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        碳基單原子催化劑的合成策略及電催化應用進展

        2024-09-29 00:00:00劉熙俊陳明英馬俊杰梁璟琦李春勝陳叢瑾何會兵
        中國粉體技術 2024年5期
        關鍵詞:合成

        摘要:【目的】單原子催化劑(single atom catalysts,SACs)由于超高電催化效率而備受關注,特別是以碳為基礎的碳基SACs,由于結構可調、孔道排列有序、原子利用率高、導電性好、孔隙率高、比表面積大和穩(wěn)定性好等特點,被認為是一類極具發(fā)展?jié)摿Φ男滦碗姶呋牧??!狙芯楷F(xiàn)狀】綜述近年來碳基SACs的合成工藝,包括熱解法、濕化學法、電化學還原法、原位合成法和球磨法;這些方法具有不同的優(yōu)缺點,可根據(jù)不同反應條件和需求選擇合適的合成方法;總結碳基SACs在氧還原反應、析氧反應、析氫反應、氮還原反應、二氧化碳還原反應中的應用?!菊雇刻蓟鵖ACs的合成工藝和性能有望得到進一步優(yōu)化和提升;碳基SACs將在能源催化及環(huán)保等領域發(fā)揮更大的作用。

        關鍵詞:碳基;單原子催化劑;合成;電化學應用

        中圖分類號:TB4文獻標志碼:A

        引用格式:

        劉熙俊,陳明英,馬俊杰,等.碳基單原子催化劑的合成策略及電催化應用進展[J].中國粉體技術,2024,30(5):35-46.

        LIU Xijun CHEN Mingying,MA Junjie,et al.Advances in the synthesis strategies of carbon?basedsingle?atom catalysts and their electrochemical applications[J].China Powder Science and Technology,2024,30(5):35?46.

        近年來,隨著工業(yè)的快速發(fā)展,造成的能源危機和環(huán)境污染等問題,對人類的生存發(fā)展造成了嚴重的影響,因此開發(fā)更高效的電催化劑并將可再生能源轉化為高附加值燃料迫在眉睫[1-7]。在眾多的催化劑材料中,單原子催化劑(single atomic catalysts,SACs)因超高的電催化活性而備受關注[8-11]。通常,SACs將單一金屬原子作為催化活性中心,而該單一金屬原子是高度分散的,可以通過與相鄰原子配位或離子相互作用而被固定在多種載體上[12-14]。SACs由于獨特的結構而具有極高的原子利用效率(理論上可達100%)、優(yōu)異的催化活性和選擇性[15-17]。在各種類型SACs的載體中,碳基材料具有極好的化學穩(wěn)定性和機械延展性、可調節(jié)的孔隙率和表面修飾、優(yōu)異的導電性和導熱性、高比表面積、可變的結構和形態(tài)組合、易于處理和低成本等優(yōu)點,因而在各種電催化反應中出類拔萃[18]。通過改變中心金屬原子、相鄰配位元素和配位數(shù),可以有效地調節(jié)碳基SACs的電荷分布及催化活性。碳基SACs的活性中心(金屬-配體-碳載體)相對容易確定和控制[19-20],使其成為有效增強電催化效率的理想材料。總之,在未來的綠色催化中,碳基SACs具有廣闊的應用前景,對這種催化劑進行深入研究,不僅有助于緩解目前面臨的能源危機和環(huán)境問題,而且還可以推動綠色化學的可持續(xù)發(fā)展。

        本文中綜述碳基SACs的合成方法,主要包括熱解法、濕化學法、電化學沉積法、原位合成法以及球磨法;也重點討論碳基SACs在氧還原反應(oxygen reduction reaction,ORR)、析氫反應(hydrogen evolution reaction,HER)、析氧反應(oxygen evolution reaction,OER)、氮還原反應(nitrogen reduction reaction,NRR)、CO2還原反應(carbon dioxide reduction reaction,CO2RR)等電催化領域中的前沿應用。本綜述中涉及的主題摘要圖如圖1所示。特別是在ORR和HER中,碳基SACs表現(xiàn)出優(yōu)異的電催化性能,為綠色化學的可持續(xù)發(fā)展提供了一種新的解決思路與方案。

        1碳基SACs的合成方法

        在碳基SACs的合成研究中,碳基SACs的制備通常與碳基載體的合成并行或交錯進行。目前,碳基SACs的合成主要采用熱解法、濕化學法、電化學沉積法、原位合成法以及球磨法等合成方法。這些合成方法給研究者提供了有利的借鑒,有助于研究者探索和合成更高效的碳基SACs[21-22]。

        1.1熱解法

        熱解法是指在將金屬前驅體和載體在高溫氣氛(如Ar、N2和NH3)下進行熱解處理的方法,使前驅體中的金屬原子以配位結合的方式固定到載體的表面上而形成SACs的一種方法[10,23]。高溫處理能使金屬原子和載體間形成共價鍵,從而顯著地加速金屬原子在載體表面的固化,單原子分散度和穩(wěn)定性也得到改善。該方法具有易于操作、廉價且易于獲得原材料的特點,但由于SACs易形成金屬納米粒子和納米簇,因此不容易實現(xiàn)SACs的高負載量[24]。

        Xie等[25]以具有三維孔道結構和超高比表面積的金屬有機框架為前驅體,采用熱解法設計合成了金屬有機框架衍生的碳基Fe-SACs。在作為質子交換膜燃料電池陰極催化劑時,壓強為0.2 MPa,所組裝的燃料電池的能量密度可達0.84 W/cm2。Han等[26]通過熱解聚合物制備了鎳負載量高達5.92%的SACs,并研究了對CO2-CO電催化性能的影響。該研究為設計合成具有高活性、高選擇性和優(yōu)異耐久性的SACs提供了重要的參考。Zhao等[27]也提出了一種用于合成Fe-SACs的創(chuàng)新熱解策略,首先將鐵卟啉(DFTPP)FeCl3(DFTPP=2,6-二氟四苯基卟啉)與咪唑配位組裝在咪唑化聚乙烯醇涂層的炭黑上,然后對炭黑進行熱處理得到催化劑C@PVI-(DFTPP)Fe-8005,鐵原子被嵌入到氮、氟摻雜的多孔碳納米材料中,形成Fe-N共活性位點。將Fe引入碳載體后,該催化劑的ORR性能顯著提高,碳載體中摻雜的氟原子還可以調節(jié)ORR活性。該方法為在分子水平上制備具有Fe-N活性位點的電催化劑開辟了一條新的途徑[28]。

        1.2濕化學法

        濕化學法是目前研究中最為廣泛的合成碳基SACs的方法,包括浸漬法和共沉淀法[29]。由于單個金屬原子具有高表面能,因此在制備期間,活性金屬原子傾向于形成具有低金屬負載的納米簇,以減少表面能。浸漬法是通過將載體浸漬于金屬前體溶液,通過干燥和焙燒來獲得碳基SACs的方法[30]。在浸漬法得到的碳基SACs中,大部分的活性金屬組分被置于碳基載體表面,使金屬原子的使用效率大幅提高。共沉淀法是指將金屬前驅體液與載體前驅體液混合得到混合前驅體液,再向其中添加沉淀劑,使它們相互作用生成沉淀,通過過濾、分離、洗滌、干燥和焙燒來獲得碳基SACs的方法。該合成方法能得到高分散性的碳基SACs,這是因為金屬前驅體與載體前驅體在液相中均勻分散,二者之間會產生相互作用,使金屬原子于載體上趨向在一定距離內負載。使用共沉淀法合成過程中會導致一部分活性金屬被載體包覆,導致這部分活性金屬不能參與到催化反應中而造成浪費。

        Kustov等[31]用浸漬法制備了一種含鋅、鐵單原子的碳基SACs,該催化劑具有良好的CO2加氫選擇性和活性。Li等[32]提出了多巴胺介導氨活化的策略,采用液相共沉淀法合成了以多孔碳為載體的ZnCo-SACs催化劑。

        1.3電化學沉積法

        電化學沉積法是指通過在電化學三電極體系上施加外加電壓,使電解液中的金屬離子基團在電解質中定向向電極遷移的方法。當施加瞬時電壓或瞬時電流密度的增大時,金屬晶體的生長速度加快,并且靠近電極附近的電解液中的金屬離子也更快地被還原[33]。當沉積速率較慢時,電解質中的離子有足夠的時間來補充離子濃度,導致擴散層更薄,使得金屬原子沉積更均勻。美中不足的是,當外加電壓超過析氫電位時,沉積過程伴隨著HER副反應[34]。HER的出現(xiàn)降低了電沉積過程的法拉第效率(faraday efficiency,F(xiàn)E),進而降低了電能的利用效率,而且這種方法還需要額外電解池設備,操作相對復雜。

        Zhang等[35]利用電化學沉積法制備了30余種碳基SACs。由于陰極和陽極上SACs的電子態(tài)不同,陰極上的SACs更容易發(fā)生HER,而陽極上的SACs更容易發(fā)生OER。其中,Ir-Co(OH)2 SACs陰極在過電壓為8 mV時就能獲得電流密度10 mA/cm2,是一種有希望實現(xiàn)大規(guī)模制造的SACs。Luo等[36]利用三電極體系裝置在CoP-CNT上合成Pt單原子。實驗中,以Ni泡沫上的CoP-CNT載體作為工作電極,將Pt薄片在溶液中進行電離、溶解、再沉積到CoP-CNT上。這樣的無黏合劑催化劑具有厘米級的大小,有利于工業(yè)推廣。

        1.4原位合成法

        原位合成是指將金屬前驅體直接導入到載體表面或內部,然后通過機械加工得到SACs的方法[37]。原位合成工藝簡單、反應條件溫和、反應過程可控制、比表面積大、催化活性高,是一種新的合成方法。通過對制備過程中的溫度、時間和濃度等反應條件進行控制,可使催化劑的物理和化學性質發(fā)生變化,進而改變催化劑的催化活性。

        Fang等[37]結合高溫熱解原位合成了在N,S共摻雜碳納米片上負載Co原子的Co-SACs電催化劑。Wang等[38]報道了一種用氣相發(fā)泡法制備的超薄氮摻雜多孔碳基Fe-SACs,比表面積高達1 126 m2/g。原位合成法合成碳基SACs示意圖如圖2所示。在反應電位為0.863 V,塔菲爾斜率為68.3 mV/dec時,超薄氮摻雜多孔碳基Fe-SACs比Pt-C具有更好的氧還原活性和更快的氧還原動力學。結果表明,超薄氮摻雜多孔碳基Fe-SACs在鋅-空氣電池中具有較好的穩(wěn)定性和可逆性,鋅-空氣電池的循環(huán)效率可達60.8%。

        1.5球磨法

        球磨法通常是將原料放入球磨機中,利用球磨機的高速旋轉和摩擦力將原料研磨成微小顆粒,能夠高效制備碳基SACs的方法[39]。機械碰撞可使催化劑原位產生高缺陷密度,從而顯著增強催化劑的活性,促進化學反應的高效進行[40]。該方法不僅反應速度快,能耗低,而且能合成某些傳統(tǒng)合成方法不能合成的物質,是適應當今化工可持續(xù)發(fā)展及“綠色化學”理念的新型合成技術[41-42]。

        Wang等[41]通過高能量球磨,使前驅體在KCL表面均勻分布。正如實驗所證實的那樣,碳納米籠表面成功地摻入了N和Co單原子,且二者分布均勻。由于獨特的籠狀結構和Co、N、Co-Nx配合物的協(xié)同催化作用,所制得的最佳催化劑在初始電位0.924 V(相對于可逆氫電極)的條件下具有較高的氧還原活性。另外,該催化劑的穩(wěn)定性和對甲醇的耐受性也比市面上的Pt-C催化劑好得多。由此可見,該合成方法具有簡單通用的特點,其中碳納米籠的合成方法可以作為模板推廣應用。Gan等[43]用2種具有非常類似性質的乙酰丙酮化合物作為原料,采用球磨法制備了Pt均勻分布于Co納米顆粒表面的碳基Pt(Co)單原子合金催化劑。球磨法合成碳基SACs的示意圖如圖3所示。研究結果表明,該催化劑對5-羥甲基糠醛(HMF)的加氫脫氧合成2,5-二甲基呋喃(DMF)具有良好的催化活性。在此條件下5-羥甲基糠醛的轉化率和2,5-二甲基呋喃的選擇性分別達到了100%和92.9%。

        2電催化應用

        迄今為止,國內外已經報道了許多關于碳基SACs用于ORR、OER、HER、NRR和CO2RR的研究報道。接下來將重點綜述碳基SACs在上述5個典型電催化反應中的前沿應用。

        2.1 ORR

        ORR是燃料電池和金屬空氣電池陰極發(fā)生的關鍵反應,氧的吸附和解吸代表了氧的擴散和交換,是ORR催化的關鍵步驟。催化劑和中間物質之間的吸附和解吸取決于碳基SACs中活性位點的電子結構。目前ORR電催化領域一個嚴峻挑戰(zhàn)是提升選擇性,因為H2O還原生成過氧化氫是ORR反應的主要競爭反應,從而使ORR反應產率下降。目前碳基SACs作為一種新興材料通過超高的活性位點以及卓越的導電性,大大提升了O2解離速率,從而有效提升ORR催化效率,ORR的通用反應方程式[44]通??梢员硎緸?/p>

        O2+4H++4e-→2H2O。(1)

        Zhang等[45]開發(fā)了一種制備聚磷腈納米球的方法,并作為前驅體制備了碳基Co-SACs。密度泛函理論計算(density functional theory,DFT)表明,在反應電壓為1.23 V時,具有碳基載體的最優(yōu)催化劑對應ORR的反應中間體自由能能壘顯著低于對比催化劑。使得O2在最優(yōu)催化劑上的吸附能較低,對H2O的吸附能較高,因此,碳基Co-SACs能夠更有效地結合O2以引發(fā)反應,對H2O的弱結合可以大大削弱副反應,從而有效提升ORR反應的選擇性。Su等[46]使用精準合成的S-Co(N,C)SACs作為正極材料構建了Zn-O2電池。理論和實驗證實,碳基底的引入使得該電池表現(xiàn)出色,電流密度約為400 mA/cm2,最大功率密度為260 mW/cm,顯著優(yōu)于商用Pt-C和其他鈷基催化劑。

        2.2 HER

        HER是指通過電催化水分解產生氫氣,為生產綠色氫氣提供了一條有吸引力的途徑。與能量轉換效率低的風、水和太陽能等常見的可再生能源作為生產H2的方式相比,電解水制氫已成為備受矚目的高效制氫策略[47]。其中,HER是水分解反應中的一個半反應,具有特殊配位結構的碳基SACs可以有效地優(yōu)化活性中心對H原子的吸附過程,從而顯著降低HER反應中間體的吸附能壘,進而提高HER電催化活性,HER的反應方程式[47]通常表示為

        2H++2e-→H2。(2)

        Xue等[48]開發(fā)了一種Mo單原子錨定在摻N碳纖維上的SACs合成方法,Mo原子與N、C、O原子配位,以實現(xiàn)高效的HER。碳基SACs在HER中的應用:H2O產生H2的機制如圖4所示。

        由于配位的O原子在酸性條件下容易形成羥基,學者構建了MoC3-OH、MoC2N-OH、MoCN2-OH和MoN3-OH模型,以探索多個雜原子配位對催化性能的影響。態(tài)密度理論計算表明,C、N和O原子的協(xié)同配位顯著地調節(jié)了單原子Mo的電子結構。其中,MoC2N-OH和MoC3-OH對反應中間體H*的吉布斯自由能接近0,這顯著提高了HER的電催化效率。Mo-C鍵在水解過程中可能是不穩(wěn)定的,而N配位的模型能量計算較小,結構更穩(wěn)定,因此,MoC2N-OH結構的HER性能總體上是最好的。基于最優(yōu)催化劑的氫電池來獲得氫,所收集的H2體積與理論值吻合較好,表明最優(yōu)催化劑具有近100%的法拉第效應。Luo等[49]制備了多種過渡金屬(Co、Ni、W)錨定在富氮石墨烯上,可以廣泛應用于HER領域。通過高倍率透射電鏡對3種SACs(Co、Ni、W)的表征表明,孤立原子以M-N4C4實體的形式均勻分散在氮增強石墨烯表面,并通過同步輻射進一步印證該結論。這種摻N的碳載體可以為高效碳基SACs的設計提供借鑒和思路。

        2.3 OER

        OER是指在電化學過程中,水分子(或其他氧化物)被氧化成氧氣的反應。在水電解中,OER是水分解的關鍵步驟之一,發(fā)生在陽極上,反應機制表達式如(3)所示。由于OER反應通常需要高能量輸入以及催化劑的催化作用,因此尋找高效的催化劑成為本領域的研究熱點。

        2H2O→O2+4H++4e-。(3)

        Huang等[50]報道了一種將單原子過渡金屬(Fe、Co、Ni)均勻分布在富氮石墨烯中的一般合成策略,都具有共享的金屬-N4C4結構,該共享結構大大降低了OER反應中間體的自由能能壘,從而顯著提升電催化OER的選擇性。

        Hou等[51]將S作為摻雜劑引入到從石墨烯箔中提取的多孔碳納米片中。與商用Ir?C相比,該材料表現(xiàn)出較低的電勢和優(yōu)越的電流密度,具有出色的OER電催化性能。通過DFT計算表明,S原子與碳載體之間的電子相互作顯著提高了該催化劑的OER性能。

        2.4 NRR

        氨(NH3)是一種工業(yè)和農業(yè)不可或缺的化工生產原料。傳統(tǒng)合成NH3的方法是Haber?Bosch工藝,但需要消耗大量能源并產生大量溫室氣體。具有反應條件溫和、綠色可持續(xù)特點的電催化NRR獲得廣泛關注。電催化NRR利用H2O、N2和電能在環(huán)境條件下生成NH3,是一種綠色、低能耗、安全的新型合成NH3方法[52]。由于N2過于惰性以及HER副反應,電催化NRR過程的FE和NH3產率相對較低[53]。為了提高電催化NRR效率,亟待設計出能夠有效抑制HER并降低N,N三鍵解離能的高活性催化劑。NRR的通用反應方程式[53]通??梢员硎緸?/p>

        N2+6H++6e-→2NH3。(4)

        Han等[11]通過控制Mn-O鍵的結合能,成功地將特殊的Mn-O3N1位點錨定在多孔碳上,制備出了可用于高效NRR催化的Mn-SACs。研究發(fā)現(xiàn),Mn-O3N1位點與N2的結合強度明顯強于Mn-N4位點(Mn-O3N1為0.83 eV,Mn-N4為0.09 eV)。原因為在Mn-O3N1結構中,Mn原子突出于平面之外,N2只能吸附在Mn原子之上;O原子的配位調節(jié)了Mn的電子結構,該位點有利于N2的極化和活化。Mn-O3N1結構顯著降低了NRR反應中間體的自由能能壘。從Bader電荷分析來看,N2在Mn-O3N1結構上獲得了更多的轉移電子,這是導致提升NRR活性的本質。Kong等54]利用沸石咪唑酯骨架,通過高溫熱解法合成了一種碳基Zn-SACs。由于獨特的多孔絲狀結構和獨特結合方式,Zn-SACs納米纖維在堿性條件下表現(xiàn)出優(yōu)異的NRR性能,碳基SACs在NRR中的應用:N2還原為NH3的反應機制如圖5所示。

        該催化劑制NH3的反應速率和選擇性均高于普通的Zn基催化劑。基于實驗和理論進一步研究發(fā)現(xiàn),Zn-SACs附近石墨氮化合物的存在加速了加氫反應的動態(tài)特性,降低了關鍵中間體*NNH的自由能能壘,大大提高了電催化NRR活性。

        2.5 CO2RR

        電催化CO2RR可以將CO2轉化為各種原料化學品[55-57]。該反應的轉化效率受CO2本身高穩(wěn)定性以及析氫副反應的影響很大[58]。目前,不同單原子摻雜的碳基SACs中的活性位點不僅可以抑制HER反應,還可以優(yōu)化*CO和*COOH的吸附能以提高催化性能[59-60]。

        Zhang等[61]探索了Mn-SACs的C原子配位結構對CO2RR催化活性的影響。用原位XAS光譜研究反應過程,發(fā)現(xiàn)CO2RR過程中的C配位對Mn原子的氧化態(tài)存在顯著的影響。此外,它還可以促進Mn原子的重構,從而形成穩(wěn)定的平面結構。DFT還表明,額外的C配位能夠有效地調節(jié)Mn中心的電子結構,增強與CO2和*COOH的吸附,并促進關鍵中間體*COOH形成。特別是,與未結合C原子配位的Mn-SACs相比,配位C原子的Mn-SACs具有更高的*H中間體的吸附能,從而有效地抑制了HER副反應。基于實驗和計算結果,作者提出了活性中心的結構演化:特殊的碳配位活性中心可以有效穩(wěn)定地吸附反應中間體,促進最終的CO脫附過程,從而獲得卓越的催化選擇性。Liu等[62]發(fā)現(xiàn),在反應過程中,F(xiàn)e-SACs通過質子供給效應有效地促進了CO2RR的催化活性。制備了具有Fe-N4S結構和S原子二次配位的Fe-NSC催化劑。摻雜S原子不僅有效地調節(jié)了Fe單原子和碳載體彼此間的電子結構,促進了CO2的活化和吸附,而且有效降低了反應中間體*COOH反應能壘,提升了CO的選擇性。

        3結論

        碳基SACs作為一種具有高活性、高選擇性和高穩(wěn)定性的新型高效電催化劑,在未來的催化領域中具有廣闊的發(fā)展前景。特別是,從原子利用率和資源可持續(xù)利用的觀點出發(fā),碳基SACs的開發(fā)應用對緩解溫室效應、解決能源危機以及促進可持續(xù)發(fā)展具有十分重要意義。本文中綜述了碳基SACs材料的合成及電催化應用,并對碳基SACs在催化方面的應用潛力和優(yōu)點進行了深入的探討。

        1)碳基SACs的合成方法,包括熱解法、濕化學法、電化學沉積法、原位合成法和球磨法等,合成方法在國內外已有較多的報道。通過對催化劑的合成條件的優(yōu)化,可以使催化劑的形貌和組成發(fā)生變化,從而對催化劑的催化活性進行調控和優(yōu)化。

        2)碳基SACs被廣泛應用于ORR、HER、OER、NRR以及CO2RR等電催化反應領域,而且在金屬空氣電池、燃料電池以及光催化等催化領域也有著廣泛的應用前景。碳基SACs催化劑通過有效地調節(jié)金屬原子在催化劑表面的配位環(huán)境和電子結構,從而改善催化劑的催化性能,并能有效提高反應選擇性和產品收率。

        3)目前碳基SACs的合成方法大多復雜且成本較高,限制了大規(guī)模工業(yè)化生產和應用。在電催化應用中仍存在穩(wěn)定性較差、活性不足、選擇性較低以及催化機制不明確等問題,在未來研究中需要根據(jù)目前存在的不足更精準的設計碳基SACs催化劑以提高實際應用價值。

        4)通過理論計算,可以更深入地探究碳基SACs的催化活性增強機制,更精確地預測目標催化劑的設計方案,從而提高碳基SACs實際應用前景。利用原位光譜表征技術,研究碳基SACs的結構、電子態(tài)以及表面活性,為進一步深入研究碳基SACs催化活性中心提供理論基礎,更好地應用于電催化等領域。

        利益沖突聲明(Conflict of Interests)

        所有作者聲明不存在利益沖突。

        All authors disclose no relevant conflict of interests.

        作者貢獻(Authors’Contributions)

        劉熙俊、陳明英、馬俊杰參與了論文的設計和撰寫。梁璟琦、李春勝、陳叢瑾、何會兵參與了審查和修改。所有作者均閱讀并同意了最終稿件的提交。

        The review was designed and written by LIU Xijun,CHENMingying,and MA Junjie.The manuscript was revised by LIANG Jingqi,LIChunsheng,CHENCongjin,and HE Huibing.All authors have read the last ver?sion of paper and consented to its submission.

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        Advances in the synthesis strategies of carbon?based single?atom catalysts and their electrochemical applications

        LIU Xijuna,b CHEN Mingyinga,MA Junjiea,LIANG Jingqia,LI Chunshenga,CHEN Congjina,HE Huibinga

        a.School of Chemistry and Chemical Engineering,b.School of Resources,Environment and Materials,Guangxi University,Nanning 530001,China

        Abstract

        Significance To address global challenges such as environmental pollution and energy crisis,there is an urgent need for a new and highly efficient energy-saving catalyst that can effectively respond to energy and environmental challenges as well as improve economic efficiency.In recent years,single-atom catalysts(SACs)have attracted significant attention due to their ultra-high electrocatalytic efficiency.Carbon-based SACs,in particular,are considered promising new electrocatalytic materials due to their tunable structures,ordered pore arrangements,high atom utilization,good electrical conductivity,high porosity,large spe?cific surface area,and excellent stability.These features make them particularly suitable for addressing the pressing energy and environmental issues in China.

        Progress In recent years,various synthesis techniques for carbon-based SACs have been extensively explored,including ther?mal decomposition,wet chemistry,electrochemical reduction,in situ synthesis and ball milling.Among these,the thermal decomposition method is noted for its simplicity in operation and high yield;the wet chemical method is prized for its high prod?uct purity,controllable structure and high catalyst activity;electrochemical deposition method offers simplicity in operation,suitable for large-scale production and has high catalyst activity;in-situ synthesis allows for controllable structure and morphol?ogy;and the ball milling method has a fast reaction speed,low energy consumption,and uniform product dispersion.In short,each method has its own merits and can be selected based on specific reaction conditions and requirements.In addition,the advancements in the application of carbon-based SACs in various electrochemical reactions,including oxygen reduction reaction(ORR),oxygen evolution reaction(OER),hydrogen evolution reaction(HER),nitrogen reduction reaction(NRR),and car?bon dioxide reduction reaction(CO2RR),are summarized.Taking ORR as an example,studies have shown that carbon-based SACs can effectively improve the activity and selectivity of ORR,while also greatly improving its industrial prospects due to their ultra-high atom utilization rate and excellent electrical conductivity.These catalysts also exhibit robust performance in HER,OER,NRR,and CO2RR.Furthermore,carbon-based SACs have many superior properties,including high specific surface area,controllable active sites,and good electron transport properties.These advantages give theman edge over many challenges faced by conventional catalysts and lay a solid foundation for their wide application in electrocatalysis.

        Conclusions and Prospects Carbon-based SACs will play a pivotal role in the future of energy and environmental protection.Ongoing research aims to further optimize and improve the synthesis process and performance characteristics of these materials for broader application in production.With their unique properties,carbon-based SACs are ideal candidates for a variety of applications requiring high performance and sustainability.As the field evolves,these catalysts are expected not only torevolu?tionize the field of energy catalysis,but also to significantly contribute to environmental protection efforts.Their ability to store and convert energy efficiently,while also being recyclable and environmentally friendly,makes them key players in the green revolution.Carbon-based SACs,as a new type of highly efficient electrocatalysts with high activity,high selectivity and high sta?bility,have a promising future in the field of catalysis.They are particularly significant for mitigating the greenhouse effect,addressing the energy crisis,and promoting sustainable development through optimal atomic and resource utilization.In the future,carbon-based SACs are expected to find broader application in the following aspects.

        Optimization of synthesis methods:With the continuous development in synthesis technologies,the synthesis methods of carbon-based SACs will be simpler,more efficient and controllable.Novel synthesis strategies may further improve the activity and stability of the catalysts,broadening their applications in various reactions.Diversified electrocatalytic applications:In addition to the well-researched oxygen reduction,hydrogen precipitation,and carbon dioxide reduction reactions,carbon-based SACs are also expected to impact other important electrocatalytic reactions,such as nitrogen reduction and organic electrocataly?sis.Future research will explore more possible application scenarios.

        Design and realization of multifunctional catalytic performance:Future research will focus on the design of carbon-based SACs with multifunctional performance,such as efficient catalysis of both oxygen reduction and hydrogen precipitation reac?tions.Such multifunctional catalysts can improve the efficiency of energy conversion and advance sustainable energy technologies.

        Composite applications with other materials:Future research will explore the composite applications of carbon-based SACs with other functional materials,such as metal-organic frameworks and carbon nanotubes.Such composites aim to leverage the strengths of each material to improve catalytic performance and stability.Overall,carbon-based SACs,as a promising new type of catalyst,have great potential for synthesis and electrocatalytic applications.Future research will continue to focus onoptimiz?ing synthesis methods,expanding application areas,designing catalysts with multifunctional properties,and exploring compos?ite applications with other materials,to promote the application of carbon-based SACs in the fields of environmental protection and energy transition.

        Keywords:carbon-based;single atom catalysts synthesize;electrochemical application

        (責任編輯:武秀娟)

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