Preparation of nitrogen and sulfur co-doped ultrathin graphitic carbon via annealing bagasse lignin as potential electrocatalyst towards oxygen reduction reaction in alkaline and acid media

Renewable lignin used for synthesizing materials has been proven to be highly potential in specific electrochemistry.Here,we report a simple method to synthesize nitrogen and sulfur co-doped carbon nanosheets by using bagasse lignin,denoted as lignin-derived carbon(LC).By adjusting the ratio of nitrogen source and annealing temperature,we obtained the ultrathin graphitic lignin carbon(LC-4-1000)with abundant wrinkles with high surface area of 1208 m2g_1 and large pore volume of 1.40 cm3g_1.In alkaline medium,LC-4-1000 has more positive half-wave potential and nearly current density compared to commercial Pt/C for oxygen reduction reaction(ORR).More importantly,LC-4-1000 also exhibits comparable activity and superior stability for ORR in acid medium due to its high graphitic N ratio and a direct four electron pathway for ORR.This study develops a cost-effective and highly efficient method to prepare biocarbon catalyst for ORR in fuel cells.

Promotion of activation ability of N vacancies to N2 molecules on sulfur-doped graphitic carbon nitride with outstanding photocatalytic nitrogen fixation ability

Nitrogen vacancies and sulfur co-doped g-C3N4 with outstanding N2 photofixation ability was synthesized via dielectric barrier discharge plasma treatment. X-ray diffraction, ultraviolet–visible spectroscopy, N2 adsorption, scanning electron microscopy, X-ray photoelectron spectroscopy, photoluminescence spectroscopy, and temperature-programmed desorption were used to characterize the as-prepared catalyst. The results showed that plasma treatment cannot change the morphology of the as-prepared catalyst but introduces nitrogen vacancies and sulfur into g-C3N4 lattice simultaneously. The as-prepared co-doped g-C3N4 displays an ammonium ion production rate as high as 6.2 mg·L^-1·h^-1·gcat^-1, which is 2.3 and 25.8 times higher than that of individual N-vacancy-doped g-C3N4 and neat g-C3N4, respectively, as well as showing good catalytic stability. Experimental and density functional theory calculation results indicate that, compared with individual N vacancy doping, the introduction of sulfur can promote the activation ability of N vacancies to N2 molecules, leading to promoted N2 photofixation performance.

Enhanced photocatalytic hydrogen production from Co-MOF/CN by nitrogen and sulfur co-doped coal-based carbon quantum dots

A novel composite photocatalyst for photocatalytic decomposition of water for hydrogen evolution was successfully synthesized by in-situ growth of nitrogen and sulfur co-doped coal-based carbon quantum dots(NSCQDs)nanoparticles on the surface of sheet cobalt-based metal-organic framework(Co-MOF)and graphitic carbon nitride(g-C_(3)N_(4),CN).The structure and properties of the obtained catalysts were systematically analyzed.NSCQDs effectively broaden the absorption of Co-MOF and CN in the visible region.The new composite photocatalyst has high hydrogen production activity and the hydrogen production rate reaches 6254μmol/(g·h)at pH=9.At the same time,NSCQDs synergy Co-MOF/CN composites have good stability.After four cycles of hydrogen production,the performance remains relatively stable.The tran sient photocurrent response and Nyquist plot experimental results further demonstrate the improvement of carrier separation efficiency in composite catalysts.The semiconductor type(n-type semico nductor)of the single-phase catalyst was determined by the Mott-Schottky test,and the band structure was analyzed.The conductive and valence bands of CN are-0.99 and 1.72 eV,respectively,and the conduction and valence bands of Co-MOF are-1.85 and 1.33 eV,respectively.Th e mechanism of the photocatalytic reaction can be inferred,that is,Z-type heterojunction is formed between CN an d Co-MOF,and NSCQDs was used as cocatalyst.

Boosting lithium storage performance of Si nanoparticles via thin carbon and nitrogen/phosphorus co-doped two-dimensional carbon sheet dual encapsulation

Silicon(Si)is a promising anode candidate for next-generation lithium-ion batteries(LIBs),but it suffers from poor electronic conductivity and dramatic volume variation during cycling,which poses a critical challenge for stable battery operation.To mitigate these issues simultaneously,we propose a"double carbon synergistic encapsulation"strategy,namely thin carbon shell and nitrogen/phosphorus co-doped two-dimensional(2D)carbon sheet dual encapsulate Si nanoparticles(denoted as 2D NPC/C@Si).This double carbon structure can serve as a conductive medium and buffer matrix to accommodate the volume expansion of Si nanoparticles and enable fast electron/ion transport,which promotes the formation of a stable solid electrolyte interphase film during cycling.Through structural advantages,the resulting 2 D NPC/C@Si electrode demonstrates a high reversible capacity of592 mAh·g^(-1) at 0.2 A·g^(-1) with 90.5%excellent capacity retention after 100 cycles,outstanding rate capability(148 mAh·g^(-1) at 8 A·g^(-1)),and superior long-term cycling stability(326 mAh·g^(-1) at 1 A·g^(-1) for 500 cycles,86%capacity retention).Our findings elucidate the development of high-performance Si@C composite anodes for advanced LTBs.

N,P co-doped 3D porous carbon with self-assembled morphological control via template-free method for potassiumion battery anodes

The larger ionic radius of potassium ions than that of lithium ions significantly limits the accomplishment of rapid diffusion kinetics in graphite electrodes for potassium-ion batteries(PIBs),resulting in comparatively poor rate performance and cycle stability.Herein,we report a high-rate performance and cycling stability amorphous carbon electrode achieved through nitrogen and phosphorous co-doping.The as-prepared N,P co-doped carbon electrodes have distinct 3D structures with large surface areas,hierarchical pore architectures,and increased interlayer spaces resulting from the direct pyrolysis of supramolecular self-assembled aggregates without templates.The obtained electrode N3P1 exhibits a reversible specific capacity of 258 m Ah·g^(-1)at a current density of 0.1A·g^(-1)and a good long-term cycle performance(96.1%capacity retention after 800 cycles at 0.5 A·g^(-1)).Kinetic investigations show that the N3P1 electrode with the welldeveloped porous structure and large number of surface defects exhibits capacitive-driven behavior at all scan rates,which may be attributed by N and P co-doping.Ex-situ transmission electron microscopy analyses in the fully discharged and charged states demonstrate structural stability and reversibility owing to the expanded interlayer space.The suggested synthesis approach is simple and effective for producing heteroatom-doped carbon materials for PIBs and other advanced electrochemical energy storage materials.

Convenient room-temperature synthesis of sulfur and nitrogen co-doped NiCo-LDH coupled with CNTs on NiCo foam as battery-type electrode for high performance hybrid supercapacitor

The convenient synthesis of the composite electrode with high supercapacitance performance plays an important role in practical application but is challenging.Herein,the carbon nanotubes(CNTs)coupled with lowcrystalline sulfur and nitrogen co-doped Ni Co-LDH(denoted as SN-Ni Co-LDH)nanosheets array are grown on Ni Co foam(NCF)substrate by two convenient steps of metal induced self-assembly and corrosion engineering,which present the advantages of operating at roomtemperature and low preparation costs.Benefiting from the S–N co-doping and low-crystallinity of Ni Co-LDH,the prepared SN-Ni Co-LDH@CNTs@NCF electrode presents a topping charge capacity of 2470 C·g^(-1)(4.94 C·cm^(-2))at 5 m A·cm^(-2).Furthermore,the fabricated asymmetry supercapacitor(ASC)achieves an extraordinary energy density of 77 Wh·kg^(-1)(0.617 m Wh·cm^(-2))at a power density of 438 W·kg^(-1)(3.5 m W·cm^(-2))and outstanding stability(91%capacity retention after 5000 cycles at20 m A·cm^(-2)).Impressively,the structure evolution of Ni Co-LDH during the charge/discharge processes has been thoroughly elucidated by in-situ Raman spectra.Therefore,this work verifies a powerful strategy and practical value for preparing composite electrodes with high supercapacitance performance,and also provides guidance for the rational design of the smart electrodes.

Facile carbon cloth activation strategy to boost oxygen reduction reaction performance for flexible zinc-air battery application

Flexible and all-solid-state zinc-air batteries(ZABs)are highly useful and also in demand due to their theoretical high energy densities and special applications.The limitation in their performance arises due to their catalyst-coated cathode electrodes in terms of catalytic activity and stability as well as cost.In this paper,a novel and environmentally friendly activation strategy is developed to activate the carbon cloth(CC)for the electrodes.The activated CC serves as a catalyst-free air cathode with high conductivity,excellent mechanical strength,and flexibility,in addition to low cost.The strategy is performed by simply electro-oxidizing and electroreducing CC under ultrahigh direct current(DC)voltage in a diluted NH4Cl aqueous electrolyte.It is found that the electro-oxidation not only results in the formation of a graphene-like exfoliated carbon layer on the surface of CC but also induces the incorporation of oxygen-containing groups and doping of nitrogen and chloride atoms.After the electroreduction,theπ-conjugated carbon network of CC is partially restored,leading to the recovery of electroconductivity.Such an electroactivated CC shows excellent oxygen reduction reaction activity.The aqueous flexibility and all-solid-state ZABs are assembled using such an electroactivated CC cathode without any catalyst loading.Both ZABs can achieve good durability and deliver high peak power density and an energy density as high as 690 Wh kg^(−1),demonstrating the excellent potential of this electroactivated CC in practical devices.

Preparation of highly luminescent nitrogen and sulfur co-doped carbon nanoparticles for iron(Ⅲ)ions detection and cell imaging

Highly photoluminescent nitrogen and sulfur co-doped carbon nanoparticles（CNPs） ca. 56 nm have been prepared through a green one-step hydrothermal synthesis route by using millet powder as carbon sources, in which the nitrogen and sulfur co-doping improves the photoluminescent efficiency of the CNPs. The as-prepared CNPs display excellent fluorescent properties and low biotoxicity with a relatively high quantum yield of 30.4%, which have been applied for bioimaging and highly sensitive and selective detection of iron（III） ions.

A new strategy to access Co/N co-doped carbon nanotubes as oxygen reduction reaction catalysts

Carbon nanotubes(CNTs),as one-dimensional nanomaterials,show great potential in energy conversion and storage due to their efficient electrical conductivity and mass transfer.However,the security risks,time-consuming and high cost of the preparation process hinder its further application.Here,we develop that a negative pressure rather than a following gas environment can promote the generation of cobalt and nitrogen co-doped CNTs(Co/N-CNTs) by using cobalt zeolitic imidazolate framework(ZIF-67) as a precursor,in which the negative pressure plays a key role in adjusting the size of cobalt nanoparticles and stimulating the rearragement of carbon atoms for forming CNTs.Importantly,the obtained Co/N-CNTs,with high content of pyridinic nitrogen and abundant graphitized structure,exhibit superior catalytic activity for oxygen reduction reaction(ORR) with half-wave potential(E_(1/2)) of 0.85 V and durability in terms of the minimum current loss(2%) after the 30,000 s test.Our development provides a new pathway for large-scale and cost-effective preparation of metal-doped CNTs for various applications.

苏北潮滩湿地不同生态带碳、氮、磷分布特征

通过对比苏北潮滩湿地不同生态带的表层以及柱状沉积物中总有机碳、总氮、总磷和有机磷含量,并结合不同植被不同植株部位中碳、氮、磷的含量变化,分析了潮滩沉积物中碳、氮、磷的垂向和水平分布特征与规律,探讨了不同生态带以及潮滩植被对碳、氮、磷等生源要素的富集作用。对比分析结果表明:苏北潮滩湿地各生态带对不同的测量指标有着不同的富集作用,互花米草滩的总有机碳、总氮和有机磷含量要远大于其他几个生态带,光滩沉积物中总磷的含量最高;粒度效应是控制互花米草前缘地带以及互花米草滩沉积物中有机碳和氮分布的一个重要因素,盐蒿和芦苇滩中有机碳和氮的分布更多的是受粒度之外的其他因素影响;不同生态带表层沉积物中的C/N比值分布,大致可反映其有机物来源的差异,而不同生态带中柱状沉积物中的C/N比值相对接近,很难根据C/N比值大小来对不同生态带中的有机物来源进行判断,这可能是埋藏在柱状沉积物中的有机物更多的受到了早期成岩作用造成的。植被对潮滩湿地中碳、氮、磷的分布有着重要影响,3种物质在互花米草、盐蒿和芦苇中的含量差别不是很大,因此潮滩植被对沉积物中上述3种物质的贡献差别主要是由不同植被的生物量和其所处环境的沉积动力差异造成的。

青藏高原东部不同草地类型土壤养分的分布规律

调查分析了青藏高原东部高寒草甸、高寒灌丛草甸、亚高寒草甸、沼泽化草甸、荒漠化草原、林间草地、盐渍化沼泽土壤碳氮磷含量垂直分布特征。结果表明,7种草地类型中,土壤有机碳含量大体随着土层的深入而降低,0～15cm土层土壤有机碳的累积量从高到低依次为林间草地>高寒灌丛草甸>高寒草甸>沼泽化草甸>盐渍化沼泽>亚高寒草甸>荒漠化草甸(P<0.05);随土层深度变化土壤全氮含量与有机碳相似,0～15cm全氮累积量从高到低依次为沼泽化草甸>林间草地>高寒灌丛草甸>高寒草甸>盐渍化沼泽>荒漠化草原>亚高寒草甸(P<0.05);荒漠化草原、林间草地和土壤全磷含量随土层深度无明显规律性,0～15cm土层全磷累积量由高到低依次为高寒灌丛草甸>沼泽化草甸>高寒草甸>盐渍化沼泽>亚高寒草甸>荒漠化草原>林间草地(P<0.05);随土层深度的增加不同草地类型养分含量顺序不同。除沼泽化草甸,不同草地类型下土壤有机碳与全氮呈显著正相关。

A-A^2/O工艺处理低碳源城市污水的除磷脱氮效果

文章以南方某污水处理厂的实际运行情况为例,介绍了A-A2/O工艺在处理低碳源城市污水的效果。运行结果表明,工艺对BOD5、COD、SS的去除效果良好,达到《城镇污水处理厂污染物排放标准》(GB18918-2002)一级A标准。对于氮磷去除,出水NH4-N<0.5mg/L,TN<15mg/L,TP<1.5mg/L,但TN平均去除率只有45%左右;TP大多数的去除率在30%～50%之间。造成这种结果的主要原因是碳源不足。为提高除磷脱氮效果,采取了投加PAC来辅助除磷,并提出了进一步的改进措施,供同行参考。

山东南部近海沉积物中碳、氮、磷的分布特征

对山东近海31个站位表层沉积物中的总氮、总磷和总有机碳的含量和分布特征进行了研究。结果表明,总氮、总磷和总有机碳含量均较低,高值区主要分布在胶州湾及湾口和北部海域,总氮浓度范围为0.31～0.75mg/g,平均值为0.52mg/g,总磷浓度范围为0.18～0.32mg/g,平均值为0.24mg/g,总有机碳浓度范围为0.17%～0.49%,平均值为0.33%。相关性分析表明,总氮和总有机碳的相关性较好,总有机碳和总氮比值(TOC/TN)略高于Redfield比值,表明这两种生源要素的来源可能是一致的。

毛乌素沙地湖滨带沉积物碳氮磷生态化学计量学特征

为了阐明毛乌素沙地湖滨带沉积物生态化学计量学特征及其指示意义,对不同类型区湖滨带沉积物有机碳、全氮和全磷含量进行了测定与分析。结果表明:不同类型区湖滨带沉积物有机碳和全氮含量变化趋势一致,表现为距离湖泊中心位置愈远其含量愈低;湖滨带沉积物有机碳、全氮、全磷含量剖面分布具有一定层次性,表现为0—10cm>10—20cm>20—40cm,湖滨带沉积物全磷的变化相对滞后于有机碳和全氮,其水平分布特征与有机碳和全氮不同,剖面分布相似;土壤含水率和土壤容重是影响沉积物养分分布的关键因子,同时也是影响C/P和N/P变化的主要因素;生态化学计量学特征分析表明,除相对远离湖泊中心的类型区C/N和C/P与土壤碳储量的变化趋势一致外,靠近湖泊中心的类型区碳与养分比值未表现出对土壤碳储量良好的指示作用。

磷酸活化汉麻布活性炭纤维的孔结构

以汉麻布为原料,采用磷酸活化法制备了汉麻布活性炭纤维,并利用低温氮气吸附和密度泛函理论（DFT）对样品的孔结构进行了分析。结果表明,随着活化温度的升高,磷酸活化的汉麻布活性炭纤维的BET比表面积和总孔容都呈现先增大后减小的变化趋势。不同方法计算得到的样品比表面积值呈相同的变化规律。样品的孔分布集中在2 nm以下的微孔范围内,既有极微孔又有超微孔,只有少量中孔,基本没有大孔。所有样品的孔径在微孔范围内都呈现多峰分布,孔径≤1 nm和1-2 nm的范围内分别都出现了2个峰值孔径。微孔孔容基本上随活化温度的升高而增加,而中孔孔容的数值则整体上变化不大。样品表面能量分布较宽,并呈现有多个不连续峰值的多峰分布,宽的孔径分布导致宽的表面能量分布和较多的能量峰值,并使吸附位的种类也随之增多。

三江源星星海水体中碳氮磷化学计量特征

【目的】研究三江源星星海水体中碳氮磷化学计量特征,为揭示隆宝湖湿地的潜在富营养化进程提供依据。【方法】在星星海设置3个采样点采集水样,研究水体中总有机碳(TOC)、总氮(TN)、总磷(TP)的含量,对照《地表水环境质量标准》(GB3838-2002),采用超标率和超标倍数对水质进行了评价,分析了TOC与TN、TN与TP的相关性。【结果】星星海水体中TN含量为0.326 mg/L,NH4+-N含量为0.100 mg/L,NO3--N含量为0.109 mg/L,TP含量为0.014 mg/L,TOC含量为0.406 mg/L。对照《地表水环境质量标准》(GB3838-2002)TOC、TN、TP超过Ⅰ类水质标准,TN、TP超标倍数分别为0.63、0.4,超标率分别为66.7%、33.3%。相关性分析表明,TOC与TN、TN与TP的相关系数分别为R12﹦0.930 5,R22﹦0.693 2,说明碳、氮含量变化趋势相关性较好,氮、磷含量变化趋势相关性较差,水体中TN、TP来源不同。研究表明,C/N约为1.263,N/P约为23.28,表明有机质来源具有单一性,磷是星星海潜在营养化的限制因子。【结论】TN、TP的含量超过了《地表水环境质量标准》的Ⅰ类水质标准,达到了《地表水环境质量标准》的II类水质标准。星星海水体未达到富营养化状态。

草地退化对三江源国家公园高寒草甸表层土壤有机碳、全氮、全磷的空间驱动

草地退化显著削弱了三江源高寒草甸的土壤肥力及生态承载功能,但空间尺度上的驱动强度和环境调控尚不清晰。在2020年7—8月,基于三江源国家公园高寒草甸典型分布区原生植被和退化植被的60个配对采样,研究表层(0—30 cm)土壤有机碳(SOC)、全氮(TN)和全磷(TP)含量对草地退化的空间响应特征。三江源国家公园高寒草甸原生植被SOC和TN含量分别为(2.45±2.05)%(平均值±标准差,下同)和(0.25±0.20)%,配对样本t-检验的结果表明草地退化导致SOC和TN分别极显著(P<0.001)下降了44.0%和35.6%。TP对草地退化无显著响应(P=0.22)。原生植被的土壤C∶N∶P平均为59.6∶6.2∶1.0,草地退化导致化学计量值平均下降28.3%。一般线性模型的结果表明草地退化对SOC和TN及土壤生态化学计量特征的空间降低强度主要取决于纬度和海拔(P<0.01),与经度和土壤深度关系较弱(P>0.30),即低纬度高海拔的高寒草甸响应相对强烈。草地退化导致三江源国家公园高寒草甸土壤碳氮损失严重,降低了土壤生态化学计量。研究结果可为三江源退化高寒草甸土壤营养功能的治理和恢复提供理论支撑。

沙田湖人工湿地植物碳氮磷动态研究

在处理水产养殖废水的表面流和水平潜流湿地复合系统中,进行了湿地植物不同组织氮磷含量以及有机碳含量的周年变化规律研究,评价湿地植物吸收对湿地系统总氮和总磷的去除作用及对有机碳的固定效果。结果表明：湿地植物组织碳、氮、磷含量具有明显的季节性差异,在生长发育的不同阶段植物组织内碳,氮、磷均具有由根部向上输送蓄积和向下＂营养回流＂的特点。氮磷在植物生长初期含量较高,随着植物的生长发育其含量呈下降趋势;有机碳含量表现为＂先升-后降＂趋势,9月份各植物有机碳含量达最高值,其中再力花最高,达59.48%。植物生长期,植物直接吸收氮磷作用明显。植物体氮磷净吸收能力随植物生长期中不同时间而变,当湿地进水氮磷负荷为301.32 g/（m^2·a）和62.64 g/（m^2·a）时,若选择10月底收割,各植物对氮的去除率为28.43%,对磷的去除率14.69%,植物氮磷吸收对人工湿地系统营养物质去除起到一定的作用。

铝镉污染对砖红壤微生物碳氮磷的影响

通过土培试验,研究铝、镉对砖红壤土壤微生物碳氮磷的影响。结果表明:铝处理对土壤微生物量碳(SMC)影响变化幅度较大。不同浓度铝处理降低土壤微生物氮(SMN),随处理浓度的增加,抑制程度增强, SMN相应降低14.28%～46.63%;而铝处理对土壤微生物磷(SMP)有显著促进作用。2～50 mg/kg镉处理对SMC无显著影响, 5～15 mg/kg镉处理显著提高SMN含量20.40%～37.55%,但随着处理浓度增加到20～100 mg/kg, SMN降低21.63%～54.69%。15～20 mg/kg镉对SMP有显著促进作用。1 000～2 000 mg/kg铝处理显著提高水溶性有机碳(WSOC)含量,土壤水溶性氮(WSN)含量也随铝处理浓度增加显著提高。镉对WSOC无显著影响,而20～100mg/kg镉处理提高WSN含量。与单一铝或镉处理不同,铝镉复合处理显著降低SMC,降低幅度为25.10%～47.75%。WSOC和WSN含量随铝镉复合处理浓度增加显著增加。试验结果表明, SMN和WSN对铝响应敏感,镉处理对SMC和WSOC无显著影响。

两级SBR无外加碳源除磷脱氮的运行模式

在已有的两级SBR除磷脱氮工艺研究成果的基础上,分析了该工艺除磷与脱氮的优势和原运行模式存在的不足,提出了采用两级SBR工艺优化除磷与脱氮的改进运行模式,讨论了采用改进后的运行模式,在无需外加碳源条件下,实现对城市污水同步高效除磷与脱氮的可行性,分析了对该两级工艺实行实时过程控制的可行性。