Cu-Based Materials for Enhanced C_(2+) Product Selectivity in Photo-/Electro-Catalytic CO_(2) Reduction: Challenges and Prospects

Carbon dioxide conversion into valuable products using photocatalysis and electrocatalysis is an effective approach to mitigate global environmental issues and the energy shortages. Among the materials utilized for catalytic reduction of CO_(2), Cu-based materials are highly advantageous owing to their widespread availability, cost-effectiveness, and environmental sustainability. Furthermore, Cu-based materials demonstrate interesting abilities in the adsorption and activation of carbon dioxide, allowing the formation of C_(2+) compounds through C–C coupling process. Herein, the basic principles of photocatalytic CO_(2) reduction reactions(PCO_(2)RR) and electrocatalytic CO_(2) reduction reaction(ECO_(2)RR) and the pathways for the generation C_(2+) products are introduced. This review categorizes Cu-based materials into different groups including Cu metal, Cu oxides, Cu alloys, and Cu SACs, Cu heterojunctions based on their catalytic applications. The relationship between the Cu surfaces and their efficiency in both PCO_(2)RR and ECO_(2)RR is emphasized. Through a review of recent studies on PCO_(2)RR and ECO_(2)RR using Cu-based catalysts, the focus is on understanding the underlying reasons for the enhanced selectivity toward C_(2+) products. Finally, the opportunities and challenges associated with Cu-based materials in the CO_(2) catalytic reduction applications are presented, along with research directions that can guide for the design of highly active and selective Cu-based materials for CO_(2) reduction processes in the future.

S-型异质结CeO_(2)/Zn_(x)Cd_(1-x)In_(2)S_(4)空心结构的构建及其可见光分解水制氢性能

层状结构材料ZnIn_(2)S_(4)(ZIS)具有强的可见光吸收、合适的能带结构、高的化学稳定性和低毒性,是优良的光催化材料。然而,ZIS的低载流子分离效率造成其光催化产氢效率较低。为了解决这一难题,本文提出了一种整合固溶体形成和异质结构建的能带结构调控策略。通过在CeO_(2)空心球表面原位生长ZnxCd1-xIn_(2)S_(4)(ZCIS)纳米片,成功制备了具有分级中空结构的CeO_(2)/ZCIS复合光催化剂。制备的1:6-CeO_(2)/Zn_(0.9)Cd_(0.1)In_(2)S_(4)样品在可见光下表现出了4.09 mmol·g^(-1)·h^(-1)的最佳产氢速率,分别是ZIS、ZCIS和CeO_(2)/ZIS的6.8、3.0和2.2倍。其光催化活性的显著增强主要归功于CeO_(2)/ZCIS的能带结构改变产生S-型异质结电荷传输通道。同时,引入Cd阳离子使得ZIS的导带和价带同时上移,为水裂解提供强还原性光电子。相比于CeO_(2)/ZIS异质结,ZCIS和CeO_(2)之间存在更大的费米能级差,可促进更多的自由电子从ZCIS转移到CeO_(2),在CeO_(2)/ZCIS界面形成强内建电场,促进载流子有效分离,提高光催化产氢效率。本研究将为S-型异质结光催化材料设计和构筑提供一种有效策略。

Transcriptional landscape of cotton roots in response to salt stress at single-cell resolution

Increasing soil salinization has led to severe reductions in plant yield and quality,and investigating the mo-lecular mechanism of salt stress response is therefore an urgent priority.In this study,we systematically analyzed the response of cotton roots to salt stress using single-cell transcriptomics technology;56281 high-quality cells were obtained from 5-day-old lateral root tips of Gossypium arboreum under natural growth conditions and different salt treatments.Ten cell types with an array of novel marker genes were identified and confirmed by in situ RNA hybridization,and pseudotime analysis of some specific cell types revealed their potential differentiation trajectories.Prominent changes in cell numbers under salt stress were observed for outer epidermal and inner endodermal cells,which were significantly enriched in response to stress,amide biosynthetic process,glutathione metabolism,and glycolysis/gluconeogenesis.Analysis of differentially expressed genes identified in multiple comparisons revealed other functional ag-gregations concentrated on plant-type primary cell wall biogenesis,defense response,phenylpropanoid biosynthesis,and metabolic pathways.Some candidate differentially expressed genes encoding transcrip-tion factors or associated with plant hormones also responsive to salt stress were identified,and the func-tion of Ga03G2153,annotated as auxin-responsive GH3.6,was confirmed by virus-induced gene silencing.The GaGH3.6-silenced plants showed a severe stress-susceptible phenotype,and physiological and biochemical measurements indicated that they suffered more significant oxidative damage.These results suggest that GaGH3.6 might participate in cotton salt tolerance by regulating redox processes.We thus construct a transcriptional atlas of salt-stressed cotton roots at single-cell resolution,enabling us to explore cellular heterogeneity and differentiation trajectories and providing valuable insights into the mo-lecular mechanisms that underlie plant stress tolerance.

Widespread incomplete lineage sorting and introgression shaped adaptive radiation in the Gossypium genus

Cotton(Gossypium)stands as a crucial economic crop,serving as the primary source of naturalfiber for the textile sector.However,the evolutionary mechanisms driving speciation within the Gossypium genus remain unresolved.In this investigation,we leveraged 25 Gossypium genomes and introduced four novel assem-blies—G.harknessii,G.gossypioides,G.trilobum,and G.klotzschianum(Gklo)—to delve into the speciation history of this genus.Notably,we encountered intricate phylogenies potentially stemming from introgres-sion.These complexities are further compounded by incomplete lineage sorting(ILS),a factor likely to have been instrumental in shaping the swift diversification of cotton.Our focus subsequently shifted to the rapid radiation episode during a concise period in Gossypium evolution.For a recently diverged lineage comprising G.davidsonii,Gklo,and G.raimondii,we constructed afinely detailed ILS map.Intriguingly,this analysis revealed the non-random distribution of ILS regions across the reference Gklo genome.Moreover,we identified signs of robust natural selection influencing specific ILS regions.Noteworthy variations per-taining to speciation emerged between the closely related sister species Gklo and G.davidsonii.Approxi-mately 15.74%of speciation structural variation genes and 12.04%of speciation-associated genes were esti-mated to intersect with ILS signatures.Thesefindings enrich our understanding of the role of ILS in adaptive radiation,shedding fresh light on the intricate speciation history of the Gossypium genus.

磷掺杂剂和石墨烯包覆层对NiCo_(2)S_(4)电催化剂析氢活性和耐久性的协同影响

探索具有优异导电性和稳定性的非贵金属电催化剂对氢经济至关重要.本研究将杂原子掺杂和石墨烯包覆相结合,以控制NiCo_(2)S_(4)(NCS)蛋黄壳微球的电子性能,并抵抗酸性介质中H_(2)O和O_(2)的腐蚀.密度泛函理论(DFT)模拟结合综合表征和实验首次揭示了在NCS中引入P杂原子不仅加速了电子从体相向表面的转移动力学,而且降低了掺杂P原子附近活性S位上的析氢反应势垒.利用DFT计算的穿透能垒预测了rGO覆盖层在P掺杂NCS(P-NCS)表面对质子的渗透性和对H_(2)O和O_(2)分子的抵抗性等重要功能,并用X射线光电子能谱对新催化剂和回收催化剂进行了验证.利用P掺杂剂和rGO覆盖层分别辅助电荷传递和质子传递,通过二者的协同作用获得了催化活性和耐久性之间的平衡.因此,优化后的P-NCS/rGO在70 mV的低过电位下实现了10 mA cm^(-2)的电流密度,并具有令人满意的80小时耐用性.本工作阐明了石墨烯覆盖硫化物催化剂可通过调控电子结构和质子/分子穿透提高电催化性能.

Interface charge separation in Cu_(2)CoSnS_(4)/ZnIn_(2)S_(4) heterojunction for boosting photocatalytic hydrogen production

The practical application of hexagonal ZnIn_(2)S_(4)(ZIS)as a visible-light photocatalyst for hydrogen(H_(2))production is hindered by rapid internal charge recombination.In this study,we successfully synthesized Cu_(2)CoSnS_(4)(CCTS)nanocrystals and loaded them onto the surface of ZIS nanosheets to create a p-n heterojunction photocatalyst.The optimized Cu_(2)CoSnS_(4)/ZnIn_(2)S_(4)(CCTS/ZIS)heterojunction exhibited a significantly higher visible-light photo-catalytic H_(2)evolution rate of 4.90 mmol·g^(-1)·h^(-1)compared to ZIS and CCTS alone.The enhanced photocatalytic efficiency was attributed to improved electron transfer and charge separation at the heterojunction interface.The formation of p-n heterojunction facilitated the accumulation of valence band electrons in ZIS and conduction band holes in CCTS,effectively suppressing the recombination of photogenerated electrons and holes.Theoretical calculations,spectroscopic,and photoelectrochemical characterizations supported the findings.This work pre-sents a promising approach for designing efficient p-n heterojunction semiconductor photocatalysts for practical applications in visible-light-driven hydrogen evolution.

IL-17 sustains the plasma cell response via p38-mediated Bcl-xL RNA stability in lupus pathogenesis

Recent studies have demonstrated a central role for plasma cells in the development of autoimmune diseases,such as systemic lupus erythematosus(SLE).Currently,both the phenotypic features and functional regulation of autoreactive plasma cells during SLE pathogenesis remain largely unclear.In this study,we first found that a major subset of IL-17 receptor-expressing plasma cells potently produced anti-dsDNA IgG upon IL-17A(IL-17)stimulation in SLE patients and lupus mice.Using a humanized lupus mouse model,we showed that the transfer of Th17 cell-depleted PBMCs from lupus patients resulted in a significantly reduced plasma cell response and attenuated renal damage in recipient mice compared to the transfer of total SLE PBMCs.Moreover,long-term BrdU incorporation in lupus mice detected highly enriched long-lived BrdU+subsets among IL-17 receptor-expressing plasma cells.Lupus mice deficient in IL-17 or IL-17 receptor C(IL-17RC)exhibited a diminished plasma cell response and reduced autoantibody production with attenuated renal damage,while the adoptive transfer of Th17 cells triggered the plasma cell response and renal damage in IL-17-deficient lupus mice.In reconstituted chimeric mice,IL-17RC deficiency resulted in severely impaired plasma cell generation but showed no obvious effect on germinal center B cells.Further mechanistic studies revealed that IL-17 significantly promoted plasma cell survival via p38-mediated Bcl-xL transcript stabilization.Together,our findings identified a novel function of IL-17 in enhancing plasma cell survival for autoantibody production in lupus pathogenesis,which may provide new therapeutic strategies for the treatment of SLE.

Effects of Bi-dopant and co-catalysts upon hole surface trapping on La_(2)Ti_(2)O_(7) nanosheet photocatalysts in overall solar water splitting

Pristine and Bi-doped lanthanum titanium oxide(La_(2)Ti_(2)O_(7))nanosheets have been synthesized as photocatalysts for overall solar water splitting.The surface hole trap is a critical factor that limits the photocatalytic activity of pristine La_(2)Ti_(2)O_(7)-Deposition of cobalt phosphate(Co-Pi)and platinum(Pt)nanoparticles on La_(2)Ti_(2)O_(7) cannot remove the surface traps although they are essential for enabling the oxygen and hydrogen evolution reactions.It is interesting that doping bismuth(Bi)into La_(2)Ti_(2)O_(7) nanosheets has eliminated the surface traps due to surface enrichment of Bi.The Co-Pi/Bi-La_(2)Ti_(2)O_(7)/Pt nanosheets exhibit increasing photocatalytic activity toward overall water splitting with increasing the Bi-dopant level up to 5 at.%.Further increasing the Bi-dopant level leads to the formation of localized states above the valence band,leading to the lifetime reduction of photogenerated charge-carriers,and jeopardizing the photocatalytic activity.This work proposes an effective strategy to address the surface trapping and surface catalysis issues in the nanostructured metal oxide photocatalysts.

Epigenetic regulation of B cells and its role in autoimmune pathogenesis

B cells play a pivotal role in the pathogenesis of autoimmune diseases.Although previous studies have shown many genetic polymorphisms associated with B-cell activation in patients with various autoimmune disorders,progress in epigenetic research has revealed new mechanisms leading to B-cell hyperactivation.Epigenetic mechanisms,including those involving histone modifications,DNA methylation,and noncoding RNAs,regulate B-cell responses,and their dysregulation can contribute to the pathogenesis of autoimmune diseases.Patients with autoimmune diseases show epigenetic alterations that lead to the initiation and perpetuation of autoimmune inflammation.Moreover,many clinical and animal model studies have shown the promising potential of epigenetic therapies for patients.In this review,we present an up-to-date overview of epigenetic mechanisms with a focus on their roles in regulating functional B-cell subsets.Furthermore,we discuss epigenetic dysregulation in B cells and highlight its contribution to the development of autoimmune diseases.Based on clinical and preclinical evidence,we discuss novel epigenetic biomarkers and therapies for patients with autoimmune disorders.

Efficient charge separation in hierarchical NiS@ZnIn_(2)S_(4) hollow nanospheres for photocatalytic water splitting

In this work,hierarchical Ni S@Zn In_(2)S_(4) heterostructure was developed by constructing ultra-thin Zn In;S;(ZIS) nanosheets on hollow Ni S nanospheres for hydrogen production from photocatalytic water splitting.The Ni S@ZIS displayed a strong optical absorption ability in the visible region and a high specific surface area of 33.14 m^(2)/g.The Type-I band alignment in Ni S@ZIS heterostructure was determined by the combination of UV–vis absorption spectroscopy and Mott-Schottky curves.The photocatalytic hydrogen production of Ni S@ZIS (1.24 mmol g;h;) was nearly 5.6 times higher than that of ZIS under visible light,in the absence of any co-catalyst and sacrificial agent.The separation and migration of charge in Ni S@ZIS were characterized by a series of spectroscopy and photo/electrochemical tests,which verified the efficient charge transfer from ZIS to Ni S.