Accelerating the design of catalysts for CO_(2)electroreduction to HCOOH:A data-driven DFT-ML screening of dual atom catalysts

Dual-atom catalysts(DACs)have emerged as potential catalysts for effective electroreduction of CO_(2)due to their high atom utilization efficiency and multiple active sites.However,the screening of DACs remains a challenge due to the large number of possible combinations,making exhaustive experimental or computational screening a daunting task.In this study,a density functional theory(DFT)-based machine learning(ML)-accelerated(DFT-ML)hybrid approach was developed to test a set of 406 dual transition metal catalysts on N-doped graphene(NG)for the electroreduction of CO_(2)to HCOOH.The results showed that the ML algorithms can successfully capture the relationship between the descriptors of the DACs(inputs)and the limiting potential for HCOOH generation(output).Of the four ML algorithms studied in this work,the feedforward neural network model achieved the highest prediction accuracy(the highest correlation coefficient(R^(2))of 0.960 and the lowest root mean square error(RMSE)of 0.319 eV on the test set)and the predicted results were verified by DFT calculations with an average absolute error of 0.14 eV.The DFT-ML approach identified Co-Co-NG and Ir-Fe-NG as the most active and stable electrocatalysts for the electrochemical reduction of CO_(2)to HCOOH.The DFT-ML hybrid approach exhibits exceptional prediction accuracy while enabling a significant reduction in screening time by an impressive 64%compared to conventional DFT-only calculations.These results demonstrate the immense potential of using ML methods to accelerate the screening and rational design of efficient catalysts for various energy and environmental applications.

Supported dual-atom catalysts: Preparation, characterization, and potential applications

Developing sustainable and clean electrochemical energy conversion technologies is a crucial step in addressing the challenges of energy shortage and environmental pollution. Exploring and developing new electrocatalysts with excellent performance and low cost will facilitate the commercial use of these energy conversion technologies. Recently, dual-atom catalysts(DACs) have attracted considerable research interest since they exhibit higher metal atom loading and more flexible active sites compared to single-atom catalysts(SACs). In this paper, the latest preparation methods and characterization techniques of DACs are systematically reviewed. The advantages of homonuclear and heteronuclear DACs and the catalytic mechanism and identification technologies between the two DACs are highlighted. The current applications of DACs in the field of electrocatalysis are summarized. The development opportunities and challenges of DACs in the future are prospected. The ultimate goal is to provide new ideas for the preparation of new catalysts with excellent properties by customizing diatomic catalysts for electrochemical applications.

Dual metal atom catalysts:Advantages in electrocatalytic reactions

The dual-metal-atom catalysts(DACs)have aroused much attention as they possess the advantages of single-atom and metal alloy catalysts.And the DACs have exhibited enhanced performance in various electrocatalytic reactions,such as hydrogen/oxygen evolution and oxygen/carbon dioxide/nitrogen reduction.In this review,we mainly overview the latest understanding of the advantages of DACs for these reactions.This review will start with the familiar characterization methods for DACs,then the primary synthesis strategies for DACs will be discussed.Emphasis is given to the advantages of DACs in catalytic reactions,including the adsorption and activation,electronic structure regulation,breaking scaling relations,reducing energy barriers,cascading and coupling,synergy effect,and providing mechanism research platforms.Finally,personal perspectives and challenges for the further development of DACs are briefly discussed.

Dual atomic catalysts from COF-derived carbon for CO_(2)RR by suppressing HER through synergistic effects

The electrochemical carbon dioxide reduction reaction(CO_(2)RR)for highvalue-added products is a promising strategy to tackle excessive CO_(2) emissions.However,the activity of and selectivity for catalysts for CO_(2)RR still need to be improved because of the competing reaction(hydrogen evolution reaction).In this study,for the first time,we have demonstrated dual atomic catalytic sites for CO_(2)RR from a core-shell hybrid of the covalent-organic framework and the metal-organic framework.Due to abundant dual atomic sites(with CoN_(4)O and ZnN_(4) of 2.47 and 11.05 wt.%,respectively)on hollow carbon,the catalyst promoted catalysis of CO_(2)RR,with the highest Faradic efficiency for CO of 92.6%at-0.8 V and a turnover frequency value of 1370.24 h^(-1) at-1.0 V.More importantly,the activity and selectivity of the catalyst were well retained for 30 h.The theoretical calculation further revealed that CoN_(4)O was the main site for CO_(2)RR,and the activity of and selectivity for Zn sites were also improved because of the synergetic roles.

Improved visible-light photocatalytic H_2 generation over CdS nanosheets decorated by NiS_2 and metallic carbon black as dual earth-abundant cocatalysts

CdS nanosheets(NSs)photocatalysts modified with dual earth‐abundant co‐catalysts of metallic carbon black(CB)and NiS2were synthesized by a two‐step solvothermal/impregnation method.Allthe experiment results demonstrated that the co‐loading of CB and NiS2could significantly enhance the photocatalytic H2‐evolution activity of CdS NSs.The photocatalytic performance of the as‐prepared CdS/CB/NiS2samples was tested under visible light(λ≥420nm)by using an aqueous solution containing0.25mol L–1Na2S‐Na2SO3as the sacrifice agent.The CdS‐0.5%CB‐1.0%NiS2composite photocatalysts exhibited the highest H2‐evolution rate of166.7μmol h?1,which was approximately5.16and1.87times higher than those of pure CdS NSs and CdS‐1.0%NiS2,respectively.The possible mechanism for the enhanced H2‐evolution activity of CdS/CB/NiS2composite photocatalysts was proposed.The results showed that the enhanced photocatalytic H2‐evolution activities could be ascribed to the co‐loading of metallic CB and NiS2as co‐catalysts onto the surface of CdS NSs.The excellent synergetic effect between the CB and NiS2could obviously improve visible light absorption,promote separation of photogenerated electron‐hole pairs and boost the H2‐evolution kinetics,thus leading to an enhanced activity for H2evolution.More interestingly,the metallic CB could not only act as a cocatalyst for H2evolution,but also serve as a conductive electron bridge to promote the charge migration.This work not only demonstrates that loading CB as a co‐catalyst is a promising strategy to further boost the photocatalytic activity of CdS/NiS2composites,but also offers a new mechanistic insight into the construction of highly efficient and stable CdS NSs‐based hybrid photocatalysts with dual earth‐abundant co‐catalysts for photocatalytic applications.

Particle/metal-based monolithic catalysts dual-bed reactor with beds-interspace supplementary oxygen:Construction and performance for oxidative coupling of methane

A novel particle/metal-based monolithic catalysts dual-bed reactor with beds-interspace supplementary oxygen is constructed comprising of the upper-layer 5 wt%Na2WO4-2 wt%Mn/SiO2 particle catalyst and the under-layer 3 wt%Ce-5 wt%Na2WO4-2 wt%Mn/SBA-15/Al2O3/FeCrA1 metal-based monolithic catalyst as well as a side tube in the interspaces of two layers for supplementing 02. The reaction performance of oxidative coupling of methane （OCM） in the dual-bed reactor system is evaluated. The effects of the reaction parameters such as feed CH4/O2 ratio, reaction temperature and side tube feed 02 flowrate on the catalytic performance are investigated. The results indicate that the suggested mode of dual-bed reactor exhibits an excellent performance for OCM. CH4 conversion of 33.2%, C2H4 selectivity of 46.5% and C2 yield of 22.5% could be obtained, which have been increased by 6.4%, 4.1% and 5.5%, respectively, as compared with 5 wt%Na2WO4-2 wt%Mn/SiO2 particle catalyst in a single-bed reactor and increased by 10.7%, 31.9% and 17.7%, respectively, as compared with 3 wt%Ce-5 wt%Na2WO4-2 wt%Mn/SBA-15/Al2O3/FeCrA1 metal-based monolithic catalyst in a single-bed reactor. The effective promotion of OCM performance in the reactor would supply a valuable reference for the industrialization of OCM process.

Oxidative coupling of methane in a dual-bed reactor comprising of particle/cordierite monolithic catalysts

A dual-bed reactor was constructed comprising of a 5%Na2WO4-2%Mn/SiO2 particle catalyst and a 4%Ce-5%Na2WO4-2%Mn/SiO2 /cordierite monolithic catalyst.The reaction performance of the oxidative coupling of methane （OCM） over the dual-bed reactor system was evaluated.The effects of the bed height and operation mode,as well as the reaction parameters such as reaction temperature,CH4/O2 ratio and flowrate of feed gas,on the catalytic performance were investigated.The results indicated that the suggested dual-bed reactor exhibited a good performance for the OCM reaction when the feed gases firstly passed through the particle catalyst bed and then to the monolithic catalyst bed.A CH4 conversion of 38.2% and a C2H4 selectivity of 43.3% could be obtained using the dual-bed reactor with a particle catalyst bed height of 10 mm and a monolithic catalyst bed height of 50 mm.Both the CH4 conversion and C2H4 selectivity have increased by 2.5% and 12.8%,respectively,as compared with the 5%Na2WO4-2%Mn/SiO2 particle catalyst in a conventional single-bed reactor and by 12.9% and 23.0%,respectively,as compared with the 4%Ce-5%Na2WO4-2%Mn/SiO2 /cordierite monolithic catalyst in a single-bed reactor.The catalytic performance of the OCM in the dual-bed reactor system has been improved remarkably.

Precise construction of RuPt dual single-atomic sites to optimize oxygen electrocatalytic behaviors for high-performance Zn-air batteries

The development of redox bifunctional electrocatalysts with high performance,low cost,and long lifetimes is essential for achieving clean energy goals.This study proposed an atom capture strategy for anchoring dual single atoms(DSAs)in a zinc-zeolitic imidazolate framework(Zn-ZIF),followed by calcination under an N_(2) atmosphere to synthesize ruthenium-platinum DSAs supported on a nitrogendoped carbon substrate(RuPt DSAs-NC).Theoretical calculations showed that the degree of Ru 5dxz-~*O 2p_x orbital hybridization was high when^(*)O was adsorbed at the Ru site,indicating enhanced covalent hybridization of metal sites and oxygen ligands,which benefited the adsorption of intermediate species.The presence of the RuPtN_6 active center optimized the absorption-desorption behavior of intermediates,improving the electrocatalytic performance of the oxygen reduction reaction(ORR)and the oxygen evolution reaction(DER),RuPt DSAs-NC exhibited a 0.87 V high half-wave potential and a 268 mV low overpotential at 10 mA cm^(-2)in an alkaline environment.Furthermore,rechargeable zinc-air batteries(ZABs)achieved a peak power density of 171 MW cm^(-2).The RuPt DSAs-NC demonstrated long-term cycling for up to 500 h with superior round-trip efficiency.This study provided an effective structural design strategy to construct DSAs active sites for enhanced electrocata lytic performance.

Cu-Pd Dual Catalyst System for Amide Styrylation Reaction from Potassium Styryltrifluoroborates and Amides

An interesting reaction procedure for the cross-coupling of potassium styryltrifluoroborates and amides has been developed by using PdCl2(dtbpf)-CuI dual catalyst system. By applying this method, good numbers of amide styrylation products are formed in 85% - 92% yields.

Bimetallic ZIFs-derived electrospun carbon nanofiber membrane as bifunctional oxygen electrocatalyst for rechargeable zinc-air battery

The recharged zinc-air battery(ZAB) has drawn significant attention owing to increasing requirement for energy conversion and storage devices.Fabricating the efficient bifunctional oxygen catalyst using a convenient strategy is vitally important for the rechargeable ZAB.In this study,the bimetallic ZIFs-containing electrospun(ES) carbon nanofibers membrane with hierarchically porous structure was prepared by coaxial electrospinning and carbonization process,which was expected to be a bifunctional electrocatalyst for ZABs.Owing to the formed dual single-atomic sites of Co-N_(4) and Zn-N_(4),the obtained ES-Co/ZnCNZIFexhibited the preferable performance toward oxygen reduction reaction(ORR) with E1/2of 0.857 V and JLof 5.52 mA cm^(-2),which were more than Pt/C.Meanwhile,it exhibited a marked oxygen evolution reaction(OER) property with overpotential of 462 mV due to the agglomerated metallic Co nanoparticles.Furthermore,the ZAB based on the ES-Co/Zn-CNZIFcarbon nanofibers membranes delivered peak power density of 215 mW cm^(-2),specific capacity of 802.6 mA h g^(-1),and exceptional cycling stability,far larger than Pt/C+RuO_(2)-based ZABs.A solid-state ZAB based on ES-Co/Zn-CNZIFshowed better flexibility and stability with different bending angles.

Recent progress of electrochemical reduction of CO_(2)by single atom catalysts

Powered by electricity from renewable energies,electrochemical reduction of CO_(2)could not only efficiently alleviate the excess emission of CO_(2),but also produce many kinds of valuable chemical feedstocks.Among various catalysts,single atom catalysts(SACs)have attracted much attention due to their high atom utilization efficiency and expressive catalytic performances.Additionally,SACs serve as an ideal platform for the investigation of complex reaction pathways and mechanisms thanks to their explicit active sites.In this review,the possible re-action pathways for the generation of various products(mainly C1 products for SACs)were firstly summarized.Then,recent progress of SACs for electrochemical reduction of CO_(2)was discussed in aspect of different central metal sites.As the most popular and efficient coordination modulation strategy,introducing heteroatom was then reviewed.Moreover,as an extension of SACs,the development of dual atom catalysts was also briefly discussed.At last,some issues and challenges regarding the SACs for CO_(2)reduction reaction(CO_(2)RR)were listed,followed by corresponding suggestions.

多环芳烃双效耦合加氢催化剂制备及其加氢性能

多环芳烃加氢饱和既有利于环境保护,还能促进煤焦油的高效率利用。以煤焦油中(210~360)℃富含2-4环多环芳烃馏分为研究对象,采用加氢饱和催化剂与分子筛催化剂作为双效耦合催化剂,对不同反应条件下煤焦油催化加氢反应性能进行研究。结果表明,双效耦合催化剂具备分子筛催化剂与加氢饱和催化剂的催化特性,同时具备两者相互作用较小的稳态结构,且其在多环芳烃催化加氢反应中的活性介于分子筛催化剂和加氢饱和催化剂之间;活性金属组分Ni和Mo在催化剂表面分布稳定均匀。各操作条件对多环芳烃加氢性能存在不同程度的影响,双效耦合催化剂耦合比为4∶6时,多环芳烃催化加氢性能优于其他耦合比催化剂,在反应温度380℃、氢初压8.0 MPa、反应时间60 min和剂油比5∶100条件下,具有较好的加氢性能。馏分油多次选择性加氢后,饱和分量明显增加,胶质和芳香分量明显减少。

CoSe_(2)-CuSe_(2)NF双功能电催化剂的制备及其电解水性能的研究

随着环境污染日益严重、不可再生资源日益枯竭,对清洁、可再生能源的开发非常重要。利用电解水析氢(HER)和析氧(OER)技术生产氢气和氧气,是一种高效、无污染的制备清洁能源的方法。但是,商业贵金属电催化剂价格昂贵、地球丰度低,因此,开发价格低廉、高活性、高稳定性的非贵金属电催化剂意义重大。本研究利用水热法成功制备出一系列具有纳米花结构的双功能电催化剂(CuSe_(2)-CoSe_(2)(1∶1)NF、CuSe_(2)-CoSe_(2)(3∶1)NF、CuSe_(2)-CoSe_(2)(1∶3)NF),通过一系列的表征对催化剂的结构、形貌、元素组成、元素价态进行分析。研究发现CuSe_(2)-CoSe_(2)NF双金属硒化物中CoSe_(2)和CuSe_(2)相互协同作用,促进电子转移,提高电解水性能。此外,CuSe_(2)-CoSe_(2)NF纳米花结构具有较大的比表面积(808 m^(2)/g),暴露更多的活性位点数,进一步提升了催化剂的电化学性能。结果表明,CuSe_(2)-CoSe_(2)(1∶1)NF催化剂在1 mol/L KOH电解液、电流密度为10 mA·cm^(-2)时,HER和OER的过电位为42和204 mV,可持续稳定工作100 h,与商业Pt/C和RuO_(2)性能接近。

费托合成Co基催化剂的研究进展

Co基催化剂因具有高活性和强链增长能力等优势,成为费托合成(FTS)反应适宜的催化剂。总结了Co基催化剂FTS反应机理,并对活性相结构以及助剂与催化性能的构效关系进行了分析。同时,围绕催化剂载体的作用,总结金属-载体相互作用促进FTS反应性能的研究进展,重点分析了金属Co与分子筛耦合直接合成液体燃料的研究进展,归纳了采用双功能催化剂体系制备液体燃料的反应路线及催化剂特征。

Electronic structure and geometric construction modulation of carbon-based single/dual atom catalysts for electrocatalysis

Both carbon-based single atom catalysts(SACs)and dual atom catalysts(DACs)have garnered significant attention in the field of electrochemical reactions because of the impressive attributes,including exceptional catalytic activity,selectivity,and cost-effectiveness.The ability to modulate the electronic structure and geometric construction of active sites within SACs/DACs is paramount for unleashing their complete potential,which in turn can ultimately dictate catalytic behavior with unprecedented precision.In this review,the recent major developments of the regulation strategies for modulating electronic structure and geometric construction of carbon-based SACs/DACs are summarized.For the SACs,the recently reported modulation methods are categorized into four strategies,including adjusting the density of single atoms,defect engineering,confinement effect and strain engineering.And for the DACs,the five methods contain bonded dual-atom adjustment,non-bonded and bridged dual-atom adjustment,metal and nonmetal dual-atom adjustment,bilayer dual-atom adjustment and homogeneous dual-atom adjustment.The recently developed synthetic strategies are comprehensively summarized,especially their electronic structure and geometric configuration are discussed in detail,the different catalytic applications of electrochemical reactions,and their unique catalytic mechanism are highlighted.Finally,the challenges and prospects of SACs/DACs for tailoring their electronic structures and geometric arrangements are further discussed.

NiS和Pt双助催化剂增强BaTiO_(3)纳米纤维光催化制氢性能

采用静电纺丝、水热和光沉积的方法制备了一种以Pt和NiS为助催化剂的BaTiO_(3)/Pt/NiS双异质结光催化剂。优化后的BaTiO_(3)/Pt/NiS样品的制氢速率最高为489μmol·h^(-1)·g^(-1),是纯物质BaTiO_(3)的2.5倍。这主要归因于BaTiO_(3)与Pt之间形成的肖特基结促进了光生电子的快速转移,以及BaTiO_(3)与NiS之间构建的p-n结实现了对光生空穴的高效捕获。光电化学测试结果进一步证实了BaTiO_(3)/Pt/NiS异质结光催化剂中的光生电子和空穴被高效分离,从而具有更高的分解水制氢性能。

负载型零价过渡金属在双氧化体系下降解高稳定油田污染物

过硫酸盐单一氧化技术在过渡金属活化下可有效降解有机污染物,但存在氧化剂投加量过大、pH适用范围窄和金属离子浸出造成二次污染等问题。为了应对上述问题,采用浸渍还原法将过渡金属Cu负载至水滑石(LDHs)载体上,得到高分散负载型零价铜固体催化剂(Cu^(0)@LDHs)。通过Cu^(0)@LDHs活化过氧化氢-过硫酸钠(H_(2)O_(2)-Na_(2)S_(2)O_(8))双氧化体系降解油田高聚物羟丙基瓜尔胶(HPG)。对反应条件的优化结果表明,在pH为3~11的范围内,H_(2)O_(2)-Na_(2)S_(2)O_(8)双氧化体系对HPG均能保持较高的降解效果,25 min内降解率皆高于76.30%,且120 min后COD去除率最高可达93.91%。Cu^(0)@LDHs循环再生5次后仍能保持良好的催化活性,其对HPG的降解效率能保持在80%以上。在此过程中,·OH和SO_(4)^(·-)是主要活性物种并且二者间存在协同作用。反应前后Cu^(0)@LDHs的XRD、SEM、BET表征结果表明,该催化剂所表现出的高活性主要归结于高度分散在水滑石载体表面的Cu^(0)具有良好的活性以及稳定性。

浆态床合成气制二甲醚双功能催化剂的性能

在浆态床合成气制二甲醚过程中，在２８０℃、４ＭＰａ、尾气流量４５００ｍＬ／ｇｃａｔ·ｈ条件下，考察了甲醇合成和甲醇脱水催化剂组成的双功能催化剂对合成的影响。随二者质量比的增加，合成气的转化率、二甲醚生成速率逐渐增加，在催化剂比例４～７时达最高值后降低。随催化剂比例的增加，二甲醚、烷烃的选择性逐渐降低，甲醇选择性逐渐升高。当催化剂比例为４～５时二甲醚生成速率最高达１５～１６ｍｍｏｌ／ｇｃａｔ·ｈ，甲醇当量生成速率接近最高值≈３９ｍｍｏｌ／ｇｃａｔ·ｈ，二甲醚选择性≈７５％，烃类选择性５％以下，为合成气制二甲醚最适宜催化剂比例。

新型硫醇氧化双功能催化剂CoSPc/Mg(Al)O的研究

在实验室以镁铝氧化物固溶体 (Mg(Al)O)固体碱负载磺化酞菁钴 (CoSPc)制成的双功能催化剂 ,对硫醇氧化反应具有良好的催化活性。载体的碱性强弱、催化剂制备过程中使用的溶剂种类及催化剂中溶剂的含量对催化剂活性有显著影响。不同结构硫醇氧化反应结果表明 ,大分子、异构硫醇较难氧化。此外 ,利用双功能催化剂进行了小型固定床喷气燃料脱臭试验 ,取得了初步成果。

浆态床CO加氢制二甲醚的工艺条件研究

在反应温度为２６０～３００℃，反应压力为３．０～５．０ＭＰａ，进料空速为４０００～７０００ｍｌ／（ｇ．ｈ）范围内，研究了浆态床ＣＯ加氢制二甲醚过程中工艺条件对双功能催化剂的性能的影响。在２６０～２８０℃温度范围内，ＣＯ、Ｈ２转化率、二甲醚生成速率及其选择性均随反应温度的升高而增加，２８０℃达到最高值。在进料空速为４０００～６０００ｍｌ／（ｇ．ｈ）范围内，提高进料空速可提高二甲醚和甲醇当量生成速率，但ＣＯ单程转化率降低，继续提高进料空速，二甲醚生成速率反而降低，而甲醇生成速率几乎不受空速的影响。随着反应压力的增加，ＣＯ转化率、二甲醚生成速率以及甲醇生成速率均增加。