Continuous electroproduction of formate via CO2 reduction on local symmetry-broken single-atom catalysts.

Atomic-level coordination engineering is an efficient strategy for tuning the catalytic performance of single-atom catalysts (SACs). However, their rational design has so far been plagued by the lack of a universal correlation between the coordination symmetry and catalytic properties. Herein, we synthesised planar-symmetry-broken CuN3 (PSB-CuN3) SACs through microwave heating for electrocatalytic CO2 reduction. Remarkably, the as-prepared catalysts exhibited a selectivity of 94.3% towards formate at -0.73 V vs. RHE, surpassing the symmetrical CuN4 catalyst (72.4% at -0.93 V vs. RHE). In a flow cell equipped with a PSB-CuN3 electrode, over 90% formate selectivity was maintained at an average current density of 94.4 mA cm-2 during 100 h operation. By combining definitive structural identification with operando X-ray spectroscopy and theoretical calculations, we revealed that the intrinsic local symmetry breaking from planar D4h configuration induces an unconventional dsp hybridisation, and thus a strong correlation between the catalytic activity and microenvironment of metal centre (i.e., coordination number and distortion), with high preference for formate production in CuN3 moiety. The finding opens an avenue for designing efficient SACs with specific local symmetries for selective electrocatalysis.

Photochemical Acceleration of Ammonia Production by Pt1-Ptn-TiN Reduction and N2 Activation.

Stable metal nitrides (MN) are promising materials to fit the future "green" ammonia-hydrogen nexus. Either through catalysis or chemical looping, the reductive hydrogenation of MN to MN1-x is a necessary step to generate ammonia. However, encumbered by the formation of kinetically stable M-NH1─3 surface species, this reduction step remains challenging under mild conditions. Herein, we discovered that deleterious Ti-NH1─3 accumulation on TiN can be circumvented photochemically with supported single atoms and clusters of platinum (Pt1-Ptn) under N2-H2 conditions. The photochemistry of TiN selectively promoted Ti-NH formation, while Pt1-Ptn effectively transformed any formed Ti-NH into free ammonia. The generated ammonia was found to originate mainly from TiN reduction with a minor contribution from N2 activation. The knowledge accrued from this fundamental study could serve as a springboard for the development of MN materials for more efficient ammonia production to potentially disrupt the century-old fossil-powered Haber-Bosch process.

Atomic-Level Regulation of Cobalt Single-Atom Nanozymes: Engineering High-Efficiency Catalase Mimics.

Nanozymes aim to mimic the highly evolved active centers of natural enzymes. Despite progress in nanozyme engineering, their catalytic performance is much less favorable compared with natural enzymes. This study shows that precise control over the atomic configuration of the active centers of Co single-atom nanozymes (SAzymes) enables the rational regulation of their catalase-like performance guided by theorical calculations. The constructed Co-N3 PS SAzyme exhibits an excellent catalase-like activity and kinetics, exceeding the representative controls of Co-based SAzymes with different atomic configurations. Moreover, we developed an ordered structure-oriented coordination design strategy for rationally engineering SAzymes and established a correlation between the structure and enzyme-like performance. This work demonstrates that precise control over the active centers of SAzymes is an efficient strategy to mimic the highly evolved active sites of natural enzymes.

Pt Atomic Layers with Tensile Strain and Rich Defects Boost Ethanol Electrooxidation.

Surface and strain engineering are two effective strategies to improve performance; however, synergetic controls of surface and strain effects remains a grand challenge. Herein, we report a highly efficient and stable electrocatalyst with defect-rich Pt atomic layers coating an ordered Pt3Sn intermetallic core. Pt atomic layers enable the generation of 4.4% tensile strain along the [001] direction. Benefiting from synergetic controls of surface and strain engineering, Pt atomic-layer catalyst (Ptatomic-layer) achieves a remarkable enhancement on ethanol electrooxidation performance with excellent specific activity of 5.83 mA cm-2 and mass activity of 1166.6 mA mg Pt-1, which is 10.6 and 3.6 times higher than the commercial Pt/C, respectively. Moreover, the intermetallic core endows Ptatomic-layer with outstanding durability. In situ infrared reflection-absorption spectroscopy as well as density functional theory calculations reveal that tensile strain and rich defects of Ptatomci-layer facilitate to break C-C bond for complete ethanol oxidation for enhanced performance.

Synthetic strategies for MOF-based single-atom catalysts for photo- and electro-catalytic CO2 reduction.

The excessive CO2 emission has resulted in climate changes, which has threatened human existence. Photocatalytic and electrocatalytic CO2 reduction, driven by wind electricity and solar energy, are feasible ways of tackling carbon dioxide emission, as both energies are clean and renewable. Single-atom catalyst (SAC) is a candidate owing to excellent electrocatalytic and photocatalytic performance. Methods for preparing an SAC by using metal-organic frameworks (MOFs) as support or precursors are summarized. Also, applications in energy conversion are exhibited. However, the real challenge is to improve the selectivity of catalytic reactions to yield higher value products, which is to be discussed.

Thermal Atomization of Platinum Nanoparticles into Single Atoms: An Effective Strategy for Engineering High-Performance Nanozymes.

Although great progress has been made in artificial enzyme engineering, their catalytic performance is far from satisfactory as alternatives of natural enzymes. Here, we report a novel and efficient strategy to access high-performance nanozymes via direct atomization of platinum nanoparticles (Pt NPs) into single atoms by reversing the thermal sintering process. Atomization of Pt NPs into single atoms makes metal catalytic sites fully exposed and results in engineerable structural and electronic properties, thereby leading to dramatically enhanced enzymatic performance. As expected, the as-prepared thermally stable Pt single-atom nanozyme (PtTS-SAzyme) exhibited remarkable peroxidase-like catalytic activity and kinetics, far exceeding the Pt nanoparticle nanozyme. The following density functional theory calculations revealed that the engineered P and S atoms not only promote the atomization process from Pt NPs into PtTS-SAzyme but also endow single-atom Pt catalytic sites with a unique electronic structure owing to the electron donation of P atoms, as well as the electron acceptance of N and S atoms, which simultaneously contribute to the substantial enhancement of the enzyme-like catalytic performance of PtTS-SAzyme. This work demonstrates that thermal atomization of the metal nanoparticle-based nanozymes into single-atom nanozymes is an effective strategy for engineering high-performance nanozymes, which opens up a new way to rationally design and optimize artificial enzymes to mimic natural enzymes.

The atomic-level regulation of single-atom site catalysts for the electrochemical CO2 reduction reaction.

The electrochemical CO2 reduction reaction (CO2RR) is viewed as a promising way to remove the greenhouse gas CO2 from the atmosphere and convert it into useful industrial products such as methane, methanol, formate, ethanol, and so forth. Single-atom site catalysts (SACs) featuring maximum theoretical atom utilization and a unique electronic structure and coordination environment have emerged as promising candidates for use in the CO2RR. The electronic properties and atomic structures of the central metal sites in SACs will be changed significantly once the types or coordination environments of the central metal sites are altered, which appears to provide new routes for engineering SACs for CO2 electrocatalysis. Therefore, it is of great importance to discuss the structural regulation of SACs at the atomic level and their influence on CO2RR activity and selectivity. Despite substantial efforts being made to fabricate various SACs, the principles of regulating the intrinsic electrocatalytic performances of the single-atom sites still needs to be sufficiently emphasized. In this perspective article, we present the latest progress relating to the synthesis and catalytic performance of SACs for the electrochemical CO2RR. We summarize the atomic-level regulation of SACs for the electrochemical CO2RR from five aspects: the regulation of the central metal atoms, the coordination environments, the interface of single metal complex sites, multi-atom active sites, and other ingenious strategies to improve the performance of SACs. We highlight synthesis strategies and structural design approaches for SACs with unique geometric structures and discuss how the structure affects the catalytic properties.

Atomic-Level Modulation of Electronic Density at Cobalt Single-Atom Sites Derived from Metal-Organic Frameworks: Enhanced Oxygen Reduction Performance.

Demonstrated here is the correlation between atomic configuration induced electronic density of single-atom Co active sites and oxygen reduction reaction (ORR) performance by combining density-functional theory (DFT) calculations and electrochemical analysis. Guided by DFT calculations, a MOF-derived Co single-atom catalyst with the optimal Co1 -N3 PS active moiety incorporated in a hollow carbon polyhedron (Co1 -N3 PS/HC) was designed and synthesized. Co1 -N3 PS/HC exhibits outstanding alkaline ORR activity with a half-wave potential of 0.920 V and superior ORR kinetics with record-level kinetic current density and an ultralow Tafel slope of 31 mV dec-1 , exceeding that of Pt/C and almost all non-precious ORR electrocatalysts. In acidic media the ORR kinetics of Co1 -N3 PS/HC still surpasses that of Pt/C. This work offers atomic-level insight into the relationship between electronic density of the active site and catalytic properties, promoting rational design of efficient catalysts.

Synthetic strategies of supported atomic clusters for heterogeneous catalysis.

Supported atomic clusters with uniform metal sites and definite low-nuclearity are intermediate states between single-atom catalysts (SACs) and nanoparticles in size. Benefiting from the presence of metal-metal bonds, supported atomic clusters can trigger synergistic effects among every metal atom, which contributes to achieving unique catalytic properties different from SACs and nanoparticles. However, the scalable and precise synthesis and atomic-level insights into the structure-properties relationship of supported atomic clusters is a great challenge. This perspective presents the latest progress of the synthesis of supported atomic clusters, highlights how the structure affects catalytic properties, and discusses the limitations as well as prospects.

Iridium single-atom catalyst on nitrogen-doped carbon for formic acid oxidation synthesized using a general host-guest strategy.

Single-atom catalysts not only maximize metal atom efficiency, they also display properties that are considerably different to their more conventional nanoparticle equivalents, making them a promising family of materials to investigate. Herein we developed a general host-guest strategy to fabricate various metal single-atom catalysts on nitrogen-doped carbon (M1/CN, M = Pt, Ir, Pd, Ru, Mo, Ga, Cu, Ni, Mn). The iridium variant Ir1/CN electrocatalyses the formic acid oxidation reaction with a mass activity of 12.9 [Formula: see text] whereas an Ir/C nanoparticle catalyst is almost inert (~4.8 × 10-3 [Formula: see text]). The activity of Ir1/CN is also 16 and 19 times greater than those of Pd/C and Pt/C, respectively. Furthermore, Ir1/CN displays high tolerance to CO poisoning. First-principle density functional theory reveals that the properties of Ir1/CN stem from the spatial isolation of iridium sites and from the modified electronic structure of iridium with respect to a conventional nanoparticle catalyst.

Adsorption Site Regulation to Guide Atomic Design of Ni-Ga Catalysts for Acetylene Semi-Hydrogenation.

Atomic regulation of metal catalysts has emerged as an intriguing yet challenging strategy to boost product selectivity. Here, we report a density functional theory-guided atomic design strategy for the fabrication of a NiGa intermetallic catalyst with completely isolated Ni sites to optimize acetylene semi-hydrogenation processes. Such Ni sites show not only preferential acetylene π-adsorption, but also enhanced ethylene desorption. The characteristics of the Ni sites are confirmed by multiple characterization techniques, including aberration-corrected high-resolution scanning transmission electron microscopy and X-ray absorption spectrometry measurements. The superior performance is also confirmed experimentally against a Ni5 Ga3 intermetallic catalyst with partially isolated Ni sites and against a Ni catalyst with multi-atomic ensemble Ni sites. Accordingly, the NiGa intermetallic catalyst with the completely isolated Ni sites shows significantly enhanced selectivity to ethylene and suppressed coke formation.

Chemical Synthesis of Single Atomic Site Catalysts.

Manipulating metal atoms in a controllable way for the synthesis of materials with the desired structure and properties is the holy grail of chemical synthesis. The recent emergence of single atomic site catalysts (SASC) demonstrates that we are moving toward this goal. Owing to the maximum efficiency of atom-utilization and unique structures and properties, SASC have attracted extensive research attention and interest. The prerequisite for the scientific research and practical applications of SASC is to fabricate highly reactive and stable metal single atoms on appropriate supports. In this review, various synthetic strategies for the synthesis of SASC are summarized with concrete examples highlighting the key issues of the synthesis methods to stabilize single metal atoms on supports and to suppress their migration and agglomeration. Next, we discuss how synthesis conditions affect the structure and catalytic properties of SASC before ending this review by highlighting the prospects and challenges for the synthesis as well as further scientific researches and practical applications of SASC.

Rare-Earth Single Erbium Atoms for Enhanced Photocatalytic CO2 Reduction.

The solar-driven photocatalytic reduction of CO2 (CO2 RR) into chemical fuels is a promising route to enrich energy supplies and mitigate CO2 emissions. However, low catalytic efficiency and poor selectivity, especially in a pure-water system, hinder the development of photocatalytic CO2 RR owing to the lack of effective catalysts. Herein, we report a novel atom-confinement and coordination (ACC) strategy to achieve the synthesis of rare-earth single erbium (Er) atoms supported on carbon nitride nanotubes (Er1 /CN-NT) with a tunable dispersion density of single atoms. Er1 /CN-NT is a highly efficient and robust photocatalyst that exhibits outstanding CO2 RR performance in a pure-water system. Experimental results and density functional theory calculations reveal the crucial role of single Er atoms in promoting photocatalytic CO2 RR.

Well-Defined Materials for Heterogeneous Catalysis: From Nanoparticles to Isolated Single-Atom Sites.

The use of well-defined materials in heterogeneous catalysis will open up numerous new opportunities for the development of advanced catalysts to address the global challenges in energy and the environment. This review surveys the roles of nanoparticles and isolated single atom sites in catalytic reactions. In the second section, the effects of size, shape, and metal-support interactions are discussed for nanostructured catalysts. Case studies are summarized to illustrate the dynamics of structure evolution of well-defined nanoparticles under certain reaction conditions. In the third section, we review the syntheses and catalytic applications of isolated single atomic sites anchored on different types of supports. In the final part, we conclude by highlighting the challenges and opportunities of well-defined materials for catalyst development and gaining a fundamental understanding of their active sites.

Engineering the Atomic Interface with Single Platinum Atoms for Enhanced Photocatalytic Hydrogen Production.

It is highly desirable but challenging to optimize the structure of photocatalysts at the atomic scale to facilitate the separation of electron-hole pairs for enhanced performance. Now, a highly efficient photocatalyst is formed by assembling single Pt atoms on a defective TiO2 support (Pt1 /def-TiO2 ). Apart from being proton reduction sites, single Pt atoms promote the neighboring TiO2 units to generate surface oxygen vacancies and form a Pt-O-Ti3+ atomic interface. Experimental results and density functional theory calculations demonstrate that the Pt-O-Ti3+ atomic interface effectively facilitates photogenerated electrons to transfer from Ti3+ defective sites to single Pt atoms, thereby enhancing the separation of electron-hole pairs. This unique structure makes Pt1 /def-TiO2 exhibit a record-level photocatalytic hydrogen production performance with an unexpectedly high turnover frequency of 51423 h-1 , exceeding the Pt nanoparticle supported TiO2 catalyst by a factor of 591.

SOX19b regulates the premature neuronal differentiation of neural stem cells through EZH2-mediated histone methylation in neural tube development of zebrafish.

OBJECTIVE: Neural tube defects (NTDs) are the most serious and common birth defects in the clinic. The SRY-related HMG box B1 (SoxB1) gene family has been implicated in different processes of early embryogenesis. Sox19b is a maternally expressed gene in the SoxB1 family that is found in the region of the presumptive central nervous system (CNS), but its role and mechanism in embryonic neural stem cells (NSCs) during neural tube development have not yet been explored. Considering that Sox19b is specific to bony fish, we intended to investigate the role and mechanism of Sox19b in neural tube development in zebrafish embryos. MATERIAL AND METHODS: Morpholino (MO) antisense oligonucleotides were used to construct a Sox19b loss-of-function zebrafish model. The phenotype and the expression of related genes were analysed by in situ hybridization and immunolabelling. Epigenetic modifications were detected by western blot and chromatin immunoprecipitation. RESULTS: In this study, we found that zebrafish embryos exhibited a reduced or even deleted forebrain phenotype after the expression of the Sox19b gene was inhibited. Moreover, we found for the first time that knockdown of Sox19b reduced the proliferation of NSCs; increased the transcription levels of Ngn1, Ascl1, HuC, Islet1, and cyclin-dependent kinase (CDK) inhibitors; and led to premature differentiation of NSCs. Finally, we found that knockdown of Sox19b decreased the levels of EZH2/H3K27me3 and decreased the level of H3K27me3 at the promoters of Ngn1 and ascl1a. CONCLUSION: Together, our data demonstrate that Sox19b plays an essential role in early NSC proliferation and differentiation through EZH2-mediated histone methylation in neural tube development. This study established the role of transcription factor Sox19b and epigenetic factor EZH2 regulatory network on NSC development, which provides new clues and theoretical guidance for the clinical treatment of neural tube defects.

Bismuth Single Atoms Resulting from Transformation of Metal-Organic Frameworks and Their Use as Electrocatalysts for CO2 Reduction.

The electrocatalytic reduction reaction of CO2 (CO2RR) is a promising strategy to promote the global carbon balance and combat global climate change. Herein, exclusive Bi-N4 sites on porous carbon networks can be achieved through thermal decomposition of a bismuth-based metal-organic framework (Bi-MOF) and dicyandiamide (DCD) for CO2RR. Interestingly, in situ environmental transmission electron microscopy (ETEM) analysis not only directly shows the reduction from Bi-MOF into Bi nanoparticles (NPs) but also exhibits subsequent atomization of Bi NPs assisted by the NH3 released from the decomposition of DCD. Our catalyst exhibits high intrinsic CO2 reduction activity for CO conversion, with a high Faradaic efficiency (FECO up to 97%) and high turnover frequency of 5535 h-1 at a low overpotential of 0.39 V versus reversible hydrogen electrode. Further experiments and density functional theory results demonstrate that the single-atom Bi-N4 site is the dominating active center simultaneously for CO2 activation and the rapid formation of key intermediate COOH* with a low free energy barrier.

TIGAR promotes neural stem cell differentiation through acetyl-CoA-mediated histone acetylation.

Cellular metabolism plays a crucial role in controlling the proliferation, differentiation, and quiescence of neural stem cells (NSCs). The metabolic transition from aerobic glycolysis to oxidative phosphorylation has been regarded as a hallmark of neuronal differentiation. Understanding what triggers metabolism reprogramming and how glucose metabolism directs NSC differentiation may provide new insight into the regenerative potential of the brain. TP53 inducible glycolysis and apoptosis regulator (TIGAR) is an endogenous inhibitor of glycolysis and is highly expressed in mature neurons. However, its function in embryonic NSCs has not yet been explored. In this study, we aimed to investigate the precise roles of TIGAR in NSCs and the possible involvement of metabolic reprogramming in the TIGAR regulatory network. We observed that TIGAR is significantly increased during brain development as neural differentiation proceeds, especially at the peak of NSC differentiation (E14.5-E16.5). In cultured NSCs, knockdown of TIGAR reduced the expression of microtubule-associated protein 2 (MAP2), neuron-specific class III beta-tubulin (Tuj1), glial fibrillary acidic protein (GFAP), Ngn1, and NeuroD1, and enhanced the expression of REST, suggesting that TIGAR is an important regulator of NSC differentiation. Furthermore, TIGAR enhanced the expression of lactate dehydrogenase B (LDHB) and the mitochondrial biogenesis and oxidative phosphorylation (OXPHOS) markers, peroxisome proliferator-activated receptor gamma coactivator 1 (PGC-1α), nuclear respiratory factor (NRF1), and MitoNEET during NSC differentiation. TIGAR can decrease lactate production and accelerate oxygen consumption and ATP generation to maintain a high rate of OXPHOS in differentiated NSCs. Interestingly, knockdown of TIGAR decreased the level of acetyl-CoA and H3K9 acetylation at the promoters of Ngn1, Neurod1, and Gfap. Acetate, a precursor of acetyl-CoA, increased the level of H3K9 acetylation and rescued the effect of TIGAR deficiency on NSC differentiation. Together, our data demonstrated that TIGAR promotes metabolic reprogramming and regulates NSC differentiation through an epigenetic mechanism.