt)纳米粒子的Beta沸石(Pt@Beta),应用于催化HMF合成FDCA的反应,以常压氧气为氧源,水作为溶剂,获得了高活性和稳定性以及极高的Pt原子利用率.我们采用一种不同以往的酸水解路径合成Pt@Beta沸石.首先将Pt前驱体、硅源(正硅酸四乙酯)和有机配体(3-巯丙基甲氧基硅氧烷)在弱酸性条件下水解缩合,增强了硅物种与Pt物种的相互作用,有效避免了贵金属氢氧化物的形成,这种特殊的预水解缩合环节有效促进了后续碱性环境水热合成中的Pt物种进入沸石晶内的过程,最终形成较为稳定和均匀分散的Pt纳米粒子.系统考察了配体种类、配体用量、配体加料顺序等合成条件对于催化剂制备的影响规律,获得了高分散Pt纳米粒子的适宜合成条件,结果表明,在酸水解过程中加入适量的有机配体,对于最终催化剂中Pt的高度分散至关重要.将不同Pt含量的Pt@Beta和后负载方法制备的Pt/Beta进行细致对比,XPS和TEM表征结果发现,只有直接水热合成法能够将Pt较好地封装在沸石晶体内.封装较低含量Pt的样品(0.2%Pt@Beta)在HMF氧化制FDCA反应中表现出高的收率和良好的复用稳定性.为探究其高活性缘由,测试了不同催化剂对底物、中间体以及产物的吸附性能,结果表明,0.2%Pt@Beta对于中间体2-甲酰呋喃甲酸(FFCA)吸附能力较强,能有效加速FFCA到FDCA这一决速步的反应,从而促进了FDCA的生成.此外,0.2%Pt@Beta中贵金属物种位于沸石晶内,得益于沸石刚性无机骨架的稳定化作用,该催化剂能有效阻止Pt纳米粒子在苛刻条件下的聚集,避免液固相反应体系中的溶脱流失,从而表现出优良的催化复用稳定性.     

A theoretical study on the destruction of typical biomass tar components (toluene,phenol and naphthalene) by OH radical

The detailed reaction mechanism of OH radical destroying toluene, phenol and naphthalene was studied through quantum chemical calculations in the research. Theoretical results indicate that for phenol and toluene, OH radical preferentially attack the ortho C atom due to the functional group on the benzene ring. But for naphthalene, OH radical preferentially attack the para-position C atoms because of its inherent benzo structure. To further study of the kinetics, the rate constant was calculated by the transition state theory. The comparison shows that the theoretical reaction rate constants for the degradation of tar by the OH radical were consistent with those obtained from literature experiments. And the rate constant of destructing naphthalene by OH radical was larger than that of destructing toluene, but lower than that of destructing phenol. The degradation sequence of OH radical to tar is: phenol ​> ​naphthalene ​> ​toluene. Because of the activation of hydroxyl group in benzene ring, phenol is the most easily attacked and destroyed by OH radical. The theoretical results can provide theoretical basis and data reference for further research on the removal of biomass tar and aromatics by OH radical.     

Ultrasound-assisted conversion of tannic acid to gallic acid as a strategy to obtain value-added products

In this work, ultrasound was applied for the conversion of tannic acid into gallic acid using only diluted H₂O₂ as reagent. Experiments were carried out using several types of ultrasonic horns operating at 20 kHz (VC750W processor). The following experimental conditions were evaluated: H₂O₂ concentration (0.2 to 8.5 mol L⁻¹), horn type (10 to 25 mm of diameter), ultrasound amplitude (20 to 70%), sonication time (10 to 45 min), tannic acid concentration (170 to 1360 mg L⁻¹), and reaction temperature (50 to 90 °C). Gallic acid production was monitored with ultra-performance liquid chromatography with high-resolution time-of-flight mass spectrometry (UPLC-ToF-MS). The isolated gallic acid was confirmed with nuclear magnetic resonance (¹H and ¹³C NMR). It is important to emphasize that this study was developed as a proof of concept to demonstrate the potential of ultrasound for tannic acid conversion into gallic acid using just diluted H₂O₂. Under selected conditions gallic acid production yield was 128 ± 4 mg g⁻¹ of initial tannic acid (using 170 mg L⁻¹ of tannic acid as starting material). Reaction time was set as 30 min, which was carried out using 1 mol L⁻¹ H₂O₂ and ultrasound amplitude of 50% at 90 °C. At silent conditions (mechanical stirring, from 100 to 1000 rpm), gallic acid production was halved (less than 78 ± 4 mg g⁻¹ of initial tannic acid).     

木质纤维素中C-O键选择性活化和高效转化制化学品

高效转化来源丰富且可再生的木质纤维素制备化学品和燃料对建立可持续发展社会具有重要意义。木质纤维素利用的一条理想途径是将其主要成分纤维素、半纤维素和木质素在温和条件下高选择性地催化转化为关键平台化学品。本文综述了近年报道的有关纤维素、半纤维素和木质素或其模型分子中C–O键选择性活化生成葡萄糖、葡萄糖衍生物(包括葡萄糖苷、六元醇和葡萄糖酸)、木糖、阿拉伯糖和芳香化合物的新催化剂和新策略,阐述了决定催化性能的关键因素。本文还讨论了相关反应机理以深入理解C–O键选择性活化。纤维素由葡萄糖单元通过β-1,4-糖苷键连接而成,通过水解反应,选择性切断这些糖苷键可以获得葡萄糖或其低聚物。鉴于葡萄糖在水热条件下不稳定,发展纤维素温和条件下水解的酸催化剂至关重要。众多研究表明,均相酸催化剂(如无机酸,杂多酸等)具有强Br?nsted酸,在该水解反应中显示高的催化活性。另一方面,拥有强酸性基团-SO3H的固体酸也表现出优异的水解糖苷键性能,但是-SO3H官能团易于流失,限制了这类固体酸催化剂的循环使用。最近研究显示,一些催化剂尤其是碳材料上引入能够与纤维素形成氢键的官能团时,其催化纤维素水解性能显著增强。设计合成这类具备酸性位和氢键位协同效应的稳定固体酸催化剂是纤维素水解转化的一个颇具前景的研究方向。以醇替代水为溶剂实施纤维素醇解制葡萄糖苷是高效活化糖苷键的有效策略。杂多酸被证实为该醇解反应的高性能催化剂。在相同反应条件下,醇解产物葡萄糖苷较水解产物葡萄糖更为稳定,因此可以获得高的葡萄糖苷收率。开发稳定可重复利用的固体酸催化剂是纤维素醇解的关键。耦合水解与加氢或氧化反应可以直接将纤维素转化为相对稳定且具有广泛用途的多元醇或有机酸。目前已有一系列双功能催化剂被报道,这些催化剂通常组合了具备水解功能的液体酸或固体酸和具备加氢或氧化功能的贵金属或过渡金属(譬如Ru, Pt, Ni和Au)。其中杂多酸盐或含有磺酸官能团的固体酸负载Ru或Au双功能催化剂显示出优异的生成六元醇或葡萄糖酸的催化性能。半纤维素由葡萄糖、甘露糖、木糖、阿拉伯糖、半乳糖等单糖单元通过糖苷键连接而成,糖苷键选择性活化可生成各种单糖混合物。硫酸可以有效水解半纤维素,但是同时也易于催化所生成的单糖深度转化为呋喃及其衍生物。较之硫酸,酸性较弱的有机酸特别是二元羧酸(例如马来酸、草酸等)具有较高的单糖选择性。固体酸如酸性树脂,分子筛等亦可催化半纤维素水解反应,但树脂类催化剂中官能团的流失问题有待解决。木质素是由含甲氧基等取代基的苯丙烷单元通过一系列化学键连接而成的复杂大分子,其芳香单元间包括β-O-4,α-O-4和4-O-5等三种主要连接方式,选择性切断这些C–O键可获得高附加值的芳香化合物。水解和氢解是两类普遍用以活化木质素及其模型化合物C–O键的反应。酸和碱均可催化木质素及其模型化合物水解,但是通常需要苛刻条件获取高转化率。近期研究显示,通过对木质素Cα-OH预氧化,再以HCOOH/HCOONa实施水解反应,可以成功实现温和条件下有机溶剂提取木质素及其模型化合物的高效转化。另一方面,均相金属络合物(如Ni, Fe和Ru)或多相负载型金属催化剂(如Ni, Cu, Mo, Pt, Ru, Pd或Ru等)均可有效催化木质素及其模型化合物中C–O键氢解,获得芳烃化合物。在部分多相催化剂体系中,除C–O键活化断裂外,还伴随芳环深度加氢反应,产生较多环己烷衍生物。因此,设计合成具备氢解功能同时抑制过度加氢功能的催化剂是获得芳烃化合物的关键。     

Cotton-derived oxygen/sulfur co-doped hard carbon as advanced anode material for potassium-ion batteries

Hard carbon is regarded as promising anode materials for potassium-ion batteries(KIBs)owing to their low price and easy availability.However,the limited rate capability still needs to be improved.Herein,we demonstrate the fabrication of oxygen/sulfur co-doped hard carbon through a facile hydrolyzationsulfuration process of skimmed cotton.The simultaneous dopants significantly improve potassium ion diffusion rate.When served as the anode for KIBs,this hydrolyzed hard carbon delivered a high reversible capacity(409 mAh/g at 0.1 A/g),superior rate capability(135 mAh/g at 2 A/g)and excellent cyclability(about 120 mAh/g overt 500 cycles at 2 A/g).This work provides a facile strategy to prepare low-cost doped-hard carbon with superior potassium storage property.